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hS.S Led

Tetrahedron
Vol. 48.No. 48.pp. 10443-10514.1992
Printedin GreatBritain

TETRAHEDRON REPORT NUMBER 326

SUPRAMOLECULAR PHOTOCHEMISTRY
Vincenzo Balzani
Dipartimento di Chimica Cl. Ciamician
Universid di Bologna, Bologna, Italy

(Received 3 June 1992)

Contents
1. Introduction

10444

2. Supramolecular Species

10445

3. Photochemical and Photophysical Processes

10448

4. Cage-type Systems
4.1 Cage-type metal complexes
4.1 .l Cobalt complexes
4.1.2 Ruthenium complexes
4.1.3 Lanthanide complexes
4.2 Photo-cleavable and photo-flexible cages
4.3 Photochemistry of incarcerated molecules

10454
10454
10455
10458
10461
10464
10466

5. Host-Guest Systems
5.1 Polyammonium macrocyclic receptors with Co(CN)b35.2 Aromatic crown ethers with Pt(bpy)(NH,)z*+
5.3 Lasalocid A anion with Cr(bpy)s3+

10467
10468
10471
10477

6. Rotaxanes, Catenanes, and Related Species

6.1 Catenands and metal catenates
6.2 Rotaxanes and catenanes featuring charge-transfer interaction

10479

7. Covalently-linked Molecular Components

10488

7.1

7.2
7.3

Photoinduced electron and energy transfer in two-component model

systems
7.1.1 Electron transfer
7.1.2 Energy transfer
Multicomponent systems for photoinduced charge separation
Polynuclear metal complexes for light harvesting
7.3.1 Trinuclear metal complexes of tripod-type bipyridine ligands
7.3.2 Polynuclear complexes of the bis(2-pyridyl)pyrazine bridging
ligands

10480
10483

10489
10490
10492
10493
10496
10496
10498
10502

8. Conclusion
10443

10444

V. BALZANI

1.

Photochemistry

is a natural

modern

of science,

branch

and

at

the

vision,

is

reproduction,

etc.)

and

and

suitable

rationalize

the

structural,

important

until

now

have

dealt

most

the

same

combination

knowledge
progress
new

way

as

on

molecular

materials

from
of

the

supramolecular
of

synthetic
(

e.g.,

4)

the

need

to

that

the
Up

investigations

to

chemical

supramolecular
trend:

1)

the

research

high
the

is

There

degree

of

extraordinary

continuous

small-upward
the

molecules,

species.

2)

3) the

fill

of

supramolecular

to

species;

for

to

molecules.

leads

leads

methods:

been

search

for

approach

gap

which

to

separates

biology.
most
species

processes

supramolecular

this

and

photochemistry).

atoms

shows

of

available

photochemical

to

reached

now

of

clearly

for

are

families

components

level

have

several

of

two

molecules,

properties

combination

reasons

by

organic

dynamic

(molecular

last

photochemical

complexes

species

molecular

the

and

fundamental

molecular

In

(image

remarkable

treatments

of

four

made

chemistry

variety

the

from

nanostructures);

One

of

literature

least

of

matter

biology.

technology

organometallic

states

Current

are

thousands

energetic,

molecular

moving

The

theoretical

of

rapidly
at

and

excited

with

species.

of

compounds,

most

efficacy.

(photosynthesis,

etc.).
a

and

and

and

life

to

reached

theoretical

elucidated,

as

photodegradation,

processes

coordination

well

to

world

light

physics,

importance

has

as the

between

chemistry,

as

photochemistry

photophysical

In

of

photocatalysis,

experimental

as old

at the interface

of paramount

phototaxis,

decades

phenomenon

crossroads

Photochemistry

Introduction

interesting
is their
that

aspects
interaction

may

ensue.

photochemistry.

of

the

with

light

This

is

chemistry
and
the

the
realm

of
great
of

.
In

the

last

few

years

Supramolecular photochemistry

supramolecular

photochemistry

several

directions.

are,

their

by

more

true

In this

together
with

own

nature,

review

emphasis

will

number

of discrete

by some

the four

type

types

and

derivatized

considered

laboratory,

relevant

definition
the

of

word

to which

will

have

been

components

can

not

be

other

deal

in Fig.

films,

in

some

discussed.

studied

held

we will

micelles.

from

systems

schematized

which

to split

the

in

liquid
way

be

Most

of

the

laboratories

1.

author
will

also

different

into

individual

as

According

1) or

systems,

from

such

are

individual

held

together

Fig.
The

components
Macrocyclic

1)

can

situation
are

kept

together

complexes
most

covalently-linked

of

(Fig.

their
but

clear,

1)

intrinsic

clearly

by

forces

where

for

where

and

subunits

the

catenanes,

(e.g.,

host-guest

supramolecular

systems

where

or covalent

metal

properties,

of separate

(e.g.,

defined

coordinative

identifiable

(components)

systems

however,

area

is the possibility

interlocked

be

the

distinguishes

modifications,

intermolecular

is less

on

subunits

concept,

straightforwardly

arbitrary

that

molecule

minor

molecules
by

feature

molecular

this

necessarily

depending

the

a large

or with
to

is

meanings

Conceptually,

capable,

components

species

species

species

system

existence.

maintain

have

it is applied.l-6

are

species.

Supramolecular

supramolecular

may

a supramolecular

Fig.

is even

considered.

Any

that

this

Specifically,

species

systems,

examples

2.

and

and

molecular

bond.

electrodes,

illustrated

but

along

chemistry

to supramolecular

semiconductors,

supramolecular

examples

areas,

be given

of supramolecular

crystals,

rapidly

photochemistry.

of chemical

polymers,

very

supramolecular

interdisciplinary

supramolecular

like

be

and

for

Systems

the

grown

Photochemistry

of a small

made

has

10445

ions

and

systems
(Fig.

the

bonds.
ligands
made

1) can

of
also

10446

V. BALZANI

0
cI.l
L

(i)

(ii)

(iii)

r-lB

l-lc

(4
Fig. 1.

Schematic
species:

representation
(i) cage-type

catenanes;
be

In

supramolecular

are

better

supramolecular

the

the

electronic

interaction

energy

relevant

energy

between

As

supramolecular

species

A-B

that

are

transfer

together
substantially

from

substantially
considered
a

as a large

and

the

A and

localized

delocalized

of

the

is small

Similary,

specific

leads
B,

When

A and

any

or
the

B,

the

components,

interaction
When
to other
defined

causes

an

excited

states
electron

states

species
and

of a

of bond

to excited

be

excitation
type

oxidation

substantially

and

units.

be

can

indicates

A or

of

compared

1, light

B subunits)

can

like

molecules

component

in Scheme

both

species

degree

system

on

molecule.

reduction

contrast,

large

the

viceversa).

on

species

on

subunits

(where

(iii)

molecules.

of

shown

A to B (or

supramolecular

oxidation

the

By

based

parameters,
species.

keeps

be

systems;

components.

between

subsystems

supramolecular

that

molecular

as large

can

of supramolecular

(ii) host-guest

distinction

species

types

species.

defined
the

practice,

between

systems;

(iv) covalently-linked

considered

fullerenes

of four

is

are
better

reduction
described

whereas

oxidation

of
as

Suprarnolecular photochemistry

Scheme

lo447

supramolecular

compound

large

species

molecule

*A-B
A-*B
hv

hv

c-------

A-B

t---

A-B

-ec-------

A-B

*(A-B)

A+-BA--B+

+e-

+eA--B

(A-B)-

A-B-

A+-B

-e-

(A-B)+

A-B+
and reduction

of a large

the

are

electron

(Scheme

principle,

supramolecular
isolated

the

to species

delocalized

properties

structure

components
however,

suitable
cies

substantially

leads

on

where
the

the hole

entire

or

system

1).

In

cases,

molecule

models

is not

species

species
connector

problem.
A

that
is

can

and

B would
never

bound

this is not a problem

to

of real

are

be radicals
as such.

the

components
molecular

study

molecules.

components

some
via

species

cases,

the

constitute

and

speA-L-B
L

is

unsaturated
e.g.

carbon-carbon
such

several

in a covalent

or coordinatively
In

of

In
that

of

of a supramolecular

speaking,
active

the

molecules

components
Strictly

components

from

model

exist

since

molecular

obtained

identification

a trivial

A and

the

suitable

molecular

which

connector,

of

for

in

be

can

or

the

of

when

the

bonds,

as AH and BH or

10448

V. BALZANI

AR

and

BR

properties

(R=alkyl

to A and

however,

the

electronic

subsystem

compounds

that

be

to

used

may

indeed

of

include

the

active

the

more

such

of

In other

In

as A-L

properties

identical

deeply

components.

the connector,

approach

almost

species.

interact

Photochemical

act

of

any

and

and

photochemical

of a photon

that is formed

in this way is a high

undergo

state

some

and

by a molecule

type of

case,

B-L,
B

molecule

reaction),

(ii)

in

the

processes

photophysical
(eq.

1). The

energy,

unstable

deactivation.7

can

and

emission
(iii)

occur

light

of

As

process
excited
species

shown

other

present

and

in the

of
(iv)

in

disappearance

is
state

which
Fig.

2,

excess

energy

type

(quenching

of

the

(photochemical

deactivation,

some

solution

(i)

products

(radiative

degradation

deactivation),

via

formation
of

(radiationless
species

should

(I)

deactivation

original

luminescence),

cases,
the

A + hv ----> *A
excited

in

with

such

and

photophysical

the absorption

must

be

species.

3.

first

will

B in the supramolecular

connector

supramolecular

The

group)

also

called

into

heat

of interaction

with

processes).

products

A + h$

/
*A
t

A+hJ

\
+B

A + heat

J
A and/or products
Fig. 2.

Light

excitation

electronically

of

excited

molecule

state.

and

deactivation

of

the

Supramolecular photochemistry

As
of

is well

light

known

from

absorption

absorption

(and

band)

is

thus

and

particularly

Transitions

from

the

value

are

transitions
and

allowed

to

can

excited

hardly

molecules

the

is a triplet

to

be

of

observed

ground

state

rise

in

the

can

be obtained

from

the

deactivation

this

reason,

least

three

states

excited

singlet

and

be directly

triplet)

are

as is shown

in the Jablonski

by

reaction

chemical

Emission

of

light

A@,)

is not

the

involved

number.
the

are

spectra.

by light

ground

of Fig.

represented

for

forbidden
In

most

excited

state

absorption

excited

states.

state

singlet

is

3, where
the

called

sake

of

fluorescence

AK+,)Fig. 3. Schematic
species.

energy

singlet,

kiscf

k,,

and excited

and ki,,

fluorescence,

crossing,

diagram

for

a typical

molecular

SO, S,, and Tt are the ground state singlet,

state

crossing,

level

state triplet,

respectively;

are the unimolecular

internal

conversion,

phosphorescence,
respectively.

and

rate

and

simplicity.

A(T, 1

abs

For

deactivation

kisc

but

process,

same

whereas

in a photochemical

diagram

states

bands,

lowest

of upper
(e.g.,

the

having

value

absorption

populated

(luminescence)

corresponding
of

intense

and

probability

quantum

spin

is a singlet

cannot

the

states

to

different

that

at

spin

to excited

give

states

of

the

characteristics

their

state

and

intensity

the

to

ground

spectroscopy,7

the

related

involved

spin

electronic

10449

excited
kr, kt,.

constants

for

S,PT,

intersystem

T,--+Su

intersystem

or

10450

V. BAUANI

phosphorescence

depending

on whether

same or different

spin compared

way, radiationless

deactivation

occurs

between

when it occurs
internal

states

to the ground

state

state.

is called internal

states

of different

are

conversion
and

conversion

the

when it
crossing

spin. Fluorescence

spin-allowed

intersystem

has

In the same

of the same spin and intersystem

between

phosphorescence

the excited

steps,

crossing

are

and

whereas

spin-forbidden

steps.
Each intramolecular
constant

(Fig.

lifetime,

given by

decay

step is characterized

3) and each

excited

state

by its own rate

is characterized

z =l/Ziki
where ki
process

by its

(2)
is the first order rate constant for a generic

that

causes

the disappearance

unimolecular

of the excited

state.7

For

each process one can define the quantum yield, @, which is the ratio
between

the number

produced

and

absorbed.

For example,

yield

the

of moles

of emission

(phosphorescence
following

Op=q.

where

number

of moles

making

from

the

quantum

ISC

and z

Tl

of photons

reference
lowest

yield

to Fig.

spin-forbidden
Qp)

or molecules)
that

have

been

3, the quantum
excited

can be expressed

kz

state
by the

(3)

p Tl

state from the state populated

(photons

equation

nisC is the efficiency

rl isc

of species

of population

of the emitting

excited

by light absorption

kiscl(kisc+ k, + kit)

(4)

is the lifetime of the emitting excited state

= l/(k,

+ k&

(5)

10451

Supratnolecular photochemistry

When
when

the

intramolecular

the lifetime

excited

molecule

another

solute,

may

occur

chance

to

the

involved
states

and

the

in

that

satisfy

too

fast,

i.e.

long,

the

a molecule

of

place

arguments

states
excited

called

show

other

condition

interaction
is

-9 s may

-10

with

excited

specific

taking

than

this

spin-forbidden

some

kinetic

encounters

the

molecules.
lowest

for

organic

state

for

only

have a good

solute

are

that

spin-

molecules,
coordination

10
k

encounter
complex

T,+ B +$

pA!B]+&

representation

take place following

and another
The

most

transfer7-l

chemical

important
and

either

transfer

reaction

A + B catal. deact.
of bimolecular

an encounter

processes

between

that may

an excited

state

species.8
bimolecular

electron
the

A +*B energy

+ D chemical

I k,

Fig. 4. Schematic

involve

A or products

may

a case,

longer

spin-forbidden

lowest

compounds.

live

not

to encounter

process

Simple

are

(eq. 2) is sufficiently

a chance

and

that

steps

state

2). In such

4)

states

be

excited

and

have

process.7-10

excited

allowed

may

(Fig.

those

The

of the excited

B (Fig.

bimolecular

deactivation

transfer;7-1

oxidation

or

are

energy

latter

process

processes
*12-1

the

the

reduction

energy

transfer

of

the

excited

state:
k

en
>A + *B

*A+B-

(6)

k OX
*A+B-

>A+ + B-

oxidative

electron

transfer

(7)

>A- + B+

reductive

electron

transfer

(8)

k red
*A+B-

10452

V. BALZANI

The

thermodynamic

energy

transfer

energy,

Eoeo.

processes
For

thermodynamic

the

electron

because

potentials

reductant

ground

state.

for the excited

potentials

of

potential

the

corresponding

transfer

processes,

the

energy

It should be
an

content,

the redox

may be calculated

to the zero-zero

and

excited

oxidant than the

To a first approximation,

couples

relevant

(eq. 7) and reduction

and a stronger

state

the

excitation

from the

one-electron

energy:

E(A+/*A) = E(A+/A) - E-

E(*A/A-)

Kinetic

coefficient)

(9)

= E(A/A-) + E-

parameters

(10)

(i.e., intrinsic

barrier

can also play an important

transfer

processes.lv12

Figure

molecular

quantities

characterize

that

point of view of energy and electron

Photoinduced
take

place,

energy
of

supramolecular

A-B + hv-->

course,
species,l

*A-B

in

spectroscopy

and *A/A- couples.

state couples

ground

to intervene

to its zero-zero

of its higher

state is both a stronger

state

are the oxidation

of the *A/A+

that,

corresponding

of an excited

is related

parameters

(eq. 8) potentials
emphasized

ability

transfer
also

and electronic

transmission

role in energy

and electron

shows

schematically

an excited

state

some
from

the

transfer processes.

and electron
between

transfer

molecular

processes

can

components

of

e.g:

photoexcitation

(11)
(12)

*A.-B -->

AL-*B

energy

*A-B->

A+-B-

electron

transfer

transfer

(13)

Supramolecular

10453

photochemistry

SAA

A-

E (A/K)

E (A+/A)
Fig.

In

5. Schematic
relevant

to

electron

transfer

supramolecular

components,
to

(Section

the
of

molecular

quantities

photoinduced

energy

and

processes.

constituted

energy
or

by

or electron

charge

several

molecular

transfer

steps

may

over

long

distances

separation

lead

7-2).
interesting

excitation

of

electron

transfer

intercomponent

that

can

supramolecular

species

process,

leads

which

state

take
is

the

place
so

to the direct
(Fig.

upon

called
formation

electron

transfer

electron

transfer

A-B

optical
of an

(14)

electron
(eq.

light

6):

A+-B-

photoinduced

->

event

charge-transfer

A-B + hv->

A+-B-

discussion

species

migration

Another

Both

the

successive

energy

indicating

diagram

14)

transfer
may

(eq.
be

11 plus

followed

eq.
by

13) and

optical

thermal

back

process:

(15)

V. BALZANI

10454

nuclear configuration

Fig. 6. Optical
electron

The relationships
transfer
Fig. 6.

processes

(l),

transfer

processes

between

optical,

books and review

Cage-type

species.

are schematized

and electron
discussed

transfer

supramolecular

in

processes

in a number

metal

Cage-type

of

systems

complexes

Systems made of a metal ion enclosed into a macrocyclic

encapsulated

(4)

and back electron

species

been

back

articles. v5g6*15-20

4.

4.1

have

thermal

photoinduced,

of energy

species

and

in supramolecular

in a supramolecular

Several examples

in supramolecular

(2+3),

photoinduced

by a cage-type
species.1*2v4

ligand

may

often

In this review

ligand or

be considered

as

we will only recall

Supramolecular

three

paradigmatic

presence

of

cage-type

photophysical

4-1-I

ligands

complexes.

are kinetically

because

of

metal

modifies

complexes
the

where

photochemical

orbitals.21

metal

of

decomposition

presence

the
and

is

well-known

that

the

of

electrons

in

the

Co(II1)
are very

o*M (e,)

As a consequence, reduction of the central

Co(NH3)6 3+ in aqueous
solution
causes the

of the complex.

by the following

Co111(NH3)6

It

inert while the Co(I1) complexes

the

antibonding
ion

of

properties.

Cobalt

complexes
labile

examples

10455

photochemistry

Such a reduction

may be carried out

methods: (i) pulse radiolysis,22

3++e

aq

- ->

Co1(NH3)6 2+

(16)

H30+
Co11(NH3)6

2+ ->

k> 1 x lo3 s-l

Coaq2+ + 6NH4+

(ii) ion pair charge-transfer

(IPCT) photoexcitation

(17)

(0 = 0.2),23

hv
Co111(NH3)6 3+

.I

<y-+

C011(NH3)6

2+ .I

(18)

H30+
C011(NH3)6

2+

or (iii) intramolecular
photoexcitation

Coaq2+ + 6NH4+ + l/2X2

. I ->

ligand-to-metal

charge-transfer

(19)

(LMCT)

(Q = 0.16)23
hv

c0111(NH3)6

3+ +

Co(NH3),(NH3

CoH(NH3)$NH3

+ 3+
)

H30+
+ 3+ -->
Coaq2+ + 5NH4+ + products
)

(20)

(2 1)

10456

V. Bm

Simple

chelation

because

does

Co(en)33+

reduction

loses

excitation

undergoes

In
of

1977

(en

its

encapsulated

with

redox

coworkers24

ion

so

with

NH3

octaazabicyclo-[6,6,6]-icosane)-cobalt(II1)
sepulchrate,
type
and

Co(sep)3+.

complexes
studied

of

Since

a variety

by Sargesons

a great

of metal

Fig. 7. Synthesis

quite
the

and

interesting
most

of

Co(sep)3+

the
in

cannot

reduced

From

species.

radiolysis

be observed

Co(se~)~+

+ eaq-

->

Co(sep)2+

-/I->

Co,q+

was

reaction

(Fig.

called

number

ions

7). The

have

cobalt(II1)

of similar
been

cage-

synthesized

cage-type

consequence

pulse

a capping

of the Co(II1) sepulchrate

analogous

properties.

important

inertness

coaq2+

the

Q=O. 13 .23

group.25-28

NH,,CH,O

Co(sep)3+

LMCT

(1,3.6,8,10,13,16,19ion,

then,

radiolysis

upon

and CH20

obtained,

situation

pulse
and

performed

with

the

after

k > 25 s-1,22

its C3 axis

metal

change

decomposition

and

along

substantially

= ethylenediamine)

ligands

Sargeson

Co(en)3 3+

not

complexes

the

photochemical

point

of

encapsulation

is

Upon

of

view,
kinetic

reduction

of

in

formation

of

in strong

fact,

acid solution):29

Co(sep)2+

+ products

the

several

one-electron

experiments,

(except

exhibit

(22)
k < 1O-6s-1

(23)

10457

Supramolecular photochemistry

Such

a kinetic

intramolecular

inertness
LMCT

prevents

photodecomposition

and also on IPCT

excitation

(@ < 10W6) on
excitation:30

hv
CoIr1(sep)3+

Co11(sep+)3 +

Co11(sep+)3+

-//->

Coaq2+

(24)

+ products

(25)

hv
Co111(sep)3+.

. I -//->

Co11(sep)2+
In

spite

of

Co(NH&j

3+

their
(or

absorption

spectra.

caged

und

uncaged

basis

of

Co11(sep)2+

I- e

the

Co

different

Co(en)3 3 )
These

and

complexes

energy

(27)
photochemical

Co(sep)3

differences

hexamine

(26)

2+ + products

completely

potential

LMCT

aq

.I

curves

and
can

have

behavior,
quite

similar

similarities
be

shown

between

explained
in

on

Fig.

MC(T,)\
MC( 3T, ,

h3

nuclear
Fig. 8. Schematic
Co(sep)3+.31

potential

coordinates

energy

curves

for

Co(NH,),s+

and

8.3

the

10458

V. BALZANI

Encapsulation

does

symmetry
the

of

ligand

energy

the

first

atoms

curves

spectroscopic
strong

the

caged

region

are

nearly

dissociation

along

competition

with

Encapsulation,

pattern
the

of

ground

state.3

no

the

longer

other
of

cage

hydrogen.

8).

to

large
of the

positions

by

the

complex

potential

energy

(Fig.

8). so that

ligand

radiationless

decay

have

to

the

properties.g~10*14~40
well

known

as (i) a photoluminescent
electron

chemiluminescent

and

the

as relays

and

electron

as
anions

processes,

ten

years

attention

combination
The

Ru(bpy),z+

and

species,

(ii)

and

of

these

is extensively

used

state

an excited

of light

several

ground

prototype

an excited
(iii)

Ru(II)-

of

of

electrochemiluminescent

in the interconversion

be used

of

last
the

a unique

compound,

transfer

can

products,

30,38,39

attracted

state
the

of

reduction

water32-37

In

excited

a mediator

(Fig.

sepulchrate

photooxidation

because

(iv)

in

IPCT)

curve

from

groups

in

(or

complexes

complexes.

complexes

and

the

one-electron

research

energy

curve

state

fixed

of their

for
of

Ruthenium

complexes,

for

MLCT

hydrogen

evolution

polypyridine

the

to the dissociation

with

Co(III)

photosensitizers

4.1.2

for

to

constraints

almost

steep

the

is due

energy

ground

compete

inertness

photogeneration

simultaneous

in

in

and

transfer

kept

Therefore,

of

excitation

nuclear

particulary

by an upward

of the

Co(sep)3+
for

bonds.

branch

can

Because

are

the

potential

accounts

potential

to

by

photodecomposition

(or IPCT)

decay

the

complexes

The

IPCT)

and

constituted

Thus,

which

spectra.

(or

and

ion.

same,

introduces

which

is replaced

detachment

LMCT

motions

covalent

the

composition
is

uncaged

on LMCT

however,

units,

and

the
which

metal

absorption

radiationless

dissociative

curve

the

nuclear

coordinated

the

sphere

the

for

in

modify

coordination

CO(NH~)~ 3+

of

amplitude

substantially

surrounding

similarity

reaction

not

reactant

state
reactions,

and

chemical

in

product
and
energy.

Supramolecular photochemistry

10459

(CT)Ru(bpy);

+1.26V
Ru(bpy);

Ru(bpy$

of Ru(bpy)32+.41

relevant

are

scheme

of

data

Fig.

concerning

9.

ideal

photosensitizers

main

drawbacks

radiationless
(with,

the

the

proceeds

via

of

undergo

that

level

between

containing

reformation

p4

solutions

containing

the

ligand

radiationless

to a distorted

3MC

monodentate

bpy

either

of

loss

of Ru(bpy)32+.

decay

with

of a ligand
dependent

water

at

Cl- ions).

room
It is

reaction

transition

from

the

with

the

ground

state

an

intermediate

to

formation

or

and

level,

ligand.44v45
bpy,

lifetime

photosubstitution

activated

bond

state

strongly

_ 10-S in

the

ground

occurrence
is

that

fast

state

(from

radiationless

Ru-N

(b) the

for

relatively
the

excited

efficiency

in CH,Cl,

a thermally
3CT

competition

whose

to

the

needed

the

state

in

shows

(a)

short

and

conditions

agreed

luminescen;

cleavage

reaction

requirements

are

excited

efficiency),

to -10-I

generally

3CT

summarized

luminophores43

a relatively

experimental

temperature

and

the

Ru(bpy)32+

of

luminescence

photosubstitution

complex

with

p42
of

decay

this

Comparison

as a consequence,

a small

can

Ru(bpy)r

Fig. 9. Ground and excited state properties

Some

on

-1.28V

===

chelate

of
Such

ring

an

subsequent
and

intermediate
closure

with

10460

V. BALZANI

Ligand photodissociation
linked

together

suitable

to

cage-type

make

structure,

processes

with consequent

does

not

geometry

a cage

ligand

molecular

lifetime.

can be prevented

can

thereby

the metal

and/or suitable

the

confer

slowing

down

It may also happen,

allow

around

also

increase

if the bpy ligands are

ruthenium

more

rigidity

to attain

that

an appropriate

Ru-N bond distances.

decay

intensity

the cage-type

to the

the radiationless

of both emission

however,

ion.

and

ligand

coordination

In such a case, the

3MC level would drop below the 3CT level and most of the valuable
properties

of the complex

would disappear.

Molecular

that this must be the case for the bpy.bpy.bpy

will

see later,

such a ligand

symmetry-demanding
the octahedral
confirmed
complex
ligand47

coordination

required

by the lack of luminescence

claimed
shown

(a)

for

the

larger,

not

by Ru2+. This is apparently

at room temperature

to be the [Ru c 1]2+

in Fig.

cryptate.

10a is clearly

The

more

suitable

Cage-type

ligand

suitable

and (c) representation

from a
cage-type

for Ru2 +

(cl

(b)

synthesis

1. As we

cryptand

Eu3+ ion, but it is clearly too rigid to create

(a)
Fig.10.

is appropriate

models show

for

RuZ+

coordination;47 (b)

of the cage

complex.48

10461

Supramolecularphotochemistry

coordination
allow

the

because
bpy

coordination
been

ligands

via

of Ru(bpy)J2+

room

The

a template

Ru(bpy)j2+

(about

49 This

capable

because

not

ions,

luminescent

and long-lived excited

efficiency

to those of

state lifetime

towards
high

at

an extremely
ligand

turnover

number

Eu3+

supramolecular

luminescence
point

use for a variety

lanthanide

lowest excited

similar

and

a strong

a fundamental

particulary

complex (Fig. 10~)

stability

Molecular

of exhibiting

of their potential

has

is used as a photosensitizer.

complexes.

only from

very

a quite

octahedral

from a derivative

and, as expected,

assures

and

of this ligand

a longer excited

times)

104

Lanthanide

interesting

ideal

starting

spectra

vs 0.8 us)

when the Ru-cage bpy complex

species

almost

reaction

complex,

(1.7

photosubstitution.

4.1.3

an

Ru(I1) complex

and emission

temperature

greater

create

(Fig. lob). Such a Ru(I1) cage-type

absorption

the parent

spacers make the cage flexible

to

environment.

prepared48

exhibits

its larger

are

of view,

but also

of applications.

and Tb3+,

possess

states. For example

quite

Some
strongly

(Fig. ll),

the

state of Euaq3+, 5D0, lives 3.2 ms and emits with an

of 0.8 in D,O solution.50

very poor light absorbers.

Unfortunately,

The strongest

absorption

these ions

band of Euaq3+

EJA17Fo)+heat
EG(Fo)&

.-

*Euaq
3+rqJ /
\

E~;(7Fo)+ hd

~0.02111
H,O
0.8h-i b0

t =O.llms in Hz0
3.2ms in D#

Fig.11.

Excitation

and deactivation

are

of Euaq3+.50

10462

V. B~UZAN~

occurs

in the near UV and visible region

coefficient

absorption
excellent

emitting

absorption

coordinating

but

ability.

cage

to overcome

ions

cage-type

(i) the complexes

(ii)

light

do not
ligands,

molar

to find

the lack of

the cage-type

can

(solvent)

radiationless

decay

Following

these

synthesized

the Eu3+ complex

displays

coupling

with

excellent

spin-forbidden
5D,,f-f

state,

effect);

(iii)

the

rate

which mainly

co-workers52

properties.

have

ligand 1, which
The

energy

is shown in Fig. 12.53 Excitation

by intersystem-crossing

level
in the
to the

3LC level that lies at higher energy than the

level of Eu 3+. The efficiency

of energy transfer

from the 3LC level of the bpy ligand to the 5D u metal level
sufficiently
molecular

high (n = 0.1). so that such a complex

device

of

O-H vibrations.5 1

of the bpy.bpy.bpy

ILC bands is followed

luminescent

and

by the

energy can then

decreasing

excited

Lehn

luminescent

important

ion from interaction

the high energy

guidelines,

diagram for this complex

spin-allowed

thereby

of the luminescent

via

strong

metal ion (antenna

molecules,

takes place

exhibit

be assured

ligand can shield the lanthanide

water

is, of

can be fairly stable because

absorption

to the luminescent

ligands

three

groups on the ligands, and electronic

be transferred

lowest

with

one has thus

ion with suitable

lanthanide

By using

effect;

chromophoric

indeed

ions
i.e.

states,

of the lanthanide

goals can be reached:

with

of these

their excited

a possibility,

of the

nm

bands.

Complexation
course,

393

lower than 3 M-lcm- 1. To make use of the

properties

ways to populate

at

for the conversion

is

is an efficient

of UV light absorbed

by the

ligands into visible luminescence

emitted by the metal ion. Even in

very

(-10m5M)

dilute

convert

about

photonss4,
particular

aqueous

solution

1% of the incident
a quite interesting

for labelling biological

this complex

UV photons
result

into emitted

for several

materials.

is able to
visible

applications,

in

Supramolecular photochemistry

Ligand

10463

Metal

30'3
e
p

20-

5
l&llo-

Fig.12.
Considerable

effort

luminescence
caging
be
not

into

imply

levels

at

the

(b)

or

by

be efficient;
a close

light
this

the

presence

of

of

ligand-centered
higher,

contact)

of

otherwise,

the

luminescence

efficiency

absorption

to

some

between

or

level;

the

the

energy

the

degree

the metal

and

metal

should

that

of

the

channels

level
be

for

would

be

compromised;
excited

centered

of interaction

to

charge-transfer

new

ligand-centered

other

have

ligand

than

would

the

by using

(a)

from

implies

complexes

improve

requirements

luminescence

transfer

energy

further

additional

slightly

decay
the

to

two

metal-centered

and

populated

that,

occurrence

lower,

devoted

of Eu3+ and Tb3+

In doing

radiationless

available

currently

consideration:

luminescence
fast

is

properties

ligands.55

taken

Energy level diagram for [Eu~l]~+.ss

states

levels
(and,

the coordinated

should
therefore,

atoms

of the

the

Eu3 +

ligands.
Excellent

luminescent

complexes

of

Promising

results

2,56

properties

and

have

by the Tb3+

also

like 4,58 5, 5g and 660 which

been

are

by

complexes

obtained

incorporate

exhibited
of

by using
N-oxide

256

and 3.5 7

cryptate

ligands

groups.

10464

V. BU

cp
Ph

4-2

several

cages

that

different
It

can

be

well

know

due

cryptand

strand

this

photocleavable
the cryptand
to create

result,

a high

would

Lehn,

light-controlled

of the

ether

jumps

2.2.2

cation

have

polyoxadiazaLehn

alkali

the

one

decrease,

solution.

introduced
of

these

compounds

or pulses

of cation

the

ion

of one

affinity

into

and

metal

Photocleavage

recently
into

Two

reported.

by

towards

bond

In principle,

been

ago

size.

to have

excitation.

a substantial

metal

et al. 62

and

long

cavity

cause

light

recently

2.2.1,

selectivity

different

release

13).

2.1.1,

be necessary

by

have

prepared

2-nitrobenzyl
(Fig.

closed

problem

the

to the

a consequent

obtain

that

exhibit

complexation

with

to this

cages

it would

and/or

criptands,

coworkers,61

the

opened

approaches

is

photo-flexible

of applications,

types

macrobicyclic

of

and

Photo-cleavable

For

bridges

could

To
the
of

be used

concentrations,

Supramolecularphotochemistry

that would
cleavable

be quite

chelating

described.6

useful

ligands

investigations.

for physiological
for alkaline-earth

cations

R-&O:

Control

of the cavity

by taking advantage

reversible

photoisomerization

azobenzene

capped

cryptands.62

size without

obtained

crown

disruption

tram->cis

takes place,

reaction.
ether

For

metal cations

8, whose

the pyridine

nitrogens

can coordinate

are directed

in this cis

the ability

caused by a

example,

the

small metal

with UV light, the well

cavity

preferably

in the tram

towards

unit

binds large

When the azobenzene

bridge

is

conformation

the crown

plane

and

in the crown ether ring, whereas

conformation

to extract

trans-

of the azobenzene

bridge,

metal ions enclosed

this is not possible

consequence,

larger

like K+ and Rb+.64

by the 2,2-azopyridine

changes

7 binds preferentially

photoisomerization

yielding

of the cage can be

of the structural

cations such as Li+ and Na+. On excitation

co2+,

have also been

m-n-1

Fig.13. Photocleavable

replaced

Photo-

R=H:m-n=O
m-1. n-0
m-n-l

known

10465

heavy

of the bridge.

As a

metal ions (Cu2+,

Ni2+,

and Hg2+ ) from aqueous solution to an organic phase can be

photocontrolled.
containing

two

described.66

photoresponsive

isomerizable
In

towards

various

towards

the rate

of hydrolysis

photocontrolled.

azo-benzene

azobenzene-capped

ability

cylindrical

substrates

units

the

ether

also

been

has

cyclodextrin,
and

crown

the

catalytic

of p-nitrophenylacetate

bridging
activity
can

be

V. BALZANI

7
Vogtle

and

macrocyclic

species

light excitation,

have

co-workerse8

synthesized

9 which contains

the very

three azobenzene

each unit can undergo a trans->cis

with a consequent

interesting
units. Upon

isomerization

change in the size of the cage cavity. All possible

configurational isomers (E,E,E,; E,E,Z; E,Z,Z,; Z,Z,Z) have been isolated.

For a review

on structural

changes

in photoflexible

systems,

see

chapter 7 of ref. 1.
H

9
4.3.

Photochemistry

Two main families

are

currently

fullerenes.70

of

incarcerated

of spherical-type

attracting

much

molecules

molecules
attention:

with internal
carcerandseo

voids
and

10467

Supramolecular photochemistry

In carcerands
molecules,

the internal

providing

characteristics
phase.
reactions

them

and

The

are
then

these

is large

inner

which

possibility

within

cavity

new

phases

arises

perform

reactive

species

radicals

prepared

and studied

in appropriate

first,

exciting

photochemistry
Cram

and

is

the

photofragmentation
and found

that

imprisoned

or unstable

Interesting

questions

nm) required

example

species.

of

the

guest

Many highly
can

this

new

of cyclobutadiene
studied

of a-pyrone

within

irradiation,

the

likely

be

branch

of

performed

by

photoisomerization/

a carcerand-type

species

cyclobutadiene

remains

arises

is effective.

luminescent

in argon

of cyclobutadiene
Absorption

based

translocation
chemical

on

of a large-cavity

systems

fundamental
the

carried

of
to

the

light

at 8 K.
(200-250

and its reaction

to

by

genes,

study

which

Systems

out

crown

compound

studied.71

recognition,

(enzymes,

discovery
way

Host-Guest

molecular

processes

matrix

by the dimethoxybenzene-

three Cu+ ions have been recently

is

and exists

is a possibility.

properties

5.

is

breaks down to

as to how the exciting

for the formation

acetylene

cyclobutadiene

when is prepared

type units and photosensitization

opened

where

inner phases.

They

On further

as it does

Life

bulk

photochemical

isomers

of the two photoproducts

acetylene,

contains

peculiar

of the

stable in the inner phase at room temperature,

as a singlet.

The

matter

other

into the cage while CO, escapes. The cyclobutadiene

thermally

give

of

with other

taming

co-workers.@e

to

phases

to interact

very

exhibit

regardless

is prevented

The

which

to host

maintained

molecule

like

enough

ethers
of

transformation,
extremely

antibodies,
by

complicated
etc.).

Pedersen72

molecular

and

The

in 1967

recognition,

lo468

V. BALZWI

transformation,

and

synthetically

accessible

concave-oriented
almost

exclusively

have

prepared

been

species

a great

(guests).

processes

This

and

photochemical
on

structure-specific

electron

intermolecular

and

The
is

in Section

approach

the

adducts

are

properties
photochemical

separated

5.1

characterized

by

Reviews

of

on

elsewhere.

the

ion-pairs,74-77

chromoionophores

can be found

species

the

and

compounds,84-87
Cage-type

described
capable

and

compounds

separated

species

to

give

and
are
of

those

section

host-guest

photophysical

studied;

properties

compared

in this

to

photochemical

photophysical
then

Polyammonium

hydrogen

in determing

the

(iii)

the

adduct

are

exhibited

by

the

components.

Because

adduct

and

where

Supramolecular

not

properties

inclusion

molecular

two

and

role

be discussed.

cyclodextrin

(ii)

the

as

complementarity

but

in the investigations

chosen;

of

investigated

(i)

light-induced
defined

properties.

not

molecular

4.

taken

following:

will

the

(hosts)

components

a key

complexes,78.79

of DNA,*4188

are discussed

play

forces

photophysical

fluoroionophores,su-84

of

systems,

synthetic

shapes)

previously

of convex

examples

photophysical

donor-acceptor

adducts

of

years

species

(particularly,

convex

25

to complement

molecular

host-guest

made

interactions

photochemical

begun

last

simple,

chemistry

illustrates

in

and

based

thus

the

complexation

interactions

structure-specific

systems

section

species

concave

In

of concave

selective

occur

supramolecular

has

variety

for

that

between

species.

convex-oriented

and

with

processes

molecular

chemistry73

developed,

the

translocation

macrocyclic

of their
bonds,

formation.

high

cyanide

electric

receptors

charge

complexes

Co(CN),3-

gives

are
rise

and
very

with

their

CO(CN),~-

capacity

suitable

to very

stable

to form

species
I:1

for

adducts

10469

Supramolecularphotochemistry

with

the

shown

protonated

in Fig.

the same

as that of free
partners

transfer

transitions.

constants
a

of

the

The resulting

14.8g

between

with

forms

that

peripheral

cannot

give

The relatively

contribution

nitrogen

absorption

CO(CN)~~-,~~

(103- 106 M-1) reflect

large

polyazamacrocyclic

of

atoms of the polyammonium

to
values

for

adducts
charge-

of the association
interaction,

hydrogen

bonds

complex

anion

the

is essentially

low-energy

an ionic-type

from

atoms

spectrum

as expected

rise

high

receptors

probably

between
and

the

hydrogen

cation.

ZJ
-(CH& 4
HN

NH
I--(CH&--;

[32]ane-Ng

[32]ane-N6-Cg

[24]ane-Ng

[24Jane-N3

Fig.14.

Structures

CO(CN),~- undergoes
28)

that

can

COAX-

near

be easily

+ H,O ->

of some polyazamacrocyclics.

a very

clean photoaquation

followed

Co(CN)&H,O)*-

where

UV

region,

throughout

the

photoreaction

is high

two

from

isosbestic

.points

The
and

changes

@ = 0.30

+ CN-

photoreaction.
(@,=0.30)

spectral

reaction

quantum

independent

are

in the
(28)

maintained

yield
of

(eq.

of

the

excitation

V. BALZANI

wavelength,
primary

acidy

of the solution

photochemical

significant

concerted

is predicted

process

photodissociation.

simple

is

1.2-5.0),

and solvent.

thought

to

dissociative

rearrangement

initial

be

step

of the five coordinate

The
CN-

without
fragment

theoretically.g 1

When

the

COAX-

containing

solutions

aqueous

photoexcited,

same

photoaquation

the

reaction

adducts

are

exhibited

by

alone, i.e. CN- release, is observed. However, the quantum

yield

of the photoreaction

free

COAX-

introduce

(Table

Co(CN),j-,

formation

reduces

to a multiple
discrete

is noticeably

lower than that found

1). g2 Since

adduct

new energy levels at low energy,

that the reactive

free

(pH

excited

formation

does

for
not

it seems fair to assume

state of the adducts is the same as that of

One striking
the quantum

observation

(Table

1) is that adduct

yield @ to values essentially

equal

of (1/6)@u, which suggests that in the adducts only a

number

of

CN-

groups

are

permitted

to

undergo

photodissociation.
Table

1.

Quantum yields for the photoaquation of COAX-

alone

(@O) and its adducts with polyazamacrocycles (Q>)a.

Co (CN)

63-

1.0

0.33

1.2-5.0

0.30

([24]ane-N6H6)6+ .CO(CN)~~-

2.5

0.15

([24]ane-N8H,)7+.Co(CN)63-

2.5

0.15

([24]ane-N8H8)8+ .CO(CN)~~-

1.0

0.16

([301ane-N10H10)10+ .CO(CN)~3-

2.3

0.14

((32Iane-N6H6-C9)6+ .CO(CN)~~-

1.2

0.11

([32Jane-N8H8)8+.Co(CN)63-

2.5

0.10

aAqueous solution, room temperature; from ref. 92.

10471

Supramolecular photochemistry

In

agreement

results

obtained

adducts

with

cobalt

ligands

only

2 of

are

indications

be

large

can

the

the

can
the

complex

CN-

with

rationalized
32-atom

be enclosed

involved

macrocycles,

encirclement

and the most

likely

free

of

structure

in

the

models,

following

receptors,

within

ligands

space-filling

ring

the

in hydrogen

CN-

of

bonding
to

CO(CN),~-

(Fig.

escape.

For

in Fig.

In

octahedral
so that

by the ring

is that shown

way.

the

macrocycle

the

four

15a).

leaving

the

smaller

is not possible,

15b, with

3 labile

CN- ligands.g2

(gbi p+Ny
-N++NH+

Fig.15.

Proposed
in

supramolecular

solution

macrocyclic

Besides
adduct
of

offering

formation

mixed-ligand

toward
appears

5-2

specific
also

the

charge,

receptors

by

products.

crown

properties
residual

protection

find

complexes

interesting
orienting

In

with

interaction

to

give

ability

size.92

against

photodissociation,

applications

cases,

in the case

complex
stable

of the adducts.

the

metal

which

adducts,

reactions

photochemistry

Pt(bpy)(NH,)22

on

formed

polyammonium

for the structure

a square-planar

needed

adducts

the

photosubstitution

favorable

probe

ethers

of

and

of different

also

NH+

COAX-

a generic

might

Wwy)WH3)22+ is
of

between

to be a valuable

Aromatic

structures

NH+
-NH+-

exhibits

namely
ion,

and

most
electric

residual

V. BALZANI

10472

-electric
y

hydrogen bonds

~-unfilled

coordination sphere

IC- fl stacking

Fig.16.

interaction

reaction

and

a variety
is

on

this

Furthermore,

both

photophysical

absorption
are

and

Because

the

NH,

undergoes
at low

of

ligands

of these

design

clean

and

adducts

of

by

addition

and

practically

acetonitrile,

is insoluble
of

emission

18C6

identical

showing

that

Pttbpy)(NH3)22+

hydrogen

bonds.

The

(Fig.

spectra

between

to

temperature

in

Pt(bpy)(NH3)22+

photochemical

of the

there

CH2C12,

adduct

and

of

free

intense

nm are due to spin-allowed

The

structured

18C6,

which

absorption

with

nn*

band

its

a 1:l

electronic
are

kept

maxima
on the
maximum

(Z = 25 PS) at 77 K and at 488 nm (Z = 100 ns) at room

19). These

metal-perturbed

data

indicate

triplet

that

the luminescent

ligand-centered

adduct.
(Fig.

The
18)

Pt(bpy)(NH3)22+

transitions

shows

but it can be

in CH2C12

is a negligible

and

luminescence

in

17) to give

those

307

(Fig.

16).

photochemical

high

properties,

(Fig.

interest.g4

[Pt(bpy)(NH3)2](PF6)2
dissolved

bpy

luminescence

of solvents.g3
for

an excellent potential guest.93

complex

exhibits

suitable

interactions

Pt(bpy)(NH&*+,

ability

charge

level.

excited
When

in

interaction
together
at

319

bpy
at

by
and

ligand.
486

nm

temperature
state

is a

aromatic

Supramolecular

lo473

photochemistry

onon

3
w

18C6

DB30ClO

DB24C8

Aono?i-v-

(xJwuJ 43
0

DB36C12

0700
[

0-0

BMP32ClO

8)
e/o
0

BPP28C8

BPP34ClO

fPo~@-onoAo

(wJ@eL/o I
DN30ClO

BPP40C12

l/5-DN38ClO
DA42ClO

Fig.17.

Crown

ethers

used as hosts

for Pt(bpy)(NH3)22+.

V. BAUANI

10474

!J

;_
290

340
\
A , nm

spectra

of DB30ClO

0
Fig.18.

Absorption

Pt(bpy)(NH3)z2+

\
1

)&_

390-

(-.-.), and of the adducts of

with 18C6 (---) and DB30ClO (-).g3

.
Y.

300

400

Fig.19.

Luminescence

4r

.-

----Pm

600
700
500
A ,nm
spectra of DB30ClO (---.), and of the adducts

of Pt(bpy)(NH3),z+

with 18C6 (---) and DB30ClO (-).g3

Supramolecular photochemistry

macrocyclic

polyethers

adducts

are

crystal

X-ray

again

that,

betweeen

the

Figs.

17 have

18 and

strong

changes

(see,

e.g.,

of

the

against
adduct

anthracenophane

host

photocyclization

reaction
2+,

Pt(bpy)(NH,),

photo
decomp0sition

band

hJ
7

19).

with
is

the

in

0
ck

/NH3

;Pt

ON
CJ

in

causes
of

the

a new,

broad,

region

of the
+

interesting
When

CH2C12

photoreaction

shown

Pt(bpy)(NH3)22

17).g7

20).

behavior

As shown

Particularly

photoexcited

no

place.

ethers

cases

Furthermore,

(Fig.

take

quenching

in the red

place

(donor)

formation

appears

(Fig.

however,

the

In several

DA42ClO

takes

crown

and

This

interaction

can

adducts

photoreactivity.

assumes

photochemical

aromatic

spectra

single

polyether

in detai1.g3*g4*g7*g8

absorption

Fig.

nn *

(acceptor)

of DB30C10,

luminescence

is protected
case

investigated

I:1

complex.95*96

macrocyclic

the

18C6,

receptor

and

of

DB30C10,

the

metal

complex

of the two components.

spectrum

the

in the

short-lived

guest

the

with

19 for the case

luminescence
and

been

that

the

photophysical,

2+ adducts

with

bonding,

of

of the metal

spectroscopic,

Pt(bpy)(NH,),

showed

hydrogen
units

in the place

adduct

around

besides

ligand

used

the

studies

aromatic

and the bpy

in Fig.

For

configuration

suggests

of

17) are

formed.

diffraction

U-shaped

The

(Fig.

10475

is

the

free

solution,

In

its

adduct

is

observed.

a
with
This

12+

NH3
I

+ ADDUCT h3_

Fig.20.

Photochemical
their

adduct.

behaviour

of Pt(bpy)(NH3)22+,

DA42Cl0,

NO
photoreact ion

and

10476

V. BALUNI

h3-

hJ-

h3

Host

1
a
Fig.21.

Schematic

Solvent

of

explanation

behavior

the

of Pt(bpy)(NHg)22+,

different

DA42Cl0,

photochemical
and their

adduct

(see text).

suggests

that,

between

the

as schematized
two

aromatic

a structure

which

solvent

prevents

and

an energy

level

reactivity

of

the

accounted

for

by

luminescent
In

the

host
the

conclusion,

appropriate
towards
spectroscopic

the

supramolecular
photoreactions
and

the

of

guest

the Pt complex

the

anthracenophane

from

photoreaction
of

the

host.

host

In

quenching

of the

luminescence

guest

adduct

formation

and

on

of a charge-transfer

excited

states

assembly

of

structure
and

photophysical

is inserted

the

photocyclization

presence

reactive

21,

moieties

protects

diagram,

and/or

in Fig.

can

of the
two

can

two

protect

with

the

terms

of

and/or
can

be

below

the

components.

components

profoundly

properties.

state

in

the

into

an

components

change

their

Supmmolecular photochemistry

5.3

Lasalocid

The

absorption,

&=25000

the

nm,

centered

nature
lifetime

of

and

of
the
is

photodecomposition

ligand

in CH,CI,

22)

have

slightly
salt.

the

excited

state.

luminescence

(LC)

band

solvent

and

ionic

strongly

affected

can

be observed

Cr(bpy)33+

Me

studies

is nearly

strength,
by

Et

and the lasalocid

spectrum

have

from

the

the

medium.g

Me

A anion LAS-.

nm,

the *E

shown

independent

solution.

is

luminescence

while

in CH2C12

as a

( &a,=307

originates

of

extensively

in CH,Cl,

The Cr(bpy)33+

Detailed
band

been

absorption

c=70 JJS for the PF6- salt)loO

(MC)

properties

soluble

Its

centered
solution).

Me

Fig.22.

is only

photochemical

Fig.

hexafltiorophosphate

M-cm-

energy

complex

by an intense

(h max =728
metal

This
or

dominated

Cr(bpy)33

luminescence,

investigated.gg
perchlorate

with

(bpy=2,2-bipyridine,

3+

Cr(bpyI3

anion

lo477

that

of

the

luminescence
g

No

10478

V. BALZANI

The lasalocid
nonpolar

A anion (LAS,

solvents.

This molecule

Fig. 22) exists as a monomer

contains

an aromatic

ring

in

which

displays a XX* absorption band at 307 nm (&=4550 M-lcmW1) and a

strong fluorescence
The fluorescence

band (h,,,
intensity

=418 nm; r=6 ns) in CH,Cl,

solution.

is much weaker for the protonated

LASH

species.
Cr(bpy)33+ and

Since
in

the

absence

Cr(bpy)33+
contrast,

of

electronic

solution

should

at the beginning

interaction
cause

addition

an increase

the absorbance

for the contribution

that Cr(bpy)33+

electronic

interaction

the metal

complex.

luminescence

and LAS

Confirmation

of

1:l

state lifetime

LAS - luminescence

fluorescence

quenched

was

measurements.
increase

for

intensity

from
addition

of LAS-

is very short (6 ns) and the

by a static

a strong

increase

An association

both
of

values

absorption

LAS-

also

higher

than

about 6 times higher

lifetime.

of the

mechanism.
in the LAS
for LAS

constant
and

causes
unity,

of -106
emission

a noticeable
at 728 nm;
a plateau

is

than that observed

in the absence of LAS-. A parallel increase was also observed

luminescence

of

present in the solution.

in the intensity of the Cr(bpy)33+ luminescence

with an intensity

comes

intensity

up to values close to those expected

obtained
The

formation

fluorescence

take place

LAS- causes

[LAS-]/[Cr(bpy)33+]

reached

for

clearly

is very low (2x10-5 M), quenching

can only
of

behavior

until the amount

of LAS

in the absence of the Cr complex.

M -l

and only

By

in the LC band of

adduct

The

measurements.

concentration

addition

to a

give rise to a 1: 1 adduct where

added is close to the amount of Cr(bpy)33+

Since the excited

This

causes a strong perturbation

LAS - at 418 nm is strongly

Further

LAS

in absorbance.

decreases

of the added LAS-.1oo

indicates

Cr(bpy)33+

of

3+] ratios higher than one it increases as expected

[LAS-l/[Wbpy)3

from

LAS- absorb in the same spectral region,

in the

lo479

Supramolecular photochemistry

Looking

at

carboxylate

group

intraligand

The

This

ligand,

interaction

leads

anions

sphere

account

the

for

under

lifetime

6.

(Fig.

a linear
23b)

(ii)

the

as a consequence,

in

level

(Fig.

species

with

and

are formed
bulky

composed

groups
of

or

of

the

interaction

can

intensity

and

while
the

the

effects

increase

luminescence

related

by a ring
on either
interlocked

a
Fig.23.

the

solvent

rigidity

for

ligand,

intensity)

species

which

is threaded

end.

Catenanes

rings.

Catenanes,

b
Schematic
knots.

in

of Cr(bpy)33+.100

catenanes,

23a)

account

electronic

with

absorption

fluorescence,
can

fragment
are

in

(iii)

centered

a bpy

electronic

to

complex.

and

interaction

The

the
an

LAS-

and parallel

(i)

increasing

ion.

LAS-

and

from

the

by replacing

close

are

that

Cr3+ ion in an

around

of

(iii)

metal

the

Rotaxanes,

Rotaxanes

and

variation

of

points

(and,

of the 2E metal

by

observed

quenching

described
the

PFg-),
of the

of LAS-

moiety
ion

see

(presumably

association

phenyl

can
the

approach

ring

this

of the Cr3+

(e.g.,

one

of LAS- wrapped

of
the

screening

static

can

the phenyl

results

coordination

the

LAS-

the tail

between

some

other

of

with

expected

(ii)

models

molecular

pocket of the metal complex

PF6- anion).
a bpy

CPK

representation

of

rotaxanes,

C
catenanes .

and

10480

V. BALZANI

rotaxanes

and

related

supramolecular
viewpoint.

architectureslo

much attention,

analytical

fairly

knots,

(like

very attractive

The design of such sophisticated

received
and

species

high

helicates,

methods

yields.

etc.

photophysical

but only recent

have

made

Nowadays

have

been prepared,

investigations

23~)

has since long

achievements
their

catenanes,

in synthetic

synthesis

with

rotaxanes,

knots,

but a few photochemical

have

been

are

from an aesthetical

systems

possible

several

Fig.

performed

so far

and

on such

species.
6.1

Catenands

A clever
synthesis

and

metal

route

around

tetrahedral-type

catenates

to obtain
a

interlocked

metal

complex.

Taking

coordination

geometry

imposed

ion and its affinity

Sauvage

catenates

Cu(2-cat)+ 12 and Cu2(3-cat)2+

leads

and 13,

where

and

16,

Starting

from

coworkers102

to the corresponding
the coordinating

cases of Cu2(3-cat)2+
species

is the template

advantage

of

have

prepared

14.

free

contains

the free

a catenate

catenands

the

metal

of these

(catenands)

are disentangled.

14, partial demetalation

which

(dap)

Demetalation

ligands

subunits

yields

11

In the

the Cu(3-cat)+

and a catenand

a number

the

by the Cu+ metal

for the 2,9-dianysil-l,lO-phenanthroline

unit 10,

catenates

species

of catenates

moieties.
of other

metal ions have also been prepared.lo2

The

luminescence

catenates

have

been

moieties,

as expected,

properties

of

investigated

(Table

behave essentially

unit 10. Upon addition of trifluoroacetic

however,

the

dup.lo5

showing

independent

properties

dap units,

around a proton
Zn(2-cat)2+

that

of

the

but involves

species

exhibit

catenands

2).103*104
as the dup

The

and

catenand

chromophoric

acid to the CH2C12 solution,

catenands

catenand

in a catenate-type

several

differ

protonation

does

coordination
structure.lo4

ligand-centered

from
not

those

of

concern

of two dup units

The Li(2-cat)+

(LC) fluorescence

and
and

10481

=-CH,+CEC

16

j*CH2-

b=-CH2Cti2fOCH2CH2j,

M -CuU) M'-Com)

15

phosphorescence,
divalent

ion.

luminescent,

considerably
The

more

Co(2-cat)2+ and

as expected

because

which occurs
and

via low energy

complexes
Cu2(3-cat)2+

spectral

region,

charge transfer

16, as expected,

the

luminescence

in the case

of the

Ni(2-cat)2+

complexes

are not

of

displays

catenand
of

radiationless

decay

excited

to the lowest-energy

triplet

state. The Cu(3-cat)+

species

two luminescence

and
the

a fast

metal-centered levels. The Cu(2-cat)+

exhibit an emission band in the red

that can be assigned

metal-to-ligand

from

perturbed

catenate

catenand

bands,

moieties,
moiety,

which originate

respectively.

however,

is

The
strongly

10482

V. BALZANI

quenched

by the adjacent

emission

can

G-catenate

be observed

at room

unit.lo3

For Ag(2-cat)+

temperature,

whereas

no

in rigid

matrix at 77 K a very intense band is observed at 498 nm (7=0.012

s) that can be assigned to the lowest 3LC level.lo4
CuCo(3-cat)3+
indicates
of

species

15

does

that the Co-containing

the

Cu-containing

derivatives

one.

display

behavior.

In particular,

not
moiety

In

luminescence.

quenches

conclusion,

varied
their

exhibit

and

The mixed metal

the luminescence

11,

13,

interesting

luminescence

This

and

their

photophysical

can be tuned

over

the

whole visible region (Table 2).

Table 2.

Luminescence

properties

of 2-cat. 3-cat, and their metal complexesa

(nmlb

max

(ns)e

@d

dap

396

2.2

0.29

2-cat

400

2.0

0.42

H(2-cat)+

555

11.0

0.022

Li(Z-cat)+

400

2.5

0.35

Cu(2-cat)+

730

175

0.0011

Ag(2-cat)+

Zn(2-cat)2+

463

2.0

0.082

3-cat

400

2.4

0.33

Cu(3-cat)+
Cu2(3-cat)2+

400;725
730

2.4;181
177

0.0007

Co(2-cat)2+
Ni(2-cat)2+

0.054;0.0011

CuCo(3-cat)3+
aCH,Cl,
bMaximum

solution, room temperature;

of the luminescence

CLifetime of the luminescent

dLuminescence
eNo luminescence

quantum

from refs. 103 and 104

band

excited state

yield

at room temperature;

at 77 K: hmax = 498 nm, E = 0.012 s.

10483

Supramolecularphotochemistry

6.2

Rotaxanes

and

catenanes

featuring

charge-transfer

interaction

Electron
highly

donor-acceptor

efficient

catenate

18

groups

involved

template-directed

performed

by

hydroquinol

bipyridinium

(paraquat,
macrocycle

provides

synthesis

Stoddart

in the electron

electron-rich

tetracatianic

interaction

and

of

and

PQ2+)

units.

17 and

19 is threaded by a hydroquinol
Si-derivatives

the tetracationic

macrocycle

19 is interlocked

two hydroxiquinol

(21).

PO-

Ol

0
0

cep,

OSIPI$

17

the

unit that
18

with the macrocycle

18

r 0-

are the

In the catenane

units.

17

The

electron-deficient

In the rotaxane

with bulky

Pr!#0

rotaxane

interaction

the

is then stopped

20 which contains

for the

coworkers.106-108

donor-acceptor

units

the basis

21

V. BALZWI

The

have

electrochemical

been

obtained

investigated.
on

(DMB)
in

electron

which

between

displaced

splitting

paraquat

units

paraquat

oxidation

of

paraquat

more

(i)

the

that

is

unit,

unit,

the

first

which

reduction

tetracationic

oxidation
some
Both

electronic
such

in 18,

is indeed
the

waves

waves

and their

an expected

electron-acceptor
more

difficult

units are not equivalent.

be

interacts

with

oxidized,

interacts

with

correlations

can

be observed

17, 18,

and

their

of

electrochemistry
monoelectron
the

negative

and

two

only

the

paraquat

of

paraquat

reduction
two

characterized

processes.

For

units

reduced

paraquat

potential

is

than

are

paraquat
between

the

simultaneous

reduction

of

units

Reduction
17

is

similar

of

the

to that

the

since

repulsion

both

in the

components

electrostatic

rotaxane

the

is

units

which
to

positive

unit is involved

of

with

hydroquinol

their

1,4_dimethoxybenzene

potentials

interaction

and

a more

units.

This

the results

to
The
one

inside
unit,

is

only at a much higher potential.

Similar

potential.

at

there

positive

the

17 and 18

18,

20 two distinct

than in 20.

makes

unit,

17,

units

the two hydroquinol

hydroquinol

hydroquinol

19,

the

and (ii) the two hydroquinol

alongside

oxidized

place

the

is much larger
because

oxidize,

17 takes

indicates

towards

behavior

of

reduction

of

to

of

24 and 25 compare

19. For the macrocycle

observed,

properties

because in 17 the hydroquinol

donation

interaction
are

to

as expected

macrocycle
are

and

Oxidation
compared

spectroscopic

lo8 Figs.

oxidation

components.
potential

and

by

two

25).

cyclophane

simultaneously

at

units.
more

macrocyclic

bis-paraquat

at

decreases

charged

The

consecutive

bis-paraquat

follows

bis-paraquat
of the

(Fig.

reduction

two

electrochemical

less
the

Second
negative
ring

cyclophane

of
19,

Supramolecular photochemistry

+2.0
I

Fig.24.

+ 1.0
I

Oxidation

of

10485

rotaxane

17,

catenane

18,

their

and

components.108
except

the

reduction

of

the

interaction

because
hydroquinol
does

not

the

spontaneously

alongside

interaction
unit.

unit

positional

units

creates

second

reduction,

paraquat

units

first

indicating

and

18

spectroscopy.

is

also
108

for

occurs
that

electron

obtained
The

model

with

species,

stoppers,

bead
18

the

two

otherwise

gradient

(Fig.

25).

charge-transfer

donor-acceptor

absorption

the

to the inside paraquat

of the paraquat

from

which

in donor-acceptor

at the same potential

the

the

In the catenane

between

an electrochemica1

potentials

units

involved

compared

difference

however,

evidence

paraquat

reduction.

is less

very weak after the first reduction

Clear

the

negative

triisopropylsilyloxy

after

paraquat

more

in a rotaxane

with the hydroquinol

Such

identical

bulky

at

of

unit. Interestingly,
have

unthreads
the

occurs

that

spectra

of

for both

interaction

is

units.
interaction

absorption

The

and
17

in 17
emission

and 18

are

V. BALZANI

-1.0
I

21

19

i;
I

17

\
\2

Fig.25

Reduction

of

17, catenane

rotaxane

18,

and

their

components.*u*
noticeably

different

components.
visible

In

region

transfer

from

the

sum

a broad,

both

17 and 18 that

transition

from

the

paraquat

bands

coincide

nm),

nature

of

molar

absorption
that

units

of 20

consistent

(A=478
interacting

of 17,

with

fluorescence
quenched

in both

Investigations
rotaxane

and

can

suggesting

that
a

the

present

be assigned

because

of

in 18

nm)
both

residue.
results

hydroquinol

units

is

the

is

these

identical
the

practically

hydroquinol-type

This

which

of

to

Furthermore

of 18
the

the

units

maxima

cases.

in

to a charge

The

two

luminescence

the

is

respective

hydroquinol

A=478

paraquat

of the

band

expected
in

(at

the

of

units

with

weak

residues.

as

coefficient

interact

spectra

z-electron-rich

the n:-electron-deficient

twice

the

particular

for

the

of

conclusion
show

almost

that

is
the

completely

17 and 18.
are

catenane

presently
structures.

extended
The

to

more

supramolecular

complex
system

10487

4 PF;

Pr3Si

xx
O&
0

-o-

o-o,0

+N*+

4+

=
=
=
=-

-=

+N

Fig.26.

in Fig.

shown

A molecular

26 consists

units

and

experiments

have

demonstrated

forth

between

species

at

temperature.

a bis(paraquat)
that

the two hydroquinol

rate

which

groups

interactions

between

due

to

the x-electron

the bead and the n-electron

thread. The free energy

donor

much

smaller

than

rate

hydroquinol

units

luminescence

of the hydroquinol

The

shuttle

construction

of

of

decay

shown

in Fig.

molecular

bead could be controlled

26

the

transfer
residues

stations
process

the

the

is 13.2 kcal

the shuttle
of

in

in

frequency

photoexcited

only 50% of the

is quenched.1 to

is a first

machines.to8.*09

by an external

varying

one of the two

paraquat

(z = 1 ns). As a consequence,
residues

back and

charge

barrier to the shuttling

the

NMR

of the bead along

hydroquinol

which means that at room temperature

Dynamic

by

favorable
acceptor

two

of the supramolecular

positions

the

containing

shuttles

are those in which the bead surrounds

hydroquinol

is

bead

controlled

The two most favorable

the thread

mol-I,

the

be

chain

bead.109

stations

can

N+

shuttle.l@J

of a polyether

hydroquinol

step

towards

If the position

the

of the

signal, such a shuttle might

V. BAIZANI

be used as a molecular

memory

to reach

one should first make a shuttle

such a result,

in a molecular

computer.

In order
where

the

bead prefers to stay in one of the two stations. This can be done by
using

two different

electron

reside on the better electron

(X) should be destabilized
In principle,

donors:

the

into

chemical

maintains

life on the earth,

electron

transfer

ordered

arrays
to

artificial

sites

electron
controlled

arrays

and

in Section
molecular

manner.

is

fuels)

that

energy

and

fossil

light

chemical

is absorbed

excitation

centers)

The reducing

where

reactions

species

to be used

by

energy
a

and oxidizing

is

charge
species

which lead to

aim of current chemical

2, supramolecular
components

for

research
building

is
up

transfer

species

can also be

via covalent

bonds (Fig.

to synthesize

of molecular

energy

sunlight

systems.

1). In this way it is possible

dimensional

plants,

(reaction

An important

by linking

firewood,

and the resulting

of supramolecular

As mentioned
obtained

In green

takes place.

photosynthetic

where

process

(food,

give rise to secondary

the final products.

components

is based on photoinduced

of pigments,

reaction

the design

energy

processes.

specific

or light signals could then be

molecular

natural

converted

or (more difficult)

abacus.

Covalently-linked

Photosynthesis,

preferentially

in order to displace the bead to station Y.

oxidation of X. Electric

7.

so obtained

will

donor, X. Then, the more stable station

used to play with this molecular

separation

bead

this can be done by electrochemical

photochemical

channeled

the

linear

components
processes

can

or bi- and tri-

where
take

photoinduced
place

in

Supramolecularphotochemistry

7.1

Photoinduced

component

In

the

model

last

investigations
electron
the

electron

few

years

many

explored

and energy

transfer

the
processes,

linked by rigid connectors.

A detailed

discussion

of electron

and energy

several books and reviews

electron
species

transfer

(Section

two-

theoretical

photoinduced

two

emphasis

on

components

of the theoretical

processes

can be found

in

processes

in

3).

and

made

of

with particular
between

supramolecular

in

and

mechanism

interaction

Photoinduced

transfer

experimental

electronic

aspects

of

energy

systems.

have

problem

and

10489

energy

of two

transfer

covalently-linked

molecular

a
01

0b

,electron

*A-L-B

back
electron
transfer

A-L-B

A-L-B

Fig.27. Schematic representation of photoinduced electron (a) and

energy (h) transfer processes
made of two components

components

can

photoinduced

electron

transfer

process,

be

(A and B) linked

schematized
transfer

and energy

in a supramolecular

as

is followed
transfer

in

Fig.

system

by a connector

27.

In

(L).

general,.

by a fast back electron

is followed

by the radiative

104!lO

V. BUAM

and radiationless

deactivation

From an experimental
cause

the quenching

(A).

Formation
by

spectroscopy

viewpoint,

the

experiments.

be demonstrated
experiments.

transient

recording

its

and A-L-*B

The presence

mentioned

experimental

species)

transfer

of the absorbing

species

B-

absorption

information

A+-L-B-,

and energy

A+-L-

species

can

spectrum

in

of the A-L-*B

by flash spectroscopy

Kinetic

state of the acceptor.

both electron

of the luminescence

of

demonstrated

of the excited

electron

systems

based

examples

as well as by luminescence

(i.e.,

the lifetime

of the *A-L-B,

can also be obtained

will be discussed

coworkers11

by the above

processes

molecular

transfer.

electron

donor

schematic

Verhoeven,

transfer

length

group

and

processes

and

Fig.

is possible.

27a),

A-B distances

the

methoxynaphthalene-spacer
of the connector

A-L-B
A-L

species
model.

an

L the rate constants

in systems

electron
spacers

systems

various

and rigid,

and

investigated

span

A and of 4 to 12
transfer step (Fig.
by comparing

that

of

a linear

decrease

of

of the A

solvents
with

acceptor

freedom

of -7-15

For

on the

unit (A in the

are saturated

27a) has been studied in various organic

and

of these systems are an

norbornylogous

The

Hush

that take place

C-C bonds. The kinetics of the electron

of

reviews

investigations

chromophoric

(L). The spacers

range of centre-to-centre

fluorescence

A few other

Paddon-Row.

are such that no orientational

B components

interposed

of

(B),

as connectors

the attachments

species.

out systematic

dimethoxynaphthalene

representation

dicyanovinyl

in supramolecular

see chapters 5 and 6 of ref. 1.

like those shown in Fig. 28. The components

electron

of photo-

in the next section. For detailed

l-l l4 have carried

photoinduced

transfer

on covalently-linked

Electron

7.1.1

can

techniques.

and energy

of these processes,

flash

species

In this section we will illustrate only a few examples

induced

be

the

suitable

arrangement

exponentially

with

Supramolecular photochemistry

10491

CN
CN

two-component

Fig.28. Dimethoxynaphthalene-dicyanovinyl
systems

increasing

length

1.2~10*~,

and

detailed
for

and

dipole

free

distance.

by

using

very

values

agreement

conductivity

signal

the

charge-separation
of
28)

systems
shows

that

two

of

by

the

the

the
energy,

the

of

with

the

been
state

therefore

electron

used

are

to

obtain

rate

rates

lie

much

slower

in

through

D) are

decay

of

in
the

27a)

the
the

the

of

for

the

reaction.

Marcus

than

bent

l2 The

constants

the

of

been

disappearance

Fig.

between

stereochemistry

transfer

the

the

have

(26-77
The

transfer,

Comparison

the

values.

to monitor

electron

reactions.
in

expected

and

(back

moments

on

compounds

conductivity.*

the dipole

energy

depend

microwave

for

that,
that

free

reorganizational
series

parameters

namely

same

fact

time-resolved

has

differing

separation.

states

charge-recombination
and

12-bond

3.3x10*,

charge-separated

charge-recombination

region12

example,

A+-L-B-

charge-separated

Such

On

obtained

substantial

and

energy,

sphere

for

is complicated

activation

of the

measured

constants

outer

being,

for 6-, lo-,

reaction,

and

moment

high

s-l

separation

the

solvent

connector,

of these

the

change

the

1.3~10~

charge

determine

both

of

analysis

14

with rigid bridges.tts*t

inverted

activationless
rate

constants

connectors

bridges

is

(Fig.
slower

lo492

V. BAUANI

with respect
transfer
with

to the stretched

ones. These results show that electron

takes place via a through-bond

theoretical

predictions

that

coupling

and are consistent

an all-trans

arrangement

of (T

bonds is the optimum one for through bond interactions.1*5*1 l6

In several
transfer,

cases,

Section

charge transfer

3,

observed.117g118

Fig.

6)

and

Such processes,

coefficient

the radiative
yield

and

acceptor

electronic

Energy

7.1.2
electron
features

radiationless

developed

be used

(exchange)

band

in

and

by quantum

to calculate

the

donor-

species

This

where

both

between

two-component

is

for some time that

transfer

even

more

processes
two

have

may

electronic

supramolecular

certain

apparent

in

be viewed

as

states.1

Recent

has

further

species

this concept.

Closs, Miller, and coworkers17*120-122 have synthesized

of A-L-B species where A is benzophenone,
are steroid-type

connectors.

benzophenone

Following

chromophore,

benzophenone

is populated

with formation

of its lowest

and L

pulsed laser excitation

of the

the
and

lowest

energy

triplet,

energy

transfer

which

is

processes

about

twice

fall-off
that

triplet

transfer

takes place,

is exponential,

obtained

for

systems. 7.123 Such a relationship

the basis of the fact that exchange

a double electron

transfer.

a series

B is naphthalene,

scheme of Fig. 27b. As usual for triplet-triplet

energy transfer occurs by an exchange mechanism.

analogous

been

because the molar

(obtained

energy

19

transitions

on

also

absorption

It has been recognized

common.1

supramolecular

work

and

in

can

electron

coupling.

transfer.

transfei

transfer

of the emission

data)

have

are important

of the charge

rate constant
lifetimes

emission

(optical

that have not been represented

Fig. 27a for the sake of simplicity,

absorption

absorption

to

state

of

naphthalene,

according

to the

processes,
this
The rate of the
with a coefficient

electron

transfer

in

can be explained

on

energy transfer can be viewed as

Supramolecularphotochemistry

Singlet-singlet
and

energy

transfer

co-workers124,125

previously

discussed

carbonyl

group

systems

the

replacing

bonds in the bridge.

of

twice

exponential

indicates

7.2.

systems

transfer

identical

(Fig.

dicyanovinyl

extent

28),

to

the value

on the number

for electron

of

again an exchange

the

rate

these

component
of C-C

fall-off

transfer

As far as the mechanism

dependence

for

In

of the exponential

obtained

those

except

fragment.

depending

The coefficient

Multicomponent

by Verhoeven

the dimethoxynaphthalene

the same connectors.126-128

the

A-L-B

the

to a different

about

has been studied

for electron

fluorescence

is quenched

again

on

lo493

is

across

is concerned,

constant

on

distance

mechanism. 24

systems

for

photoinduced

charge

separation.
In an A-L-B
components
too

(dyad),

short-lived

strategy

system,

i.e.

the photoinduced

to be

useful

the

number

pentads131,132

the

photosynthetic

For

reaction

importance

photosynthetic

transfer

purposes,

together

by

sequence

purposes.

charge separation

is to

Several

tetrads18.20,129-131

and

and their photochemical

and

charge

of events

will

mimic

their

the function

development

the design

is

of
of

of artificial

connectors.

Pel)

amine (electron
As

separation
(rate

briefly

constants

discuss

the

triad

which is made of a porphyrin

photosensitizers,

Rel) and an aromatic

rigid

we

et aLI

acceptor,

photoinduced

few

on the way towards

by Wasielewski,

(electron

is usually

components.

This species
centre

separation

active

systems.

illustration

developed

of two

conversion

have thus been synthesized

has been investigated.

paramount

energy

molecular
and

made

charge

and long-lived

of

triads15.16.18.20,129-131

behavior

for

to obtain an efficient

increase

in a system

illustrated

process
for

quinone

(electron

donor,

Rel) linked

in

29,

involves
butyronitrile

Fig.
the

the

following

solutions):

(1)

lo494

V. BALZANI

h3

Ret'

Pel

T2

-A

I
0
1 /.....""""/,
...
...j."'

eW
:

.....'
/ ..
fj....."
, 14
1

1
o

diagram,

energy

bE

I/'

&,,hJ

Fig.29. Block

//i

molecular

and

srructure,

one-electron

level diagram for a triad.133 The porphyrin

role of photosensitizer

(Pel);

the quinone

amine play the role of electron

plays the

and the aromatic

acceptor and electron

donor,

respectively.
light

absorption;

(2) electron
s-l);

the

quinone

(l.lxlO*~

the

oxidized

porphyrin

the

design

efficient

charge

separation

illustrated

must
reaction
charge

(1.4~1010

a multicomponent

prevail
3

and

over
must

recombination

excited

prevail

over

reaction

29),
state
the

6 must

from

all

of

to

electron

decay

4,

to

the amine

to

since
be

back

electron

be

as slow

In

reaction

electron

trzinsfer

transfer
as

an

several

satisfied.

transfer
the

out that

performing

simple

have

porphyrin

be pointed

capable

at

the

excited

It should

requirements

(Fig.

the

s-1).

not

the

transfer

system
is

kinetic

example

from

(3) electron

of

thermodynamic
the

transfer

possible,

5,

the
and

Supramolecular

the converted

energy

Fig. 29, the charge

and stores
constant

photochemistry

must be as large as possible.

separation

reaction

occurs

compared

with

photosyntetic

the

reaction

performance

bacteria

where

of

-0.6

eV

to play the role

multicomponent

supramolecular

of electron

systems.10~19

(bpy=2,2-bipyridine)
structures

configuration).

leads

electron
respect

The

center

produced

with

of
100%

are an electron
p-anisylamine

lie

on

(trans-type

on the Ru(trpy)22+
acceptor
).t35

( MV2+)

also

good

photosensitizers

building
where

the

in

M(bpy)s
up

of

components

close to each other (cisof

where

are

with the basic

to systems

species

components

based

transfer

the

geometry

to the photosensitizer

A triad

complexes

M(trpy),

on the contrary,

supramolecular
acceptor

Fig.30.

reaction

are

are relatively

(trpy=2,2:6,2-terpyridine).
to design

of the rate

6). This result can be

the

However,

arrangement,

linked to the photosensitizer

type

with 71% efficiency

and stored for -0.1 s.

Ru(I1) and Os(I1) polypyridine-type

candidates

In the triad of

1.39 eV for 2.5 us (which is the reciprocal

of the charge recombination

efficiency

10495

the

offers

complexes
the possibility

electron

opposite

donor

directions

configuration,

photosensitizer.
and an electron

and
with

Fig. 30). In

A and
donor

D
(di-

V. BALVWI

10496

addition,
do

M(trpy)2

not

lead

complexes

to

isomeric

substituted

M(bpy),

dyads

triads

and

bearing substituents
mixtures

contrary

systems.134
illustrated

Detailed

in

Fig.

at the 4-position

to

their

equivalent

investigations

30

have

on

been

the

recently

performed.l35$136

7.3

Polynuclear

metal

The possibility
transfer

useful
the

of governing

in supramolecular

of photochemical

of

light absorption

for

a specific

complexes

appear

to

energy

that

be particularly

of

devoted

to

exhibit

electronic

site (antenna

a variety

is presently

systems

and where the resulting

towards

of electronic

that can perform

much activity

multicomponent

channeled

harvesting

may open the way to the design

devices

Therefore

light

the direction

arrays

molecular

functions.137

synthesis

complexes

excitation

effect).

useful

extensive
can be

Transition

building

metal

blocks

for

systems of this type.

In the last few years
to obtain

polynuclear

synthetic

metal

strategy

complexes

has been developed

of desired

nuclearity

of both

the metal

(M) and the ligands

(L) in the

reaction
M+

nL

-->

M(L),

(29)

The place of M can be taken by mono- or oligonuclear

that contain
taken

by

chelating

and

Such a strategy is based on the use of complexes

chemical structure.
in the place

a synthetic

easily
mono-

replaceable
or

ligands,

oligonuclear

sites (complexes

complexes

and the place of L can be

complexes

that

contain

free

as ligands

as metals and complexes

strategy).

7.3.1

Trinuclear

Using
possible

metal

the tripod-type

complexes

of tripod-type

bipyridine

ligands

to obtain homo- and heteronuclear

shown in Fig. 32. In such complexes

shown

bipyridine

ligands.

in Fig.

31, it is

trimetallic

each metal-based

complexes

as

unit exhibits

Supramolecular photochemistry

Fig.31. Tripod-type

Fig.32. Trimetallic

tris-bipyridine

complexes

of

the

lo497

ligands.138

tripod-type

ligands

Fig. 31; M,., M,,, and Mc may be Ru and/or OS.

its

own

absorption

regardless

of

present

in

the
the

investigations,
electronic

decreases

number

energy
as

excited

and

and

transfer
expected
energy

show

of

in

takes

place

because

of

levels.

properties,

metal-based

units

structure.138
that

The

as the size of the spacer

mixed-metal

from

Ru-based

relative

efficiency

which

links

that

are

Luminescence

the

the

in

138

electrochemical

type

supramolecular

however,

components,
lowest

spectrum

shown

complexes
to

OS-based

position
of

energy

the three

arms

of

their

transfer
of the

10498

V. BALZANI

tripod
the

ligand

increases.

compounds

energy

with

transfer

transfer

Detailed
larger

investigations

spacers

there

does not take place

have shown that in

are conformers

and conformers

where

where

energy

is very fast.

7.3.2 Polynuclear
ligands.

The

synthetic

complexes

complexes

strategy

has

synthesis

of polynuclear

as metal

ions,

as 2,3-

and

2,3-

as metals
revealed

(bpy) and/or 2,2-biquinoline

Species

with

nuclearity

metals,

bridging

obtained.*39-14s
tridecanuclear
schematic

The
compounds

view

of

the

Ru(II)

(BL).

(biq) as terminal

between

ligands,

containing

ligands

and

2 and

structural

the

Os(I1)

(abbreviated
2,2-bipyridine

ligands
the

different

have

been

decanuclear

and

in Figs. 34143 and 35,145 A

formulas

of

compound is given in Fig. 36.143

@=@

OS2

L=Q-Q
by

biq

Q+-o
23 - dpp
Fig.33. Components

and/or

13, containing

of

are illustrated

and

for

ligands (L) (Fig. 33).

terminal

syntheses

as ligands

successful

2,5-bis(2-pyridyl)pyrazine

bridging

bridging

and complexes

particularly

complexes

and/or

2,5-dpp)

of the bis(2qyridyl)pyrazine

of the polynuclear

complexes.

decanuclear

10499

Supramolecular photochemistry

Fig.34

Synthesis

of a decanuclear

compound.143
L

BL

b-

BL

BL
BL

BL

BL

BL

1:3
LwBLB$BLBLyL

4
Bt

P-

e;

BL

BL

Fig.35.

These

polynuclear

properties
and

including:

visible

nuclear

region

of a tridecanuclear

Synthesis

complexes
(i)

very

(E = 133000

intense

compound.145

several

absorption

interesting

bands

in

the

uv

at 544 nm for the trideca-

Ru((~-2,3-dpp)Ru(bpy)(~-2,3-dpp)Ru[(~-2,3-dpp)Ru-

0vY)2121 3UF6)26 compound);

(ii) luminescence

at 77 K and

at room

electrochemical
each

exhibit

M-1 cm-t

ligand

concerned,

in

fluid

behaviour
can

the

solution
(each

be

reduced).

interest

of these

metal
As

both

temperature;
center
far

compounds

as
lies

can

in rigid
(iii)
be

energy
on the

matrix

a very

rich

oxidized

and

collection

is

fact

that

the

10500

V. BALZANI

Fig.36.
site

containing

controlled.
energy
the

Schematic
the

Each

levels

the

be

predetermined

in

the

in fact,

which

in

the

choice

the

be synthetically

of

same

by its

of the metal

units),

and

the
energy

blocks

transfer

bridging

and

array

building

ligand

own
of

the position

supramolecular

Exoergonic

share

can

is characterized

by the nature

units

a suitable

compound.143

state

by the surrounding

reaction.

units

can
used

between
takes

place

efficiency.

In the

shown

by

excited

mainly

metal-based

synthetic

metal-based

transfer

block,

slightly

various

100%

energy

building

and

of

been

lowest

(determined

ligands,

with

view of a decanuclear

case

possible
can
in Fig.

of the
to

be

design

tetranuclear
species

predetermined

37.140C In the case

compounds,
where
according

for example,

the

direction
to

the

of the decanuclear

of
four

it has
energy
patterns

compounds,

six

10501

Supramolecular photochemistry

A
v
A
Lc,4c~Md
y(
AA
La

(
r/>

Lav

Ma

(i)

BLa

BL$Lb

Lc

Lti

Made-to-order

Fig.37.

transfer
(i)

(i i i)

control

of electronic : energy

of the direction

in tetranuclear

(iv)

compounds:

M=Ru2+; BL=2,3-dpp; L=bpy.

(ii) Ma=Mb=Mc=Ru2+; Md=Os2+; BL=2,3-dpp; L=bpy.

(iii) M=Ru2+; BLa=2,5-dpp: BLb=BLc=2,3-dpp;

L=bpy.

(iv) M=Ru2+; BL=2,3-dpp; La=La,=biq; Lb=Lb=Lc=Lc,=bpys

different
energy

complexes
migration

Because
redox

groups,
polynuclear
point

of

patterns
the

been

shown

presence
and

centres,

complexes

of view

investigations

have

of

intervalence

multielectron

transfer

an

the

transfer

and

fields

ordered

array

catalysis.

exhibit

the

of chromophoric

luminescent
interest
its
of

centres,
not

only

applications,
photo-,

electrochemistry,
transfer,

which

38.143

potentially

electrochemiluminescence,
chemistry,

in Fig.

are of outstanding

of energy
in

synthesized

but

these

from

the

also

for

chemi-,

and

spectroelectro-

photosensitization,

and

V. BAUANI

10502

4
Fig.38.

Schematic
in

the

representation
decanuclear

exoergonic

Ruz+

positions,

circles

components,

the

energy

compounds.

energy

indicate

of

transfer

and

steps.

Os2+,

and

arrows

Empty

respectively.

squares

respectively.

The

transfer

The

indicate

indicate

and
In

full

the

M(bpy),

bridging

processes
the
circles

peripheral
and M(biq),

ligands

are

2,3-dpp

in all cases.l43b

8.

A photon
information.
used

for

obtained

is at the same
The

interaction

energy

or

depend

on

simplest

form

Conclusion

time

of light

information
the

a quantum
with

matter

purposes.

degree

of

of energy

and a bit of

can

The

results

organization

of

therefore

be

that

be

the

can

receiving

matter.
The
atoms

in a molecule.

cause

simple

acts,

of organization
The

such

interaction
as

is that

of a small

of photons

a change

in

the

with

number

molecules

molecular

of
can

structure

10503

Supramolecular photochemistry

which

(isomerization),
energy

and information

converted

in

(and

norbornadiene
laser

spiropyran

can

number

stored

write

level

forces

of
or

bonds.

by

types

luminescence

spectrum,

it

is

possible

integrated

of elaborating
complex

perform
light

the

into

molecular

can be

isomer,149

and

information

on

by

hydrogen

components

carry

the

prefabricated
light-related

state

state redox properties,

and

organized
molecular

energy,151

lifetime,
etc. That is,

and

functionally

devices)l37a

information

(light

bonds,

by covalent

desired

excited

(photochemical

species.

intermolecular

to put together

structurally

energy

of a discrete

input

photons

to

harvesting,1401 143 conversion

of

collection

of

of

capable

information

in a

shift register,152 etc.).

and

of a supramolecular
sometimes

structure

of the various
current

a positive

excited

electrical

geometrical

refine

both

transforming

supramolecular

interactions,

spectrum,

functions

Interrogation
important,

of

attained

it is possible

to design

systems2

be

molecular

that

absorption

bits

to yield

(coulombic

components

properties:

by

is the assembly

can

together

By these routes

molecular

solar energy

energy

erase)

for

molecules.150

components

linking

principle,

quadricyclene

also

organization

various

chemical

energy

(and

in

For example,

of organization

of molecular

Supramolecular

exploited,

as)

higher

photochromic

A higher

be

purposes.

in its

beams

etc.)

can

pieces

and on the degree

components.
theories

feedback

unique,

species

by photon

of

can yield

information

of reciprocal

on

perturbation

This, in turn, may help to extend

of chemical

reactivity

and spectroscopy

on the design of more valuable

its

and
with

supramolecular

systems.
Research

in the

area

of supramolecular

photochemistry

been made possible by the high degree of knowledge

field
We

of molecular
are,

however,

photochemistry
at

very

and
early

reached in the

supramolecular
stage

of

has

chemistry.

development

of

V. Bm

supramolecular
structures

photochemistry.
that

investigations

have

photochemical

and

true for host-guest

out that high quality

research

investigations

group.

Therefore,

photochemists

supramolecular

chemical

fact,

the

supramolecular

object

of

photochemical

with those

already

systems).

It should

is

and high quality

can hardly be carried

out by the same

required

activity

is sufficiently

the photochemical

supramolecular

for

of synthetic
the

photochemical

consolidated,

behavior

it will

be possible

to

of macroscopic

assemblies

of

and less empirical

Acknowledgment.

the light-induced

occur in nature and will also facilitate

molecular

della Pubblica

of

in the field of supramolecular

species in a way less occasional

which

for

chemists

development

than that used so far. This will help in elucidating

Gubellini

also be

photochemistry.

photochemistry

processes

available

syntheses

strict collaboration

As soon as the research

explore

the

are very few compared

(this is particularly
pointed

been

In

devices

with the macroscopic

interfacing

world.

I would like to thank Mr. V. Cacciari and Mr. G.

the drawings.
Istruzione

II is gratefully

Financial

and Progetto

support
Finalizzato

from

the Minister0

CNR Chimica Fine

acknowledged.

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