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AdamM.Azman
19March2008
Platonic Solids(theblocks)
Solids (the blocks)
Exactly5
l
Plato
Platotheorizedtheclassicalelementswere
theorized the classical elements were
constructedfromtheplatonicsolids
Octahedrane andicosahedrane areimpossible
hydrocarbons
Tetrahedrane onlypossibleifsubstituted
and dodecahedrane sucessfully
Cubane anddodecahedrane
synthesized
Blocks Cubane
Fi
Firstsynthesizedin1964byEaton
h i d i 1964 b E
Highestdensityofallhydrocarbons(1.29gmL
g
y
y
(
g 1)
O
HO
O
Eaton,P.E.;Cole,T.W.J.Am.Chem.Soc. 1964,86,962964.
Eaton,P.E.;Cole,T.W.J.Am.Chem.Soc. 1964,86,31573158.
O
Br
Blocks Dodecahedrane
Syntheticeffortsbeganin1964(Woodward)
Synthetic efforts began in 1964 (Woodward)
Firsttotalsynthesisin1982byPaquette
1)Paquette,L.A.;Balogh,D.W.J.Am.Chem.Soc.,1982,104,774783.2)Paquette,L.A.;Ternansky,R.J.;Balogh,D.W.J.
Am.Chem.Soc.,1982,104,45024503.3)Ternansky,R.J.;Balogh,D.W.;Paquette,L.A.J.Am.Chem.Soc.,1982,104,4503
4504.4)Paquette,L.A.;Ternansky,R.J.;Balogh,D.W.;Kentgen,G.J.Am.Chem.Soc.,1983,105,54465450.
Blocks Dodecahedrane
11
10
O
I
11
10
Zn-Cu
MeOH
9
80%
4 steps
CO2Me
CO2Me
R
4
O
R
H2O2
10
CO2Me
CO2Me
11
7
100%
2) H+
77%
R
R
P2O5
O
1) H2, Pd-C
R
MeSO3H
83%
SPh2
1)
O R
2) NaBH4
O
O
HCl
O
12 of 20 stereocenters
Ester topology to direct all further reagents
MeOH
OMe
Cl
O
Cl
1) Li, NH3
2) PhOCH2Cl
48%, 2 steps
PhOCH2
OMe
OMe
1)Paquette,L.A.;Balogh,D.W.J.Am.Chem.Soc.,1982,104,774783.2)Paquette,L.A.;Ternansky,R.J.;Balogh,D.W.J.
Am.Chem.Soc.,1982,104,45024503.3)Ternansky,R.J.;Balogh,D.W.;Paquette,L.A.J.Am.Chem.Soc.,1982,104,4503
4504.4)Paquette,L.A.;Ternansky,R.J.;Balogh,D.W.;Kentgen,G.J.Am.Chem.Soc.,1983,105,54465450.
Blocks Dodecahedrane
1)Paquette,L.A.;Balogh,D.W.J.Am.Chem.Soc.,1982,104,774783.2)Paquette,L.A.;Ternansky,R.J.;Balogh,D.W.J.
Am.Chem.Soc.,1982,104,45024503.3)Ternansky,R.J.;Balogh,D.W.;Paquette,L.A.J.Am.Chem.Soc.,1982,104,4503
4504.4)Paquette,L.A.;Ternansky,R.J.;Balogh,D.W.;Kentgen,G.J.Am.Chem.Soc.,1983,105,54465450.
Dolls NanoPutians
NamedafterLilliputiansinJonathanSwifts
GulliversTravels
ll
l
2nmtallanthropomorphicmolecules
p
p
0.006ng =1.105x1014 mol=6.6x109 molecules
=currentworldpopulation
t
ld
l ti
O
NanoKid
Chanteau,S.H.;Ruths,T.;Tour,J.M.J.Chem.Ed.,2003,80,395400.
Chanteau,S.H.;Tour,J.M.J.Org.Chem.,2003,68,87508766.
Dolls NanoPutians
Chanteau,S.H.;Ruths,T.;Tour,J.M.J.Chem.Ed.,2003,80,395400.
Chanteau,S.H.;Tour,J.M.J.Org.Chem.,2003,68,87508766.
Dolls NanoPutians
Chanteau,S.H.;Ruths,T.;Tour,J.M.J.Chem.Ed.,2003,80,395400.
Chanteau,S.H.;Tour,J.M.J.Org.Chem.,2003,68,87508766.
10
Dolls NanoPutians
H
O
O
PdCl2(PPh3)2, CuI
NEt3, THF
85%
I
A
B
NanoKid
Chanteau,S.H.;Ruths,T.;Tour,J.M.J.Chem.Ed.,2003,80,395400.
Chanteau,S.H.;Tour,J.M.J.Org.Chem.,2003,68,87508766.
11
Dolls NanoPutians
O
excess diol
wave, 1-16 min
9-94%
NanoMonarch
87%
NanoPilgrim
25%
NanoAthlete
91%
NanoTexan
24%
NanoGreenBeret
85%
NanoScholar
90%
NanoJester
94%
NanoBaker
84%
Chanteau,S.H.;Ruths,T.;Tour,J.M.J.Chem.Ed.,2003,80,395400.
Chanteau,S.H.;Tour,J.M.J.Org.Chem.,2003,68,87508766.
NanoChef
9%
12
Dolls NanoPutians
O
Au surface
HO
O
O
O
O
O
O
O
O
O
O
Chanteau,S.H.;Ruths,T.;Tour,J.M.J.Chem.Ed.,2003,80,395400.
Chanteau,S.H.;Tour,J.M.J.Org.Chem.,2003,68,87508766.
OH
13
Dolls NanoPutians
14
Racecar Nanocar
Actuallyshowntomovebyrolling notsticksliporsliding
Approximately3x4nm
Shirai,Y.;Osgood,A.J.;Zhao,Y.;Kelly,K.F.;Tour,J.M.Nano.Lett.,2005,5,23302334.
15
Elevator
C
Ca.2.5nmheightx3.5nmdiameter
25
h i h 35
di
Distancebetweenfloors=0.7nm
Movementfromuppertolowerfloor
cangenerate200pN
t 200 N
Designedbasedona[2]rotaxane
Badji,J.D.;Balzani,V.;Credi,A.;Silvi,S.;Stoddart,J.F.Science,2004,303,18451849.
Badji,J.D.;Ronconi,C.M.;Stoddart,J.F.;Balzani,V.;Silvi,S.;Credi,A.J.Am.Chem.Soc.,2006,128,14891499.
16
Elevator
Stimulus B
Badji,J.D.;Balzani,V.;Credi,A.;Silvi,S.;Stoddart,J.F.Science,2004,303,18451849.
Badji,J.D.;Ronconi,C.M.;Stoddart,J.F.;Balzani,V.;Silvi,S.;Credi,A.J.Am.Chem.Soc.,2006,128,14891499.
17
Elevator
Badji,J.D.;Balzani,V.;Credi,A.;Silvi,S.;Stoddart,J.F.Science,2004,303,18451849.
Badji,J.D.;Ronconi,C.M.;Stoddart,J.F.;Balzani,V.;Silvi,S.;Credi,A.J.Am.Chem.Soc.,2006,128,14891499.
18
Elevator
Badji,J.D.;Balzani,V.;Credi,A.;Silvi,S.;Stoddart,J.F.Science,2004,303,18451849.
Badji,J.D.;Ronconi,C.M.;Stoddart,J.F.;Balzani,V.;Silvi,S.;Credi,A.J.Am.Chem.Soc.,2006,128,14891499.
Elevator
Othermolecularmachinesinclude
Motors
Switches
Shuttles
Turnstiles
Gears
Bearings
Gyroscopes
Futureisinincorporatingseveralmolecular
p
g
machinesintoafunctionalmacromolecular
machines
19