Вы находитесь на странице: 1из 35

Subscriber access provided by Washington University | Libraries

Article

Theoretical Insights into the Phosphorescence Quantum Yields of


Cyclometalated (C^C*) Platinum(II) NHC Complexes: #-Conjugation
Controls the Radiative and Non-Radiative Decay Processes
Yafei Luo, Yanyan Xu, Wenting Zhang, Wenqian Li, Ming Li, Rongxing He, and Wei Shen
J. Phys. Chem. C, Just Accepted Manuscript DOI: 10.1021/acs.jpcc.5b12214 Publication Date (Web): 25 Jan 2016
Downloaded from http://pubs.acs.org on January 26, 2016

Just Accepted
Just Accepted manuscripts have been peer-reviewed and accepted for publication. They are posted
online prior to technical editing, formatting for publication and author proofing. The American Chemical
Society provides Just Accepted as a free service to the research community to expedite the
dissemination of scientific material as soon as possible after acceptance. Just Accepted manuscripts
appear in full in PDF format accompanied by an HTML abstract. Just Accepted manuscripts have been
fully peer reviewed, but should not be considered the official version of record. They are accessible to all
readers and citable by the Digital Object Identifier (DOI). Just Accepted is an optional service offered
to authors. Therefore, the Just Accepted Web site may not include all articles that will be published
in the journal. After a manuscript is technically edited and formatted, it will be removed from the Just
Accepted Web site and published as an ASAP article. Note that technical editing may introduce minor
changes to the manuscript text and/or graphics which could affect content, and all legal disclaimers
and ethical guidelines that apply to the journal pertain. ACS cannot be held responsible for errors
or consequences arising from the use of information contained in these Just Accepted manuscripts.

The Journal of Physical Chemistry C is published by the American Chemical Society.


1155 Sixteenth Street N.W., Washington, DC 20036
Published by American Chemical Society. Copyright American Chemical Society.
However, no copyright claim is made to original U.S. Government works, or works
produced by employees of any Commonwealth realm Crown government in the course
of their duties.

Page 1 of 34

1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60

The Journal of Physical Chemistry

Theoretical Insights into the Phosphorescence Quantum Yields


of Cyclometalated (C^C*) Platinum(II) NHC Complexes:
-Conjugation Controls the Radiative and Non-Radiative Decay
Processes
Yafei Luo a, Yanyan Xu a, Wenting Zhang a, Wenqian Li a, Ming Li a, Rongxing He a,
Wei Shen a
a

College of Chemistry and Chemical Engineering, Southwest University, Chongqing

400715, China
E-mail: shenw@swu.edu.cn

To whom correspondence should be addressed. E-mail: shenw@swu.edu.cn

1
ACS Paragon Plus Environment

The Journal of Physical Chemistry

1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60

Page 2 of 34

Abstract
In this article, the radiative and non-radiative decay processes of four
cyclometalated (C^C*) platinum(II) N-heterocyclic carbene (NHC) complexes were
unveiled via density functional theory (DFT) and time-dependent density functional
theory (TD-DFT). In order to explore the influence of -conjugation on quantum
yields of (NHC)Pt(acac) (NHC=N-heterocyclic carbene, acac=acetylacetonate)
complexes, the factors that determine the radiative process, including singlet-triplet
splitting energies, transition dipole moments and spin-orbit coupling (SOC) matrix
elements between the lowest triplet states and singlet excited states were calculated.
In addition, the SOC matrix elements between the lowest triplet state and the ground
state as well as Huang-Rhys factors were also computed to descript the
temperature-independent non-radiative decay processes. And the triplet potential
energy

surfaces

were

investigated

to

elucidate

the

temperature-dependent

non-radiative decay processes. The results indicate that complex Pt-1 has higher
radiative decay rate than complexes Pt-2-4 due to the larger SOC matrix elements
between the lowest triplet states and singlet excited states. However, complexes
Pt-2-4 have smaller Huang-Rhys factors, smaller SOC matrix elements between the
lowest triplet and the ground states and higher active energy barriers than complex
Pt-1, indicating that complexes Pt-2-4 have smaller non-radiative decay rate
constants. According to these results, one may discern why complex Pt-2 has higher
phosphorescence quantum efficiency than complex Pt-1, meanwhile, it can be
inferred that the non-radiative decay process plays an important role in the whole
photo-deactivation process. In addition, on the basis of complex Pt-2, Pt-5 was
designed to investigate the influence of substitution group on the photo-deactivation
process of rigid (NHC)Pt(acac) complex.
2
ACS Paragon Plus Environment

Page 3 of 34

1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60

The Journal of Physical Chemistry

1. Introduction
In recent years, as high-efficiency phosphorescent emitters, NHC-based transition
metal complexes have aroused extensive attention in the field of organic
light-emitting diodes (OLEDs).1-4 Generally, in comparison with other coordinated
ligands, NHC ligands exhibit distinctive advantages: they possess exceptionally
strong -bonding and easily tunable steric and electronic properties. As well known,
the strong ligand field of the carbene can raise the energy of metal-centered dd
excited states, thus leading to the increase of the energy gap with the emissive excited
states, which is favorable to the improvement of phosphorescence quantum yield.
Moreover, owing to the good stability of metalcarbene bonds, these materials are
believed to have long operational lifetime when applied in organic electronic devices.
Over the past decades, phosphorescent Ir(III) and Pt(II) complexes have already been
widely doped into OLEDs as emitters because of the origination of their
electroluminescence from both singlet and triplet excited states, and thus the
achievement of utilization of nearly 100% electro-generated excitons can be possible.
5-8

Additionally, for both Ir(III) and Pt(II) complexes, a wide emission colour

tunability and luminescence quantum yield improving can be achieved via wisely
designing reasonable ligand, which has been proven in experimental and theoretical
studies.9-14 Therefore, it is a sagacious strategy to adopt NHC as cyclometalated
ligand to coordinate with Pt for obtaining the promising phosphorescent emitters with
high emission quantum yield.
To improve the phosphorescence quantum efficiency, the molecular rigidity of
transition metal complexes is an important parameter that should be attached
importance to, since it has great influence on the value of non-radiative decay rate
constant.15,16 Generally speaking, more rigid the molecule, smaller the degree of
3
ACS Paragon Plus Environment

The Journal of Physical Chemistry

1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60

structural deformation between the emissive excited state and the ground state, which
is unfavorable to the non-radiative decay process. Therefore, good structural rigidity
is desirable in designing high-efficiency molecules.

17-19

Recently, Thomas Strassner

and co-workers have synthesized a series of bidentate (NHC)Pt(acac) complexes to


explore the influence of enlarging the system on phosphorescence quantum
efficiency.20 According to their studies, enlarging the phenyl ring at the backbone of
the ligand can result in the increase in the phosphorescence quantum yield owing to
the sharp decrease in the non-radiative decay rate constants. Therein, the
phosphorescence quantum efficiency of Pt-1 is 0.40, and that of Pt-2 is 0.58 (Figure
1). By their analysis, the main cause of this result is that complex Pt-2 has stronger
rigidity than complex Pt-1. In order to further explore the influence of enlarging the
phenyl ring at the backbone of the NHC ligand on non-radiative decay rate constant,
complexes Pt-3 and Pt-4 are designed with two phenyl rings at NHC and phenyl ring
moieties, respectively, which are shown in Figure 1.
So far, although there have been abundant researches focusing on the theoretical
investigation of phosphorescent transition metal complexes, the computation and
interpretation of their emissive properties are still difficult, especially the
investigation of non-radiative decay pathways. Actually, nowadays more and more
studies demonstrate that only the simplified energy gap law is insufficient for
analyzing the non-radiative decay rate, it is desirable to make a thorough and in-depth
understanding to the complicated radiationless pathways. In this report, we make
detailed analyzes on non-radiative decay of the studied complexes. Density functional
theory (DFT) calculation is performed to obtain Huang-Rhys factors (Si) to elucidate
the relationship between molecular rigidity and non-radiative decay rate constants.
The thermally activated non-radiative photo-deactivation processes, i.e. 3ES (emission
4
ACS Paragon Plus Environment

Page 4 of 34

Page 5 of 34

1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60

The Journal of Physical Chemistry

state) TS(3ES/3MC) 3MC (metal-centered excited state) minimum energy


crossing point (MECP) conversion, are illustrated by DFT. In addition, the TD-DFT
calculation including SOC is also applied. We hope this theoretical study on
(NHC)Pt(acac) complexes would provide valuable guides for understanding and
designing high-efficiency phosphorescent transition metal complexes.

Figure 1. The chemical structures of the investigated platinum(II) complexes.


2. Theoretical background
2.1. Radiative decay rate constant
In a non- or scalar-relativistic scene, the triplet excited states get three-fold
degenerated. However, the effect of SOC can split the triplet excited state into three
sublevels which show difference in energy without the presence of external magnetic
field. Therefore, the energy difference between the sublevels is called zero-point
splitting energy, i.e., ZFS. And the radiative decay rate from each sublevel can be
calculated according to the following equations:
ir =

4 3
1
= r ( S0 , Teim ) = 0 ES T i 3 M ij
0
em
i
3t0
j{ x , y , z}

5
ACS Paragon Plus Environment

(1)

The Journal of Physical Chemistry

1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60

Page 6 of 34

where the radiative lifetime from each sublevel i (i=1, 2, 3) of triplet excited states
to the ground state is denoted as i and the fine structure constant is defined as 0
Moreover, t0 = ( 4 0 ) h3 / me e 4 , ES
2

i
0 Tem

is the transition energy between the

triplet excited states and the ground state, M ij is on behalf of the spin-orbit coupled
TemS0 transition dipole moment which can be showed as follow:

M ij =

S 0 | j |S n S n |H SO |Temi

n=0

E ( S n ) E (Tem )

S 0 |H SO |Tm Tm | j |Temi
E (Tm ) E ( S 0 )

m =1

(2)

Based on the linear response theory, the transition dipole moment from the ith
sublevel of triplet excited states and ground state can be evaluated and the Cartesian
components j { x, y, z} are used to represent spin eigenfunctions. The operators j ,

H SO represent the electric dipole and spin-orbit Hamiltonian, respectively.


According to a thermal population distribution determined by Boltzann statistics of
the three sublevels, the total radiative decay rate constant can be computed by the
following equation:

r =

1r + 2r exp ( ZFS1,2 / BT ) + 3r exp ( ZFS1,3 / BT )


1 + exp ( ZFS1,2 / BT ) + exp ( ZFS1,3 / BT )

(3)

In general, for transition metal complexes, the values of ZFS1,2 and ZFS1,3 are
typically < 200 cm-1.21,22 Thus, at the ambient temperature, the equation 3 can be
reduced to

r =

1 3 r
i
3 i =1

(4)

2.2. Non-radiative decay rate constant


According to the energy-gap law,

23

the non-radiative decay rate constant from Tm

state to S0 state can be calculated as follow.


6
ACS Paragon Plus Environment

Page 7 of 34

1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60

The Journal of Physical Chemistry

nr (Tm S 0 ) exp E (Tm ) E ( S 0 )

(5)

On the basis of equation (5), the non-radiative decay rate constant is closely related
with two main factors. One is the parameter representing the geometrical distortion
of the emissive triplet excited state from the ground state. The other is the energy
difference between the two corresponding states. In general, severe geometric
deformation

usually results in the increase of the electron-vibrational coupling

constant (Huang-Rhys factor) of the excited T1 and the ground state, thus strongly
facilitating the non-radiative decay. In the limit of the all normal modes are the
harmonic oscillators, the Huang-Rhys factors can be estimated as:

1
S j = j K j2
2

(6)

with Sj, Kj being the Hung-Rhys factor and the shift vector, respectively.

3. Computational details
In the article, the geometries of ground states and triplet excited states were
calculated via using restricted and unrestricted DFT (RDFT and UDFT) methods
without consideration of symmetry constrains. In an effort to achieve good agreement
with experiment,

four representative functionals, including B3LYP,24 PBE0,25

M062X,26 CAM-B3LYP,27 were tested and the corresponding computed geometries


parameters were listed in Table S1 and Table S2 with available experimental values.
By comparing the theoretical values with experimental ones, it can be concluded that
PBE0 is the most suitable functional. Therefore, PBE0 was employed in the
optimization of the ground states and the lowest triplet excited states for all studied
complexes. In addition, with the purpose of exploring the temperature-dependent
non-radiative decay processes, the states involved in the potential energy surface
curves

including mental centered d-d excited states (MC), transition states (TS)
7
ACS Paragon Plus Environment

The Journal of Physical Chemistry

1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60

Page 8 of 34

between T1 and 3MC states and the minimal energy crossing points (MECP), were
constructed by PBE0 method. Therein, the electron configurations of 3MC d-d states
were optimized following the methodology proposed by Perssons work.28,29 The
MECPs were computed via sobMECP, which is a modified version of Harveys
MECP program30,31 by Tian Lu. The sobMECP is a wrapper of Harvey's MECP
program to facilitate the use of the MECP program.32 The frequency calculations were
also carried out on the optimized geometries to verify the reliability of these states.
Besides, intrinsic reaction coordinates (IRC) were also computed to illustrate
reliability of TS. And stability calculations were performed on all optimized
geometries to ensure all wave-functions were stable. The Huang-Rhys factors for
normal modes were obtained by performing Franck-Condon calculation via freq=fc,
prtmat=12.
All the calculations mentioned above were realized by using Gaussian 09 program
package.33 The 6-31G(d) basis set34 was employed for light atoms (C, H, O, N) and
the transition metal atom Pt was described by LANL2DZ basis set.35
On the basis of T1 optimized geometries, the radiative decay rate constants and
zero-point splitting (ZFS) parameters were calculated via performing TD-DFT/PBE0
including SOC calculations with the zero-order regular approximation (ZORA)
36,37

Hamiltonian which were implemented in the ADF2014.04 program package.

38-40

The all electron TZP and DZP basis sets were used for Pt and non-metal atoms,
respectively.

4. Results and discussion


4.1. Ground state and the lowest triplet excited state structures
According to the results discussed in computational details, the geometry structures
of Pt-1 and Pt-2 can be reproduced reliably via PBE0 functional, and thus, the
8
ACS Paragon Plus Environment

Page 9 of 34

1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60

The Journal of Physical Chemistry

geometry structures of triplet and ground states of Pt-1-4 are optimized by PBE0
functional. The optimized ground states structures of the investigated Pt-1 and Pt-2
complexes are plotted in Figure 2. The main geometric parameters are listed in Table
1.

Figure 2. The optimized structures of the investigated Pt-1 and Pt-2 complexes.
By analysis of the main geometric parameters of S0 state of Pt-1-4, the bond
lengths of Pt1-L (L refers to the coordination atoms) change slightly (within 0.009

angstrom). Similarly, the bond angles of O1-Pt1-O2 and C1-Pt-C3 change within 0.6
and 0.4 degree, respectively. In addition, the dihedral angles C2-N1-C1-Pt1 and
N1-C1-Pt1-O1 are almost identical for Pt-1-4. These results indicate that the different
degree of extension and position of - conjugation cause little effects on the geometry
structures for all the studied platinum(II) complexes at S0 states.
As T1 excited state plays a significant role in photo-deactivation process, it
deserves to be attended. The geometric structure of T1 excited state not only
influences the values of radiative and temperature-independent non-radiative rate
constants, but also affects the temperature-dependent non-radiative rate constant. In
Table 1, the deviations of bond lengths and bond angles are no more than 0.019

angstrom and 1.1 degree during the transition of S0 to T1 excited states. Besides, the
deviations of dihedral angles are no more than 1.9 degree. In comparison with the
9
ACS Paragon Plus Environment

The Journal of Physical Chemistry

1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60

Page 10 of 34

optimized geometric structures of S0 and T1, it can be predicted that complex Pt-1
may have larger structural distortion than complexes Pt-2-4. As the structural
distortion is closely related with the temperature-independent non-radiative rate
constant, it will be discussed thereinafter in detail.

Table 1. Selected bond lengths [], bond angles and dihedral angles [deg] at S0 and T1
optimized geometries for Pt-1-4.
Pt-1
S0

T1

Pt1-C1

1.938

Pt1-C3

Pt-2

Pt-3

Pt-4

S0

T1

S0

T1

S0

T1

1.948

1.936

1.944

1.935

1.941

1.944

1.950

1.982

1.986

1.980

1.971

1.982

1.977

1.984

1.980

Pt1-O1

2.137

2.118

2.138

2.130

2.139

2.134

2.133

2.127

Pt1-O2

2.070

2.058

2.072

2.072

2.071

2.075

2.072

2.071

O1-Pt1-O2

88.4

87.3

88.2

88.4

88.2

88.4

88.9

89.0

C1-Pt-C3

80.0

79.9

80.2

79.7

80.1

79.8

80.4

79.9

C2-N1-C1-Pt1

0.0

-0.5

0.1

0.1

0.0

0.0

0.0

0.0

N1-C1-Pt1-O1

-180.0

-178.1

-180.0

-179.8

-180.0

-180.0

-180.0

-179.8

Pt-1
Pt-2
Pt-3
Pt-4
Figure 3. Spin densities computed on the triplet ground state for all investigate
complexes (isovalue = 0.002).
Apart from the main geometric parameters, the spin densities computed on the
triplet ground state for all the investigated complexes are depicted in Figure 3. As
shown in Figure 3, the distribution of spin densities largely depends on the conjugation. The spin density of Pt-1 is mainly distributed on acac ligand and metal
atom, while for Pt-2-4, the spin densities mainly lie in cyclometalated (C^C*) ligand
where has two phenyl cycles moiety. On the basis of spin densities distribution, it can
be inferred that Pt-1 may possess more 3MLCT character than other complexes.
10
ACS Paragon Plus Environment

Page 11 of 34

1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60

The Journal of Physical Chemistry

Without doubt, this character can facilitate SOC between T1 and Sn excited state for

Pt-1, thus, leading to effective radiative decay process.


4.2. Compare the optimized geometric structures

Pt-1

Pt-2

Pt-3

Pt-4
S0

T1

Figure 4. The optimized structures of both S0 and T1 for all the studied complexes.
On the basis of the energy-gap law discussed in theoretical background, the
molecular distortion between S0 and T1 excited state plays a vital role in
temperature-independent non-radiative decay process. In order to illustrate the
molecular deformations from S0 to T1 excited states, the optimized structures of both
S0 and T1 of all studied platinum(II) complexes are plotted in Figure 4. As shown in
Figure 4, when S0 jumps to T1 excited state, complex Pt-1 has distinct molecular
deformation, changing from planar to distorted coordination geometry. However, the
complexes Pt-2-4 maintain planar geometric structures both at S0 and T1 excited
states, which indicates that Pt-1 may have lager temperature-independent
non-radiative decay rate constant than Pt-2-4 due to the distinct molecular
deformation.

Actually,

this

is

only

one

factor

which

determines

the

temperature-independent non-radiative decay rate constant, the other factors will be


11
ACS Paragon Plus Environment

The Journal of Physical Chemistry

1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60

Page 12 of 34

further explored (via infra).


4.3. Phosphorescent properties

Table 3. The calculated lowest-lying triplet energy values for all the studied
complexes.a
E0-0 b
429
Pt-1
488
Pt-2
537
Pt-3
729
Pt-4
a
Energy is converted to wavelength.
b

Evert c

ETD d

Eexp. e

475
537
579
832

500
667
705
1234

454
476

E0-0 is the zero-point energies (ZPE) difference between S0 and T1 states at their

respective optimized geometries.


c

E vert is calculated by SCF method, which is the electronic-energy difference

between the T1,opt and S0 state relative to the lowest point of the optimized T1
geometry.
d

ETD is achieved by TD-DFT method at the T1,opt geometry.

The experimental values of studied complexes are obtained from Ref. 20.
In order to explore the emission wavelengths, the 0-0 transition energies and

vertical transition energies of all the platinum(II) complexes are calculated and the
corresponding computed values are summarized in Table 3. By comparing the
calculated values with the experimental ones, it can be found that there is a close
correlation between the experimental maximum emission wavelength (max) at room
temperature and Evert and 0-0 transition energy for Pt-1 and Pt-2, which suggests that
the experimental maximum emission wavelengths of Pt-1 and Pt-2 may correspond to
vertical transition and 0-0 transition of T1S0, respectively. According to the 0-0
transition energies, the emission wavelengths of Pt-2-4 with extended - conjugation
show an obvious red-shift compared with Pt-1, demonstrating that the emission
wavelengths of (NHC)Pt(II)(acac) can be effectively tuned via attaching the conjugation to the cyclometalated (C^C*) ligand. According to the Frank-Condon
12
ACS Paragon Plus Environment

Page 13 of 34

1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60

The Journal of Physical Chemistry

factor, the larger the overlap between the two vibrational wave-functions of initial
state and the final state, the vibronic transition will more probable occur, and the
higher the peak intensity corresponding to that vibronic transition.21 Without doubt,
the overlap between the two vibrational wave-functions of initial state and the final
state is closely relative to the geometric change of the two states, which can be
expressed by Huang-Rhys factor (S). On the basis of relationship between S and the
peak intensity,21 if the maximum S-values of molecules are small than 1, indicating
the geometry changes between two states are small and the 0-0 transition has the
highest intensity. Therefore, in the spectrum, the maximum absorption or emission
peaks are corresponding to the 0-0 transition, because the spectrum reflects the results
of all vibronic transition. On the contrary, the maximum absorption or emission peaks
are corresponding to the vertical transition. Due to the large geometric changes of T1
and S0 state for Pt-1, the experimental maximum emission wavelengths correspond to
vertical transition is reliable. However, the maximum S-values of Pt-2-4 are 0.58,
0.38, 0.28 (vide infra), respectively, implying that the 0-0 transitions used to elaborate
the experimental maximum emission wavelengths are reasonable. In addition, the
transition energy obtained from the SCF method is different from that obtained from
TDDFT. The main reason is that the SCF method treats only a single configuration
(as DFT is a single-determinant theory). The latter is a single-excitation theory, in
which more than one configuration is considered in solving the eigenvalues of the
excited states.
With an attempt to signify the transition character, the computation of the natural
transition orbitals (NTOs) with highest eigenvalues (i) close to 1 was performed on
the optimized T1 excited states. The plots are depicted in Figure 5, the unoccupied
NTOs denote the electron transition orbitals, while the occupied NTOs denote the
13
ACS Paragon Plus Environment

The Journal of Physical Chemistry

1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60

Page 14 of 34

hole transition orbitals. As shown, the NTO hole of Pt-1 is mainly distributed on
acac ligand and Pt atom and NTO electron is largely delocalized on acac ligand.
Therefore, for Pt-1, the transition nature of T1 emission can be mainly assigned to
metal-to-ligand charge transfer (MLCT) and intra-ligand charge transfer (ILCT).
However, for Pt-2-4, the NTO hole and electron are largely distributed on the main
ligand which has two phenyl cycles, thus the transition characters of these complexes
can be termed as ILCT. These results can again demonstrate that the extension of conjugation is an effective strategy for changing the emission propriety of
Pt(II)(NHC)(acac) complex. In addition, due to more 3MLCT contribution in electron
transition of T1 state, Pt-1 may have strong SOC and high phosphorescence quantum
yield.

electron

hole

i=1.012
i=0.981
i=1.100
i=1.004
Pt-1
Pt-2
Pt-4
Pt-3
Figure 5. The NTO plots of the studied complexes at the lowest-lying triplet excited
state (isovalue=0.02).
4.4. Phosphorescence quantum efficiency
It is well known that the phosphorescence quantum efficiency is determined by
radiative

rate

constant

and

non-radiative

rate

constants

which

include

temperature-independent and temperature-dependent non-radiative decay rate


14
ACS Paragon Plus Environment

Page 15 of 34

1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60

The Journal of Physical Chemistry

constants. The relationship among them can be expressed as equation (7).

p =

r
r + nr (1) + nr (2)

(7)

According to equation (7), larger radiative rate constant (r) and smaller
non-radiative rate constants (nr(1) and nr(2)) would lead to high phosphorescence
quantum efficiency.
4.4.1. Radiative decay rate constants

Table 4. Radiative rate constants r (s-1), ZFS parameters (cm-1) for the studied
complexes together with the available experimental values.
E(ZFS)

av r

39.12
0.42E+05
Pt-1
1.94
2.01E+03
Pt-2
0.73
0.43E+03
Pt-3
3.39
0.44E+03
Pt-4
a
the available experimental values from Ref.20.

r (Exp.) a

1.24E+05
5.50E+03

0.40
0.58

TD-DFT including spin-orbit coupling calculations with ZORA Hamiltonian can


well reproduce the phosphorescent lifetimes and ZFS parameters of organo-metallic
complexes.41-44 The calculated radiative rate constants, ZFS parameters for the studied
complexes together with the available experimental values are listed in Table 4. ZFS
parameters, as a key indicator that is in close connection with 3MLCT contribution in
emission excited state, can reflect the magnitude of radiative rate constant (r).45,46 As
shown in Table 4, the ZFS parameters of Pt-1 and Pt-4 are 39.12 and 3.39 cm-1,
respectively, which are larger than the corresponding ones of other complexes,
suggesting that Pt-1 and Pt-4 may possess larger radiative rate constants than Pt-2
and Pt-3. Seen from Table 4, Pt-1 has the largest radiative rate constant (0.42E+05
s-1), however, the radiative rate constant of Pt-4 is smaller than Pt-2. And the radiative
rate constant decreases from 0.42E+05 to 0.43E+03s-1 along with the extension of conjugation.
15
ACS Paragon Plus Environment

The Journal of Physical Chemistry

1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60

Page 16 of 34

Table 5. Transition dipole moments (Sn) (Debye) for S0Sn transitions, singlet
triplet splitting energies E(SnT1) (eV) and the SOC matrix elementsT1| HSOC| Sn
(cm-1) of Pt-1, Pt-2, Pt-3 and Pt-4 at their respective T1 optimized geometries.
Pt-1

Pt-2

Sn

(Sn)

E(SnT1)

T1|HSOC|Sn

(Sn)

E(SnT1)

T1|HSOC|Sn

S1

0.69

0.85

238.25

0.82

1.30

53.75

S2

0.62

1.06

477.70

0.61

1.56

40.41

S3

0.31

1.09

165.15

0.71

1.67

25.97

S4

1.02

1.21

335.71

1.60

1.85

47.38

S5

0.65

1.50

52.80

0.54

1.97

57.62

S6

0.71

1.61

192.12

0.35

1.98

160.68

Pt-3

Pt-4
T1|HSOC|Sn

(Sn)

E(SnT1)

1.00

0.39

1.12

1.43

8.79

1.51

32.81

0.75

2.10

98.56

0.32

1.62

140.31

0.39

2.26

22.96

S4

2.04

1.71

42.25

0.24

2.39

106.35

S5

0.66

2.02

21.82

_a

2.45

375.88

S6

1.10

2.11

19.88

3.98

2.69

61.81

(Sn)

E(SnT1)

S1

0.55

S2

1.66

S3

T1|HSOC|Sn

The value of oscillator strength is 0.18E-06.


In order to better elucidate the raidiative decay process and explore the factors

affecting the raidiative rate, transition dipole moments, singlet-triplet splitting


energies and the SOC matrix elements of Pt-1, Pt-2, Pt-3 and Pt-4 at their respective
T1 optimized geometric structure are listed in Table 5. For Pt-1, thought it has
relatively small transition dipole moments (Sn), it possesses smaller E(SnT1) and
larger SOC matrix elements than Pt-2-4, thus combining the three factors, it can be
inferred that Pt-1 has the largest radiative decay rate constant and the main determine
factors are E(SnT1) and SOC matrix elements. Compared with Pt-4, Pt-2 has small
transition dipole moments of S1, small singlettriplet splitting energies and large the
SOC matrix elements, which leads to the larger radiative decay rate constant. The
reason for the larger of the radiative rate constant of Pt-4 than that of Pt-3 is that Pt-4
has larger SOC matrix elements, especially SOC matrix elements between S1 and T1.
16
ACS Paragon Plus Environment

Page 17 of 34

1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60

The Journal of Physical Chemistry

In summary, the SOC matrix element is the key factor for determining the radiative
decay rate constant.
4.4.2. Non-radiative decay rate constants
4.4.2.1. Temperature-independent non-radiative decay rate constants

Table 6. The SOC matrix elementsT1|HSOC|S0(in cm-1) , the maximum Huang-Rhys


factor (Smax) of the normal modes and the non-radiative decay rate constants for all the
investigated complexes.

Pt-1
Pt-2
Pt-3
Pt-4

T1|HSOC|S0

Smax

knr

309.43
5.87
35.56
5.81

_
0.58
0.38
0.28

1.89E+05
3.90E+03

As discussed in computational details, the temperature-independent non-radiative


decay rate constants are proportional to the molecular deformation between S0 and T1
excited states. Therefore, the Huang-Rhys factors are computed to demonstrate the
molecular deformation for all the studied complexes, the calculated values are
summarized in Table 6 and the Duschinsky matrixes of Pt-2-4 are shown in Figure
S1-S3. Since Pt-1 has significant molecular deformation which can cause the
diffusion of Duschinsky matrix, as known, larger Duschinsky effect will lead to the
inaccuracy of Huang-Rhys factors. Thus, the Huang-Rhys factor of Pt-1 is not listed
in Table 6. In addition, on the basis of papers reported by Prof. Che,47,48 another factor
which determines the temperature-independent non-radiative decay rate constants is
the SOC between S0 and T1. According to Table 6, the SOC matrix element between
S0 and T1 excited state of Pt-1 is 309.4 cm-1 lager than that of Pt-2 (5.9 cm-1). And

Pt-1 has distinct molecular deformation, it can be inferred that Pt-2 has smaller
non-radiative decay rate constant than Pt-1. In the nutshell, because Pt-2 has smaller
SOC matrix element between S0 and T1 excited state and small Huang-Rhys factor, it
17
ACS Paragon Plus Environment

The Journal of Physical Chemistry

1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60

Page 18 of 34

may introduce Pt-2 has higher quantum efficiency than Pt-1 which has larger
radiative decay rate constant and energy-gap between T1 and S0 state. Besides, Pt-3
and Pt-4 have smaller Huang-Rhys factors than Pt-2, therein, Pt-4 has smaller SOC
matrix element between S0 state and T1 excited state than Pt-2, so it may be predicted
that Pt-4 has smaller temperature-independent non-radiative decay rate constant than

Pt-2. It can be concluded that enlarging - conjugation at phenyl moiety of main


ligand

of

Pt(NHC)(acac)

complex

may

be

beneficial

for

prohibiting

temperature-independent non-radiative decay process. The detailed Huang-Rhys


factor of normal mode is listed in Table S3-S5.
4.4.2.1. Temperature-dependent non-radiative decay processes
During the photo-deactivation process, there is an effective non-radiative decay
pathway which is 3MC state from emission state via thermal population. Therefore,
the existence of 3MC state can cause great effects on the luminescence behaviors of
the transition metal complexes. A detailed and clear picture of the excited-state
processes is crucial to the better understanding of the emissive properties of the
transition metal complexes, therefore, to get it, sufficient knowledge about the
potential energy profiles of the deactivation pathway from the 3ES via the 3MC state is
essential.
For Pt(II) complexes, possessing d8 electronic configuration planar geometries, the
3

MC states are formed by the population of d* orbital, which comes from the dx2-y2

orbital of Pt atom and orbital of the ligand. Once an electron occupies the virtual dx2
y2

* orbital, both the main and ancillary ligands become less bounded to the Pt atom,

as reflected by the longer Ptligand bond distances, thus leading to the great structural
distortion. The geometric structures of 3MC states of all complexes are optimized via
UDFT method by distorting the original geometric structures. The spin densities
18
ACS Paragon Plus Environment

Page 19 of 34

1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60

The Journal of Physical Chemistry

computed on 3MC states for all the investigated complexes are displayed in Figure 6.
The computed spin densities of Pt-1-4 are mainly distributed on the transition metal,
consistent with the nature of this state. In addition, as shown in Figure 6, the Pt-1-4
complexes adopt distorted geometric structures which mainly occur on acac ligand.
This character is in accordance with the nature of 3MC state as well.

Pt-1
Pt-2
Pt-3
Pt-4
Figure 6. Spin densities computed on 3MC state for all the investigated complexes
(isovalue = 0.002).
The 3MC states for Pt-1-4 are 69.3, 69.4, 69.2 and 68.8 kcal/mol higher than the
corresponding ground states in energy, an indicator that the extended - conjugation
has minor effects on the energies of 3MC states. However, the relative energies
between 3MC states and emission states are 0.4, 7.4, 12.8, 27.3 kcal/mol, respectively,
because the emission energies for Pt-1-4 show a tendency of decreasing.
The TS[3ES-3MC] which connects the emission state and 3MC state for 3ES3MC
conversion has been investigated. Unfortunately, the TS[3ES-3MC] of Pt-4 has not
been found out, but this has little influence on the exploration of the 3ES3MC
conversion. The vibration forms of Pt-1-3 are depicted in Figure S4-S6. In order to
prove the reliability of TS[3ES-3MC], the intrinsic reaction coordinates (IRC) are
calculated and the curves are plotted in Figure S7-S9. The active energy barriers of
3

ES3MC conversion for Pt-1-3 are 4.1, 12.1, 15.1 kcal/mol, respectively, and the

value of Pt-4 is more than 27.3 kcal/mol. These calculated data indicate that the
extension of -conjugation on main ligand is greatly unfavorable to the
temperature-dependent non-radiative decay processes. Besides, spin densities
19
ACS Paragon Plus Environment

The Journal of Physical Chemistry

1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60

computed on the TS [T1-3MC] for Pt-1-3 complexes are displayed in Figure S10.
Compared with the emission states, the transition states have more spin densities
distributed on metal atom.

Pt-1
Pt-2
Pt-3
Pt-4
3
Figure 7. Spin densities computed on the MECP [ MC/S0] for all investigate
complexes (isovalue = 0.002).
Once the 3MC state is thermally accessible, it can either return to the emission state
or jump to the minimal energy crossing point (MECP) between 3MC and the ground
state (1GS) potential energy surfaces. If the MECP is close to 3MC in energy and the
system provides enough energy for reaching the 3MC state, the radiationless process
of returning back to the ground state would be fast. The structures of S0 and 3MC at
the MECP are depicted in Figure S11-S14. The structures and energies of S0 and 3MC
at the MECP are almost identical, implying that the calculated results are reliable.
Besides, the spin densities maps are plotted in Figure 7. The spin densities of Pt-1-4
are mainly located on the metal atom, as same as 3MC state, indicating that the MECP
has notable metal-centered character. The energies of MECP are almost identical
which are 72.0, 72.0, 71.5 and 71.2, respectively, for all the investigated complexes.
4.5. Photo-deactivation mechanism

20
ACS Paragon Plus Environment

Page 20 of 34

Page 21 of 34

1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60

The Journal of Physical Chemistry

Pt-1

Pt-2

Pt-3

Pt-4

Figure 8. Schematic potential energy profiles of the deactivation pathway for the
investigated complexes.
In order to illustrate the photo-deactivation mechanisms of Pt-1-4, the schematic
Jablonski diagrams are depicted in Figure 8, which are constructed by using the
energies of the minima of the optimized triplet excited state and the average Pt-L (L
refers to the coordination atoms) bond distances. According to the above-mentioned
discussion, the emission of this system obeys the Kasha rule, which implies that the
T1 excited state is the emission state. Therefore, on the basis of the optimized
geometric structures of T1 excited state, the radiative and temperature-independent
non-radiative decay processes are explored in detail (see above). After disentangling
the radiative and temperature-independent non-radiative decay processes, the
thermally activated non-radiative photo-deactivation mechanisms are addressed. As
displayed in Figure 8, there are two rate-determining steps for the non-radiative
pathways in all the studied complexes. One is the population of the 3MC via the TS,
the other is the relative energy between 3MC and 1GS/3MC surface crossing point. For
21
ACS Paragon Plus Environment

The Journal of Physical Chemistry

1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60

the Pt-1-4, the energies of MECP above 3MC minimum are 2.6, 2.7, 2.9 and 2.4
kacl/mol, an indicator that the phenyl attached to main ligand can cause minor effects
on the second rate-determining step. However, for the first rate-determining step, the
active energy barriers are 4.4, 12.1, 15.1 and more than 27.3 kacl/mol for Pt-1-3 and

Pt-4, respectively. Therefore, it can be inferred that the extension of - conjugation is


beneficial for averting the thermally activated non-radiative photo-deactivation
processes.
4.6. New design complex-substitute effect

Figure 9. The optimized structures of the designed Pt-5 complexes.


In order to explore the influence of substitute group on photo-deactivation process
of rigid (NHC)Pt(acac) complex, the complex Pt-5 shown in Figure 9 is designed by
attaching the o-carborane (= 1,2-closodicarbadodecaborane) to the main ligand of

Pt-2. The carborane derivatives have been investigated for some metal complexes.49-53
15

Especially, carboranes can form metal-boron54,55 and metal carbon bonds,56 which

can be beneficial for building various transition complexes. Additionally, the


o-carborane cage, as a bulky group, will also suppress the formation of close
22
ACS Paragon Plus Environment

Page 22 of 34

Page 23 of 34

1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60

The Journal of Physical Chemistry

metal-metal contacts in solution and the condensed phase, thus minimizing emission
quenching caused by aggragation.57 In our previous study,58 the carborane can
enhance the phosphorescent quantum yield of Pt(II) complex. Therefore, the
o-carborane was used as well.

Figure 10. The calculated emission wavelength, radiative decay rate constant,
maximum Huang-Rhys factor and potential energy profiles of the deactivation
pathway for Pt-5.
The calculated various parameters of Pt-5 are plotted in Figure 10. According to the
computed results, , the emission wavelength of Pt-5 only red-shifts 10 nm compared
with that of complex Pt-2. And Pt-5 possesses larger radiative decay rate constant and
energy barrier between 3ES and 3MC states. More interestingly, the maximum
Huang-Rhys factor of Pt-5 is almost identical with Pt-2, which indicates that the
o-carborane causes minor effect on the rigidity of Pt-2. On the basis of the above
discussion, it can be easily speculated that complex Pt-5 has higher phosphorescence
quantum yield than complex Pt-2.

5. Conclusions
DFT and TD-DFT methods are employed to understand the influence of conjugation at main ligand of Pt(II)NHC(acac) complex on phosphorescent properties,
radiative and non-radiative decay processes. By analyzing the emission wavelengths,
23
ACS Paragon Plus Environment

The Journal of Physical Chemistry

1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60

radiative rate constants, transition dipole moments, triplet and singlet splitting
energies, Huang-Rhys factors, SOC matrix elements and the thermally activated
non-radiative photo-deactivation processes, some valuable conclusions can be drawn
below:
(1). The emission wavelengths are significantly red-shifted from 429 to 729 nm,
indicating that the emission bands can be effectively tuned via extending the conjugation at main ligand of Pt(II)NHC(acac) complex.
(2). The radiative rate constants of Pt-2-3 are smaller than that of Pt-1 , which can
be ascribed to the extended - conjugation at main ligand of Pt(II)NHC(acac)
complex, especially at NHC and phenyl moieties, which can cause the decrease of
SOC matrix elements and the increase of energy differences between T1 and Sn (n6) .
(3). Extending -conjugation at main ligand of Pt(II)NHC(acac) complex can
increase the rigidity of Pt(II)NHC(acac) complex, demonstrating that complexes

Pt-2-4 have smaller Huang-Rhys factors than complex Pt-1.


(4). The SOC matrix elements between T1 and S0 decrease from 390 to 5.8 cm-1
along with the extension of -conjugation at main ligand of Pt(II)NHC(acac) complex.
These values imply that enlarging -conjugation at main ligand of Pt(II)NHC(acac)
complex is an effective strategy to suppress the non-radiative processes between T1
and S0.
(5). The active energy barriers can be largely raised accompanied by enlarging
-conjugation at the main ligand of Pt(II)NHC(acac) complex, which makes the
thermally activated non-radiative photo-deactivation processes harder to proceed.
(6). The o-carborane cage attached to rigid can enhance the phosphorescence
quantum yield and maintain the original rigidity.
In summary, the non-radiative rate constants can be efficiently deceased via
24
ACS Paragon Plus Environment

Page 24 of 34

Page 25 of 34

1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60

The Journal of Physical Chemistry

enlarging -conjugation at main ligand of Pt(II)NHC(acac) complex, which is of great


significance in enhancing the phosphorescence quantum yields. Consequently, among
all the investigated complexes, Pt-5 may be a promising phosphorescence complex
for high-efficiency OLEDs.

ASSOCIATED CONTENT
Surporting Information
Functional test, the duschinsky matrix, the Huang-Rhys factor analysis, vibration
form of TS (transition state), intrinsic reaction coordinat (IRC) curve, spin densities
computed on the TS, structures of S0 and 3MC at MECP, Cartesian coordinates

REFERENCES
(1) Hudson, Z. M.; Sun, C.; Helander, M. G.; Chang, Y.-L.; Lu, Z.-H.; Wang, S.
Highly Efficient Blue Phosphorescence from Triarylboron-Functionalized Platinum
(II) Complexes of N-Heterocyclic Carbenes. J. Am. Chem. Soc. 2012, 134,
13930-13933.
(2) Unger, Y.; Meyer, D.; Molt, O.; Schildknecht, C.; Mnster, I.; Wagenblast, G.;
Strassner, T. GreenBlue Emitters: NHCBased Cyclometalated [Pt (C^ C*)(acac)]
Complexes. Angew. Chem. Int. Ed. 2010, 49, 10214-10216.
(3) Tronnier, A.; Poethig, A.; Herdtweck, E.; Strassner, T. C C* Cyclometalated
Platinum (II) NHC Complexes with -Ketoimine Ligands. Organometallics. 2014, 33,
898-908.
(4) Solomatina, A. I.; Krupenya, D.; Gurzhiy, V. V.; Zlatkin, I.; Pushkarev, A. P.;
Bochkarev, M. N.; Besley, N. A.; Bichoutskaia, E.; Tunik, S. P. Cyclometallated
Platinum (II) Complexes Containing NHC Ligands: Synthesis, Characterization,
25
ACS Paragon Plus Environment

The Journal of Physical Chemistry

1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60

Page 26 of 34

Photophysics and Their Application as Emitters in OLEDs. Dalton Trans. 2015, 44,
7152-7162.
(5) Baldo, M.; Lamansky, S.; Burrows, P.; Thompson, M.; Forrest, S. Very
High-Efficiency

Green

Organic

Light-Emitting

Devices

Based

on

Electrophosphorescence. Appl. Phys. Lett. 1999, 75, 4-6.


(6) Adachi, C.; Baldo, M. A.; Thompson, M. E.; Forrest, S. R. Nearly 100% Internal
Phosphorescence Efficiency in an Organic Light-Emitting Device. J. Appl. Phys. 2001,
90, 5048-5051.
(7) Baldo, M.; O'brien, D.; You, Y.; Shoustikov, A.; Sibley, S.; Thompson, M.;
Forrest,

S.

Highly

Efficient

Phosphorescent

Emission

from

Organic

Electroluminescent Devices. Nature. 1998, 395, 151-154.


(8) Sun, Y.; Giebink, N. C.; Kanno, H.; Ma, B.; Thompson, M. E.; Forrest, S. R.
Management of Singlet and Triplet Excitons for Efficient White Organic
Light-Emitting Devices. Nature. 2006, 440, 908-912.
(9) Zhang, X.; Wright, A. M.; DeYonker, N. J.; Hollis, T. K.; Hammer, N. I.; Webster,
C. E.; Valente, E. J. Synthesis, Air Stability, Photobleaching, and DFT Modeling of
Blue Light Emitting Platinum CCC-N-Heterocyclic Carbene Pincer Complexes.
Organometallics. 2012, 31, 1664-1672.
(10) Chow, P. K.; Cheng, G.; Tong, G. S. M.; To, W. P.; Kwong, W. L.; Low, K. H.;
Kwok, C. C.; Ma, C.; Che, C. M. Luminescent Pincer Platinum (II) Complexes with
Emission Quantum Yields up to Almost Unity: Photophysics, Photoreductive C-C
Bond Formation, and Materials Applications. Angew. Chem. 2015, 127, 2112-2117.
(11) Baranoff, E.; Fantacci, S.; De Angelis, F.; Zhang, X.; Scopelliti, R.; Grtzel, M.;
Nazeeruddin,

M.

K.

Cyclometalated Rridium

(III)

Phenyl-Imidazole Ligand. Inorg. Chem. 2010, 50, 451-462.


26
ACS Paragon Plus Environment

Complexes

Based on

Page 27 of 34

1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60

The Journal of Physical Chemistry

(12) Karatsu, T.; Takahashi, M.; Yagai, S.; Kitamura, A. Photophysical Properties of
Substituted Homoleptic and Heteroleptic Phenylimidazolinato Ir (III) Complexes as a
Blue Phosphorescent Material. Inorg. Chem. 2013, 52, 12338-12350.
(13) Zhao, J.; Yu, Y.; Yang, X.; Yan, X.; Zhang, H.; Xu, X.; Zhou, G.; Wu, Z.; Ren, Y.;
Wong, W.-Y. Phosphorescent Iridium (III) Complexes Bearing Fluorinated Aromatic
Sulfonyl Group with Nearly Unity Phosphorescent Quantum Yields and Outstanding
Electroluminescent Properties. ACS Appl. Mater. & Inter. 2015, 7, 24703-24714.
(14) Liu, Y.; Sun, X.; Wang, Y.; Wu, Z. The Influence of Numbers and Ligation
Positions of the Triphenylamine Unit on the Photophysical and Electroluminescent
Properties of Homoleptic Rridium (iii) Complexes: a Theoretical Perspective. Dalton
Trans. 2014, 43, 11915-11924.
(15) Prokhorov, A. M.; Hofbeck, T.; Czerwieniec, R.; Suleymanova, A. F.;
Kozhevnikov, D. N.; Yersin, H. Brightly Luminescent Pt (II) Pincer Complexes with a
Sterically Demanding Carboranyl-Phenylpyridine Ligand: A New Material Class for
Diverse Optoelectronic Applications. J. Am. Chem. Soc. 2014, 136, 9637-9642.
(16) Treadway, J. A.; Loeb, B.; Lopez, R.; Anderson, P. A.; Keene, F. R.; Meyer, T. J.
Effect of Delocalization and Rigidity in the Acceptor Ligand on MLCT Excited-State
Decay. Inorg. Chem. 1996, 35, 2242-2246.
(17) Kui, S.; Chow, P. K.; Cheng, G.; Kwok, C.-C.; Kwong, C. L.; Low, K.-H.; Che,
C.-M. Robust Phosphorescent Platinum (II) Complexes with Tetradentate O^ N^ C^
N Ligands: High Efficiency OLEDs with Excellent Efficiency Stability. Chem.
Commun. (Cambridge, England) 2013, 49, 1497-1499.
(18)CF Kui, S.; Chow, P. K.; Tong, G. S. M.; Lai, S. L.; Cheng, G.; Kwok, C. C.; Low,
K. H.; Ko, M. Y.; Che, C. M. Robust Phosphorescent Platinum (II) Complexes
Containing Tetradentate O^ N^ C^ N Ligands: Excimeric Excited State and
27
ACS Paragon Plus Environment

The Journal of Physical Chemistry

1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60

Application in Organic WhiteLightEmitting Diodes. Chem-Eur. J. 2013, 19, 69-73.


(19) Cheng, G.; Chow, P. K.; Kui, S. C.; Kwok, C. C.; Che, C. M. HighEfficiency
Polymer LightEmitting Devices with Robust Phosphorescent Platinum (II) Emitters
Containing Tetradentate Dianionic ONCN Ligands. Adv. Mater. 2013, 25,
6765-6770.
(20) Tronnier, A.; Pthig, A.; Metz, S.; Wagenblast, G.; Mnster, I.; Strassner, T.
Enlarging the System of Phosphorescent (C^ C*) Cyclometalated Platinum (II)
NHC Complexes. Inorg. Chem. 2014, 53, 6346-6356.
(21) Yersin, H. Highly Efficient OLEDs with Phosphorescent Materials. John Wiley &
Sons: 2008.
(22) Yersin, H.; Rausch, A. F.; Czerwieniec, R.; Hofbeck, T.; Fischer, T. The Triplet
State of Organo-Transition Metal Compounds. Triplet Harvesting and Singlet
Harvesting for Efficient OLEDs. Coordin. Chem. Rev. 2011, 255, 2622-2652.
(23) Wilson, J. S.; Chawdhury, N.; Al-Mandhary, M. R.; Younus, M.; Khan, M. S.;
Raithby, P. R.; Khler, A.; Friend, R. H. The Energy Gap Law for Triplet States in
Pt-Containing Conjugated Polymers and Monomers. J. Am. Chem. Soc. 2001, 123,
9412-9417.
(24) Mayo, S. L.; Olafson, B. D.; Goddard, W. A. DREIDING: a Generic Force Field
for Molecular Simulations. J. Phys. Chem. 1990, 94, 8897-8909.
(25) Adamo, C.; Barone, V. Toward Reliable Density Functional Methods without
Adjustable Parameters: The PBE0 model. J. Chem. Phys. 1999, 110, 6158-6170.
(26) Zhao, Y.; Truhlar, D. G. The M06 Suite of Density Functionals for Main Group
Thermochemistry, Thermochemical Kinetics, Noncovalent Interactions, Excited
States, and Transition Elements: Two New Functionals and Systematic Testing of
Four M06-Class Functionals and 12 Other Functionals. Theor. Chem. Acc. 2008, 120,
28
ACS Paragon Plus Environment

Page 28 of 34

Page 29 of 34

1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60

The Journal of Physical Chemistry

215-241.
(27) Yanai, T.; Tew, D. P.; Handy, N. C. A New Hybrid ExchangeCorrelation
Functional Using the Coulomb-Attenuating Method (CAM-B3LYP). Chem. Phys. Lett.

2004, 393, 51-57.


(28) Bark, T.; Thummel, R. P. [1, 10]-Phenanthrolin-2-yl Ketones and Their
Coordination Chemistry. Inorganic chemistry 2005, 44, 8733-8739.
(29) Abrahamsson, M.; Lundqvist, M. J.; Wolpher, H.; Johansson, O.; Eriksson, L.;
Bergquist, J.; Rasmussen, T.; Becker, H.-C.; Hammarstrm, L.; Norrby, P.-O. Steric
Influence on the Excited-State Lifetimes of Ruthenium Complexes with Bipyridyl
Alkanylene Pyridyl Ligands. Inorg. chem. 2008, 47, 3540-3548.
(30) Harvey, J. N.; Aschi, M. Spin-Forbidden Dehydrogenation of Methoxy Cation: a
Statistical View. Phys. Chem. Chem. Phys. 1999, 1, 5555-5563.
(31) Harvey, J. N.; Aschi, M.; Schwarz, H.; Koch, W. The Singlet and Triplet States of
Phenyl Cation. A Hybrid Approach for Locating Minimum Energy Crossing Points
between Non-Interacting Potential Energy Surfaces. Theor. Chem. Acc. 1998, 99,
95-99.
(32)URL: http://sobereva.com/286.
(33) ea Frisch, M., Gaussian 09, Revision A. 01. Gaussian, Inc., Wallingford, CT:
2009.
(34) Hariharan, P.; Pople, J. A. Accuracy of AH n Equilibrium Geometries by Single
Determinant Molecular Orbital Theory. Mol. Phys. 1974, 27, 209-214.
(35) Hay, P. J.; Wadt, W. R. Ab Initio Effective Core Potentials for Molecular
Calculations. Potentials for K to Au Including the Outermost Core Orbitals. J. Chem.
Phys. 1985, 82, 299-310.
(36) Snijders, J.; Baerends, E.; Ros, P. A Perturbation Theory Approach to Relativistic
29
ACS Paragon Plus Environment

The Journal of Physical Chemistry

1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60

Page 30 of 34

Calculations: II. Molecules. Mol. Phys. 1979, 38, 1909-1929.


(37) Van Lenthe, E.; Snijders, J.; Baerends, E. The ZeroOrder Regular Approximation
for Relativistic Effects: The Effect of SpinOrbit Coupling in Closed Shell Molecules.
The J. Chem. Phys. 1996, 105, 6505-6516.
(38) Te Velde, G.; Bickelhaupt, F. M.; Baerends, E. J.; Fonseca Guerra, C.; van
Gisbergen, S. J.; Snijders, J. G.; Ziegler, T. Chemistry with ADF. J. Comput. Chem.

2001, 22, 931-967.


(39) Guerra, C. F.; Snijders, J.; Te Velde, G.; Baerends, E. Towards an Order-N DFT
Method. Theor. Chem. Acc. 1998, 99, 391-403.
(40) Baerends, E. J.; Ziegler, T.; Autschbach, J.; Bashford, D.; Berces, A.;
Bickelhaupt, F. M.; Bo, C.; Boerrigter, P. M.; Cavallo, L.; Chong, D. P.; et al.
ADF2014, SCM, Amsterdam, year, http://www.scm.com.
(41) Wu, Y.; Shan, G.-G.; Li, H.-B.; Wu, S.-X.; Ren, X.-Y.; Geng, Y.; Su, Z.-M.
Theoretical Study and Design of Multifunctional Phosphorescent Platinum (ii)
Complexes Containing Triarylboron Moieties for Efficient OLED Emitters. Phys.
Chem. Chem. Phys. 2015, 17, 2438-2446.
(42) Mori, K.; Goumans, T.; van Lenthe, E.; Wang, F. Predicting Phosphorescent
Lifetimes

and

Zero-Field

Splitting

of

Organometallic

Complexes

with

Time-Dependent Density Functional Theory Including SpinOrbit Coupling. Phys.


Chem. Chem. Phys. 2014, 16, 14523-14530.
(43) Luo, Y.; Xu, Y.; Tian, L.; Zhang, W.; Li, M.; Shen, W. Exploration of
Phosphorescent Platinum (II) Complexes Functionalized by Distinct Main-Group
Units to Search for Highly Efficient Blue Emitters Applied in Organic Light-Emitting
Diodes: A Theoretical Study. Inorg. Chimi. Acta. 2015, 435, 109-116.
(44) Luo, Y.; Xu, Y.; Zhang, W.; Li, M.; He, R.; Shen, W. Exploring the
30
ACS Paragon Plus Environment

Page 31 of 34

1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60

The Journal of Physical Chemistry

Photodeactivation Pathways of Pt [O^ N^ C^ N] Complexes: A Theoretical


Perspective. ChemPhysChem. 2015.
(45) Yersin, H.; Humbs, W.; Strasser, J. Characterization of Excited Electronic and
Vibronic States of Platinum Metal Compounds with Chelate Ligands by Highly
Frequency-Resolved and Time-Resolved Spectra. In Electronic and Vibronic Spectra
of Transition Metal Complexes II, Springer: 1997; pp 153-249.
(46) Yersin, H.; Humbs, W.; Strasser, J. Low-Lying Electronic States of [Rh (bpy) 3]
3+,[Pt (bpy) 2] 2+, and [Ru (bpy) 3] 2+. A Comparative Study Based on Highly
Resolved and Time-Resolved Spectra. Coordin. Chem. Rev. 1997, 159, 325-358.
(47) Tong, G. S. M.; Chan, K. T.; Chang, X.; Che, C.-M. Theoretical Studies on the
Photophysical Properties of Luminescent Pincer Gold (iii) Arylacetylide Complexes:
the Role of -Conjugation at the C-Deprotonated [C^ N^ C] Ligand. Chem. Sci. 2015,
6, 3026-3037.
(48) Tong, G. S. M.; Chow, P. K.; To, W. P.; Kwok, W. M.; Che, C. M. A Theoretical
Investigation into the Luminescent Properties of d8-Transition-Metal Complexes with
Tetradentate Schiff Base Ligands. Chem.-A Eur. J. 2014, 20, 6433-6443.
(49) Visbal, R.; Ospino, I.; Lpez-de-Luzuriaga, J. M.; Laguna, A.; Gimeno, M. C. n.
N-heterocyclic Carbene Ligands as Modulators of Luminescence in Three-Coordinate
Gold (I) Complexes with Spectacular Quantum Yields. J. Am. Chem. Soc. 2013, 135,
4712-4715.
(50) Visbal, R.; Lpez-de-Luzuriaga, J. M.; Laguna, A.; Gimeno, M. C.
Three-Coordinate Gold (I) N-Heterocyclic Carbene Complexes: a New Class of
Strongly Luminescent Derivatives. Dalton Trans. 2014, 43, 328-334.
(51) Crespo, O.; Gimeno, M. C.; Laguna, A.; Lehtonen, O.; Ospino, I.; Pyykk, P.;
Villacampa, M. D. Structural and Photophysical Study on Heterobimetallic
31
ACS Paragon Plus Environment

The Journal of Physical Chemistry

1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60

Page 32 of 34

Complexes with d8d10 Interactions Supported by Carborane Ligands: Theoretical


Analysis of the Emissive Behaviour. Chem-Eur. J. 2014, 20, 3120-3127.
(52) Shi, C.; Sun, H.; Tang, X.; Lv, W.; Yan, H.; Zhao, Q.; Wang, J.; Huang, W.
Variable Photophysical Properties of Phosphorescent Iridium (III) Complexes
Triggered by closoand nidoCarborane Substitution. Angew. Chem.

2013, 125,

13676-13680.
(53) Czerwieniec, R.; Hofbeck, T.; Crespo, O.; Laguna, A.; Concepcion Gimeno, M.;
Yersin, H. The Lowest Excited State of Brightly Emitting Gold (I) Triphosphine
Complexes. Inorg. Chem. 2010, 49, 3764-3767.
(54) Prokhorov, A. M.; Slepukhin, P. A.; Rusinov, V. L.; Kalinin, V. N.; Kozhevnikov,
D. N. 2, 2-Bipyridinyl Carboranes as B, N, N-Ligands in Cyclometallated Complexes
of Platinum (ii). Chem. Commun. 2011, 47, 7713-7715.
(55)Spokoyny, A. M.; Machan, C. W.; Clingerman, D. J.; Rosen, M. S.; Wiester, M. J.;
Kennedy, R. D.; Stern, C. L.; Sarjeant, A. A.; Mirkin, C. A. A Coordination Chemistry
Dichotomy for Icosahedral Carborane-Based Ligands. Nature Chem. 2011, 3,
590-596.
(56) Yao, Z.-J.; Yu, W.-B.; Lin, Y.-J.; Huang, S.-L.; Li, Z.-H.; Jin, G.-X.
Iridium-Mediated Regioselective BH/CH Activation of Carborane Cage: A Facile
Synthetic Route to Metallacycles with a Carborane Backbone. J. Am. Chem. Soc.

2014, 136, 2825-2832.


(57) Farley, S. J.; Rochester, D. L.; Thompson, A. L.; Howard, J. A.; Williams, J. G.
Controlling Emission Energy, Self-Quenching, and Excimer Formation in Highly
Luminescent N^ C^ N-Coordinated Platinum (II) Complexes. Inorg. Chem. 2005, 44,
9690-9703.
(58) Zhang, W.; Luo, Y.; Xu, Y.; Tian, L.; Li, M.; He, R.; Shen, W. The Electronic
32
ACS Paragon Plus Environment

Page 33 of 34

1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60

The Journal of Physical Chemistry

Structures and Photophysical Properties of Platinum Complexes with C^ N^ N


Ligands: the Influence of the Carborane Substituent. Dalton Trans. 2015, 44,
18130-18137.

33
ACS Paragon Plus Environment

The Journal of Physical Chemistry

1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60

Table of content

34
ACS Paragon Plus Environment

Page 34 of 34