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Spectral and intramolecular charge transfer properties in
terminal donor/acceptor-substituted all-trans-a,x-diphenylpolyenes
and a,x-diphenylpolyynesw
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Xiaonan Ma, Linyin Yan, Xuefei Wang, Qianjin Guo* and Andong Xia*
Received 4th April 2011, Accepted 12th August 2011
DOI: 10.1039/c1cp21036j
The absorption spectra and intramolecular charge transfer (CT) properties of terminal donor/
acceptor-substituted all-trans-a,o-diphenylpolyenes (DPE) and a,o-diphenylpolyynes (DPY)
molecules with dierent conjugated bridge length and substitution modes were investigated by
using quantum chemical calculations. We calculated the ground state structures and energy of
two series of terminal donor/acceptor DPE and DPY by DFT method. The dependence of
conjugation length and substitution modes of the electronic absorption spectra was obtained by
TDDFT calculation. The hybrid-GGA XC-functional PBE0 employed in this work was selected
from several functionals by comparing the calculated electronic spectral data with experimental
value. The CIS-based generalized Mulliken-Hush (GMH) approach was further used to calculate
coupling values HAD of the CT process. The calculation shows that both the HOMOLUMO
energy gaps and average bond length alternations between unsaturated multiple (CRC and
CQC) and saturated single bonds (CC) decrease regularly with the extension of conjugation.
The eective conjugated length (ECL) of DPE and DPY with the same order MM 4 MP/PM 4
PP is found together with the regular red shift of the electronic absorption spectra with the
extension of conjugation, resulting from the dierent p-electron delocalization and conjugation
eciency. The GMH analysis further suggests that the CT process in both DPE and DPY is
predominated by the through-bond mechanism. The remarkable dierence of the conjugated
length dependence of squared CT coupling between substituted DPE and DPY is the result of the
energetic matching degree of the frontier molecular orbitals between donor/acceptor and the
conjugated bridge.
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between the initial and nal electronic states, and primarily past years, the study of one dimensional conjugated molecules
governs the CT rate,25 which can be described as, such as a,o-diphenylpolyyne (DPY) has also attracted the
interest of a number of research groups because of its unique
2p function as a simple linear molecule in nanoscale devices.52,53
kET jHDA j2 DWFC 1
h As a unique class of molecules with the simplest conjugated
bridge, both DPE and DPY represent the right model for
where DWFC is the FranckCondon factors weighted by the probing CT process with less inuence from the conguration
density of states, and is related to the nuclear motion spectrum limitations.54 Although the conjugation length dependence of
of the donor-p-acceptor system and its surroundings. the 11Ag(S0) - 11Bu transition of linear polyenes has been
To calculate electronic coupling of the CT process involving successfully interpreted in terms of the one-electron HOMO -
excited states, Newton and Cave developed the generalized LUMO transitions in the molecular orbital model,46 the
MullikenHush (GMH) approach to estimate the donor characterizing of CT coupling mechanism between terminal
acceptor interactions,26,27 based on the early models developed donor/acceptor substituted DPE and DPY compound is still
by Mulliken and Hush.28,29 This approach has been used to challenged and lack of quantitative description, in which the CT
calculate the coupling values for both ground and excited-state can be regulated in a controlled manner through such two kinds of
CT reactions. The signicant advantage of this approach is conjugated molecular bridges.55 In other words, the relationship
that one can calculate the electronic coupling without the among the structural character, conjugation property and the
transition state geometry,30 making GMH a useful method long-range CT coupling by through-bond and/or through-space
for calculating electronic coupling of the charge transfer process mechanisms within donor/acceptor substituted DPE and DPY
of large systems.31 In the early applications,32,33 the semi- compounds are still not understood. Scheme 1 shows the
empirical ZINDO/S calculation has been used to estimate the molecular structures of the donor/acceptor substituted a,o-
CT coupling in the GMH scheme. Recently, several ab initio diphenylpolyene (DPE) and diphenylpolyyne (DPY) studied
calculated methods such as CASSCF27 and TDDFT34 have been in this work. The substitution modes considered in this work
developed to calculate the CT coupling. Unlike the semi-empirical are listed in Table 1. Obviously, the DPE and DPY systems
method, ab initio calculation did not depend on the empirical with dierent conjugated length and substitution modes
parameters, therefore always supply more accurate coupling provide right model to address the question mentioned above.
values.35 However, although DFT methods show high accuracy In this article, we calculate the ground state structures and
in predicting molecular grometries and vibrational frequencies, energy of two series of terminal donor/acceptor substituted
plenty of studies indicated that TDDFT methods lead to a,o-diphenylpolyene and diphenylpolyyne by DFT method.
signicant problems in the description of CT states in large The dependence of conjugation length and substitution modes
conjugated molecules.34 Since the exact XC-functional is unknown, of the electronic absorption spectra is obtained by TDDFT
approximate XC-functionals need to be employed in practical calculation. The hybrid-GGA XC-functional PBE0 employed
calculation. The TDDFT calculations based on the approximate in this work was selected from several functionals by comparing
XC-functionals usually tend to underestimate the excitation the calculated electronic spectral data with experimental value.
energies, especially for large p-conjugated systems, doubly The two-state generalized Mulliken-Hush (GMH) approach
excited states and CT states.34,36 Moreover, the potential based on the CIS wave functions is further used to calculate
energy curve of CT state calculated by TDDFT often shows CT coupling HDA. We found that the eective conjugated
wrong sharp, in which the 1/R asymptotic behavior along the length (ECL) of DPE and DPY series shows distinct dierence
charge-separation coordinate R does not show the correct with each other due to their dierent p-delocalization and
electrostatically attractive pattern when standard XC-functionals
are empolyed.34 On the other hand, Hsu and her co-works
developed CIS-based GMH framework and its variants to Table 1 Substitution modes of the donor and acceptor in DPE and
DPY studied in this work
compute the coupling for charge transfer,18,30 excitation
energy transfer37 and triplettriplet energy transfer.38 Especially, Donor Acceptor
they demonstrated that the CIS based GMH scheme is able to
HH H H
characterize both through-bond and through-space CT coupling, MM mata-NMe2 meta-CN
with results close to experimentally derived values.30 Therefore, PM para-NMe2 meta-CN
in this work, we employed the similar calculated framework MP mata-NMe2 para-CN
PP para-NMe2 para-CN
based on the CIS method to estimate the CT coupling in the
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conjugation eciency, which is also reected by the dierent In principle, the coupling factor is an o-diagonal Hamiltonian
CT coupling strength. The GMH analysis indicates that the matrix element between the initial and nal diabatic states in
CT process in both DPE and DPY is predominated by the CT process.35 Solving the Schrodinger equation yields a set
the through-bond mechanism. The remarkable dierence of of eigenstates, but the coupling is the Hamiltonian element in a
the conjugated length dependence of squared CT coupling charge-localized space. Therefore, the GMH scheme empolys
between DPE and DPY is the result of the energetic matching an additional dipole operator to dene the charge-localized space,
degree of the frontier molecular orbitals between donor/ then the coupling can be calculated by transforming the two-state
acceptor and the conjugated bridge. Hamiltonian accordingly. On the basis of the consideration
above, in GMH scheme, the coupling factor HDA between
2. Computational methods the initial donor LE state and the nal CT state can be
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given by,31,35
The ground state geometries and corresponding absorption
spectra were calculated by DFT and TDDFT methods in m12 DE12
HDA q
2
6-31g* level, respectively. In TDDFT calculations, the calculated m1 m2 2 4m212
excited state properties are strongly dependent on the fractions
of orbital exchange in the used hybrid XC-functional. The
where m12 is the transition dipole moment between the two
functionals with small orbital exchange fraction (such as
adiabatic states in the charge transfer, (m1m2) is the dierence
B3LYP, 20%) tend to overestimate the CT properties,
in adiabatic state permanent dipole moments, and DE12 is the
therefore favor zwitterionic-like states with strong CT
energy dierence between the initial and nal adiabatic states.
character. On the contrary, functionals with large oribital
Due to the existence of the principle error of TDDFT
exchange fraction (such as BHandHLYP, 50%) is more
methods in the description of CT state in large conjugated
suitable to treat the neutral-base electronic excitation.56
systems, all of these values are obtained by CIS calculations in
In this work, the hybrid-GGA functional PBE0 was employed
6-31g* level with the DFT optimized ground state geometries.
in the structural and spectral calculations of terminal DA
Previous studies have shown that the CIS method yields
substituted conjugated systems, which is made up by the pure
reliable coupling values for a variety of CT processes.30,35
PBE XC-functional and 25% percentage of orbital exchange. Here
All of the calculations were carried out by the method
the PBE0 functional was selected from eleven well-established
implemented in GAUSSIAN 03 E.01 package.57
functionals by comparing the calculated electronic spectral data
with experimental value in references The detail information is
shown in ESI S1.w The line shape of the calculated electronic 3. Results and discussion
absorption spectra is broaden with the multiple Gaussian
3.1. Structure and energy of ground state
function related to the corresponding excitation energy and
oscillator strength from the TD-PBE0 calculations. The The most stable molecular structures of DPE and DPY in the
UVvis spectra peak half-width at half height tentatively sets ground states are fully optimized under the DFT method
as 0.3 eV (2419.66 cm1). without any symmetry constraint. The bond length alternation
The CT couplings are calculated by means of the two-state parameters (BLA) for DPE and DPY are calculated, where the
generalized MullikenHush (GMH) approximation in this work. BLA is dened as the dierence between the averages of the
Fig. 1 Bond length alternation parameters (ab) and HOMOLUMO energy gap (cd) versus the number of repeat units (n) obtained from the
DFT calculation. The (a) and (c) are for DPE series, (b) and (d) are for DPY series.
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saturated (CC) and the unsaturated (CQC in DPE and 3.2. Absorption spectra
CRC in DPY) bond lengths:58,59
The electronic absorption spectra of DPE and DPY series
%
BLA(DPE) = R(CC) %
R(CQC) (3) were calculated at TD-PBE0/6-31G(d) level based on the
optimized ground state geometries. The performance of the
%
BLA(DPY) = R(CC) %
R(CRC) (4) PBE0 functional in the calculation of electronic spectra is
shown in ESI S1.w As an example, the multiple gaussian
The evolution of the calculated BLA of DPE and DPY is function (the half-width at half-height tentatively sets as
plotted as a function of the number of repeat units (n) in 0.3 eV) broaden absorption band shapes of DPE/DPY series
Fig. 1(a) and (b) respectively. The BLA values in D/A with the conjugated bridge length (n = 6) and dierent
substituted species is slightly smaller than that in non-
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DPE DPY
BLA/A gap/eV BLA/A gap/eV
n=1 n=N n=1 n=N n=1 n=N n=1 n=N
HH 0.117 0.0645 4.313 1.7599 0.208 0.1062 4.436 1.9854
MM 0.118 0.0640 3.596 1.3156 0.208 0.1045 3.736 1.6850
PM 0.110 0.0626 3.499 1.5546 0.203 0.1048 3.711 1.6207 Fig. 2 The calculated absorption spectra of DPE (a) and DPY
MP 0.114 0.0635 3.414 1.2596 0.206 0.1057 3.352 1.7495 (b) series with conjugated bridge length (n = 6) and dierent
PP 0.105 0.0617 3.328 1.5326 0.200 0.1046 3.479 1.6726 donoracceptor substituted modes.
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wavelength for both DPE and DPY series shows regular red values estimated by eqn (6) are listed in Table 3. Because of
shift with the increasing p-conjugated bridge length (See the low calculation accuracy of PBE0 functional for the S0 -
ESI S2)w, resulting from the increase of the p-electron 11B1u band of DPY (see the ESI S1)w, we did not t the
delocalization along the conjugated chain.61,67 Meanwhile, the spectral data of this band to estimate the ECL value, although
oscillator strengths of the main absorption band for both DPE the absorption wavelength of this band also shows regular red
and DPY show the signicant increase with the prolongation of shift with the extension of conjugation (as shown in Fig. 3(c)).
conjugated bridge length, indicating that the extension of the Obviously, the DPE shows much longer ECL value than that
p-electronic system leads to strong oscillator strength.62 In the of DPY. As suggested by Luthi and his co-workers that,58,59
description of the eective conjugated length introduced by the conjugation eciency, i.e., the ability to promote electron
Meier,67 the absorption wavelength of conjugated oligomers delocalization along the conjugated backbone, determines the
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could be tted by the empirical exponential equation, ECL of conjugated oligomers. The relative short ECL results
from the much lower conjugation eciency of polyyne
ln = lN (lN l1)eb(n 1)
(5)
conjugated chain than that of polyene chain due to the
where Dl = (lN l1) are the absorption wavelength dierence relatively weak p - p* orbital interactions. In addition,
between the polymer and monomer, n represents the number of because of the very low rotational barrier about 0.05 eV per
repeat units in conjugated chain, and parameter b indicates how cylindrical triple bond,62,63 twisting the cylindrical triple bond
fast ln will saturate towards lN. From these parameters, one in DPY should break the conjugation of a single polymer
can calculate the eective conjugated length (ECL) of the chain, also resulting in the shorter ECL in DPY.
oligomer series with eqn (6), which is dened as the value of Furthermore, it is found that the terminal donoracceptor
n for which the dierence between lN and ln is less than substitution of DPE and DPY oligomers have remarkable
1 nm.68 The ECL values oer a quantitative measurement for eect on the ECL value. That is also reected by the BLA
the conjugation eciency of DPE/DPY backbone as well as evolution as well as by the dierence in HOMOLUMO
the CT characters between donor and acceptor.5859,62 energy gap with respect to the D/A substitutions. Particularly,
the ECL values of both of donor/acceptor substituted DPE
ln Dl
ECL 1 6 and DPY also show the order MM 4 MP/PM 4 PP. This
b
order is consistent well with the order of HOMOLUMO
Fig. 3 shows the conjugated length dependence of the absorption energy gap of D/A substituted DPE and DPY species. It is
wavelength and oscillator strength values of S0 - 11Bu band known that HOMOLUMO energy gap of D/A substituted
(for DPE) and S0 - 11B1u, S0 - 21B1u bands (for DPY). It is series could be contributed from two parts, the energy from
found that, the absorption wavelengths (in nm) of S0 - 11Bu p-conjugated bridge and the correction term from the CT
band (for DPE in Fig. 3(a)) and S0 - 21B1u band (for DPY in eect as described in references.6970 Therefore, the dierent
Fig. 3(b)) are tted well by the eqn (5) as a function of the ECL value in the D/A substitution series shows the summation
number of repeat units (n). The tted parameters and ECL of the alternation degree of conjugated eciency in conjugated
Fig. 3 Conjugated length dependence of the absorption spectroscopy of DPEs and DPYs. The (a)(c) are for absorption wavelength and the
(d)(f) are for the corresponding oscillator strength. The solid line stand for the tting data, the dash line is the ordinary connected line.
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Table 3 Fitted parameters of the absorption wavelength and DPY are p and p*-type orbitals that only localized
calculated ECL values for DPE and DPY Series on conjugated bridge. In this transition, the amounts of
DPE S0-11Bu DPY S0-21B1u transferred charges for this transition are very small.
In the S0 - 11Bu transition of DPE, the transition component
lN l1 ECL lN l1 ECL is domminated by the CT transition (HOMO - LUMO),
HH 1277.0 302.7 B179 561.3 173.8 B54 which are independent with the dierent conjugated length
MM 1182.7 310.4 B151 724.7 186.8 B98 and substituted mode. However, unlike the DPE, besides the
PM 1080.7 355.6 B124 602.8 188.5 B68
MP 1113.3 325.2 B132 655.3 187.2 B77
HOMO and LUMO, other p and p* orbitals also have to be
PP 1025.5 372.8 B106 583.6 197.4 B61 considered for the S0 - 11B1u transitions in DPY. The longer
the conjugated chain is, the more important is the participation
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Table 4 The calculated vertical excitation energies, oscillator strengths of the important transitions of typical substituted DPE and DPY, together
with the corresponding transition components
MM PP
DPE S0 - 1 Bu 1
DPY S0 - 1 B1u
1
DPY S0 - 2 B1u
1
DPE S0 - 11Bu DPY S0 - 11B1u DPY S0 - 21B1u
n=2 3.0988 eV/0.1674a 3.2720 eV/0.1602 5.9127 eV/1.3913 2.9919 eV/1.6104 3.0825 eV/1.2683 5.2893 eV/0.8875
H - L,b 0.89 H - L, 0.96 H2 - L + 2, 0.25 H - L, 1.00 H - L, 0.95 H5 - L, 0.62
H1 - L, 0.11 H1 - L, 0.04 H4 - L + 1, 0.22 H1 - L, 0.05 H2 - L + 3, 0.27
H1 - L + 4, 0.18 H1 - L, 0.05
H3 - L, 0.08 H1 - L + 1, 0.04
n=4 2.8062 eV/0.9648 2.7688 eV/0.2293 4.3626 eV/1.8665 2.5669 eV/2.3560 2.5663 eV/1.0512 4.1542 eV/3.7302
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Fig. 4 Schematic diagram with the calculated absolute energies and the orbital contour plots of the frontier orbitals around the gap of donor/
acceptor substituted DPE and DPY.
the dierent electronic structure feature and conguration isomers due to the lower degree of localization, and the CT
interaction properties of corresponding transitions. As shown coupling is restricted, whereas the singlet states of the meta
in Fig. 4, we found that meta-substitution blocks charge derivatives show greater CT character. Moreover, the HOMO
delocalization in the HOMO, where the wavefunction is higher energy in meta isomer of DPE increases around 0.006 eV, while
localized relative to that in para isomers. As a consequence, the LUMO decreases about 0.287 eV relative to that in non-
the local excitation of donor is somewhat limited in the para substituted species. However, substitution of donor/acceptor
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Fig. 5 Length dependence of squared electronic coupling of DPE/DPY series and its exponential decay tting.
in the para position leads to a more symmetric increase 1.1 A1 for through-bond coupling in saturated hydrocarbon
(0.307 eV)/decrease (0.297 eV) of the HOMO/LUMO, which bridges.30,8082 It is found that most of the tted b values of the
would induce a weaker electron interaction than in the meta CT coupling in DPE and DPY series are around 0.20.5 A1,
isomer (also suitable for the DPY system).76 On ther other the b value suggests that the through-bond mechanism rather
hand, as shown in Table 4 and mentioned above, TDDFT than the through-space mechanism makes the dominant
calculation indicates that the meta isomers show more complex contribution to the CT coupling. The through-bond character
contributed components of S0 - 11Bu (DPE) and S0 - 11B1u of the CT process in DPE/DPY is agreement to the signicant
(DPY) transitions than para isomers, while the contribution of contribution of conjugated bridge for the HOMO/LUMO
HOMO - LUMO component accordingly turns lower. As representation as mentioned in the beginning of this section.
shown in Fig. 4, many other frontier molecular orbitals beside Moreover, the overall coupling value is composed of two
HOMO and LUMO (such as HOMO 2, HOMO 1, contributions as shown below:83,84
LUMO + 1, LUMO + 2) are mainly contributed by the
conjugated bridge, while HOMO locate on donor and con- HDA = HSpace Bond
DA + HDA (8)
jugated bridge, and LUMO is contributed by the acceptor and
conjugated bridge. Therefore, the complex transition compo- where the rst term HDASpace is the direct through-space
nents involved plenty of frontier molecular orbitals in meta coupling contribution, and the second term HDABond is the
isomers promote the interaction between donor/acceptor and through-bond contribution mediated by the presence of a
conjugated bridge, then accordingly induces the relative high conjugated bridge. To further study the through-space/bond charge
CT coupling values. transfer mechanism in DPE and DPY, the through-space coupling
For bridge-assisted CT systems, the squared CT coupling is is calculated in partial structures containing disconnected donor
usually expected to decrease approximately with distance and and acceptor fragments with two extra lling hydrogen
is characterized by an exponential decay formula with an atoms.37 The calculated coupling values are listed in Table 5.
exponent parameter b:7779 Compared to the full molecule including the conjugated bridge
connecting donor and acceptor, it is found that the through-space
|HDA|2 = |H0DA|2exp[b(r r0)] (7) coupling values are much smaller and decay very fast along with
the donoracceptor distance. Therefore, we conrm that the CT
where H0DA is the coupling element at a reference donor process in these molecules is predominated by the through-bond
acceptor distance r0, and the parameter b represents the mechanism, which is consistent with the prediction from the
donoracceptor distance dependence of the squared CT frontier molecular orbital representation and the values of
coupling. In this work, the DA distance is dened as the tted decay parameter b.
nitrogen atom in dimethylamine to carbon in cyano. The On the other hand, the squared CT coupling of DPE and
exponential tting of the CT coupling squared (with the unit DPY series shows dierent decay pattern with the extension of
of eV2) is also shown in Fig. 5, which is dependent with the conjugation. For DPE series, the squared CT coupling follows
donoracceptor distance (with the unit of angstrom), and the regular exponential decay monotonously with the increase of
tted b values are also listed in Fig. 5. The decay parameter conjugated length, which is consistent with the calculated result
b suggests the coupling mechanism in some extent. Experimental in literature.85 However, the conjugation length dependence of
studies suggested that typical values for b range from 2.8 to the squared CT coupling of DPY is obviously dierent from
3.0 A1 may be for through-space coupling, and from 0.8 to that of DPE, where the coupling values obeys the exponential
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Table 5 Calculated CT coupling of the disconnected fragment exponential decay when the repeat units (n) is less than 4. The
without mediated bridge impact of the substituents is pronounced only in the shortest
Through space coupling 102/eV in DPE oligomers, where the donor and acceptor not only inuence
the orbital energies, they also alter the electron correlation as
MM PM MP PP discussed above.
n=1 0.42 0.60 1.57 0.43
n=2 5.46 104 5.08 104 2.08 103 4.84 104
n42 0 0 0 0 4. Conclusions
2
Through space coupling 10 /eV in DPY We have performed a series of quantum chemical calculations
MM PM MP PP
to study the conjugated length and terminal donor/acceptor
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Acknowledgements
This work was nancially supported by NSFC, 973 Programs
and Chinese Academy of Sciences.
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