Article

Cite This: J. Phys. Chem. A 2019, 123, 3937−3948 pubs.acs.org/JPCA

Dynamic Excited-State Intramolecular Proton Transfer Mechanisms

of Two Novel 3‑Hydroxyflavone-Based Chromophores in Two
Different Surroundings
Jiaojiao Hao and Yang Yang*
State Key Laboratory of Molecular Reaction Dynamics, Dalian Institute of Chemical Physics, Chinese Academy of Sciences,
Dalian 116023, China
*
S Supporting Information
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ABSTRACT: The dynamic excited-state intramolecular proton transfer (ESIPT)

mechanisms of two novel 3-hydroxyflavone-based chromophores (1 and 2) in different
Downloaded via UNIV OF GOTHENBURG on October 23, 2019 at 16:32:19 (UTC).

surroundings (nonpolar cyclohexane and polar acetonitrile solvents), which are reported
in the recent work (Chou et al. J. Phys. Chem. A. 2010, 114, 10412), are explored in
terms of the density functional theory (DFT) and time-dependent DFT theoretical
methods. The computational absorption and emission spectra for the work rendered
here were in reasonable agreement with the relevant experiment. In order to present the
molecular-level exposition of the ESIPT reactions for these compounds in two different
solvents, we calculated the hydrogen bond (HB) parameters, corresponding infrared
vibrational frequencies, frontier molecular orbitals, and maps of electron density
difference between the S0 and S1 states, and the HB strengthening tendency in S1 states
was verified, giving the probability of ESIPT reactions. In addition, to definitely expose
the ESIPT mechanisms of compounds 1 and 2, we built the potential energy curves and
potential energy surfaces in the S0 and S1 states. Calculated results exhibited that the
ESIPT reaction of compound 1 in nonpolar cyclohexane solvent was more susceptible
than that in polar acetonitrile solvent. For the asymmetric compound 2, only single-
ESIPT processes could occur in both the solvents, and double-ESIPT processes were prohibitive due to high potential energy
barriers. Moreover, the single-ESIPT processes [I (6.26 kcal/mol) and II (6.62 kcal/mol)] in cyclohexane were more
susceptible than that [I′ (6.91 kcal/mol) and II′ (6.90 kcal/mol)] in acetonitrile. Furthermore, the single-ESIPT process I had a
little advantage over the process II in cyclohexane, while the probabilities of processes I′ and II′ were roughly the same in
acetonitrile.

1. INTRODUCTION deeply from the experimental and theoretical points of view in

The hydrogen bond (HB), as one of the remarkable weak
interactions, is generally deemed to play a pivotal role in phys-
ical, chemical, and biological processes, such as water solution,1,2
DNA double-strand,3,4 α-helix,5,6 pharmacophore,7,8 and so
forth.9−13 In recent decades, as the excited-state has been
understood in depth, it is confirmed that the HB can enable
excited-state intramolecular proton transfer (ESIPT), which
gives rise to the production of tautomer with the different elec-
tronic construction from the initial excited form.14−20 Universally,
the ESIPT reaction takes place along with the four-level photo-
cycle, i.e., absorption → ESIPT → emission → ground-state
intramolecular PT (GSIPT). The great difference of charge
arrangement between the phototautomers in ESIPT process
leads to the result that ESIPT fluorophores possess peculiar
photophysical properties, such as the prominent Stokes shift,21
dual fluorescence,22 fastest chemical reaction,23 and so on.24,25
Subsequently, these properties trigger crucial applications such
as molecular switches,26 light-emitting diodes,27 fluorescence
imaging,28 and the like29−34 in organic new materials and
devices. Consequently, the ESIPT behaviors have been probed
order to create more valuable compounds.
As a rule, the majority of the ESIPT processes contain single
PT via the presence of an intramolecular HB between the
proton donor (H atom from −OH or −NH2 group) and the
proton acceptor (O atom from −CO group or N atom
from −CN group). In addition, the intramolecular HB is
enhanced after light excitation, which facilitates the occurrence
of the ESIPT reactivity. In fact, such a single PT reaction is not
competent to simulate complicated multiple PT reactions
in biochemical fields, particularly the double PT reaction.
Accordingly, the double-ESIPT reaction exerts a tremendous
fascination on researchers due to their important features
in materials and biological fields. During the past few decades,
an army of typical and excellent organic compounds with
two intramolecular HBs (i.e., double proton) has been
designed and synthesized in experiment;35−39 meanwhile, the
double-ESIPT mechanisms widely have been explored by
Received: January 29, 2019
Revised: March 28, 2019
Published: March 29, 2019

© 2019 American Chemical Society 3937 DOI: 10.1021/acs.jpca.9b00879

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combined experimental time-resolved spectroscopies and density gradient (RDG) isosurfaces for two compounds were
theoretical calculations.40−49 To date, the reaction pathways executed from the Multiwfn package.79 In addition, a series of
of the double-ESIPT processes can be outlined as follows: the DFT functional has been tested in this work and it was
stepwise and simultaneous reaction pathways.50−54 Nevertheless, verified that the B1B95 function procures the most satisfied
the previous research mainly has poured attention into the accordance with the experimental date (see Table S1 in
symmetric ESIPT compounds, but rarely has attempted to the Supporting Information).
asymmetric.
More recently, Chou et al. have synthesized two novel 3. RESULTS AND DISCUSSION
3-hydroxyflavone (3-HF)-based chromophores (shown in 3.1. 2-(4-(Diphenylamino)phenyl)-3-hydroxy-4H-
Figure 1 and 7), 2-(4-(diphenylamino)phenyl)-3-hydroxy- chromen-4-one (Compound 1). 3.1.1. Analysis of Geo-
4H-chromen-4-one (compound 1 involving one intramolecular metric Constructions. In this subsection, the configurations of
HB) and 2,2′-((phenylazanediyl)bis(4,1-phenylene))bis(3- the normal (1-N) and tautomer (1-T) forms for compound 1
hydroxy-4H-chromen-4-one) (asymmetric compound 2 in- in the S0 and S1 states have been optimized by means of the
volving two intramolecular HBs).55 They have determined DFT/TDDFT methods combined with the B1B95/TZVP
ESIPT properties for both the compounds in different solvent level in nonpolar cyclohexane and polar acetonitrile solvents,
environments by means of femtosecond fluorescence spectros- respectively (see Figure 1). The labeled numbers of the
copy. It is well known that the 3-HF and its derivatives have
been a subject of extensive investigation within the past few
decades.56−61 Until now, a multitude of studies has ascertained
the ESIPT mechanisms and dynamics of 3-HF chromophores,
such as that its normal form (N*) changes into the tautomer
form (T*) in the S1 state under light excitation, and it leads
to generate dual fluorescence in this process.62−64 Although
the compounds 1 and 2 have shown resemblance to the
excited-state behaviors of 3-HF and its derivatives with the
aid of spectral measurements, the Chou’s study regarding
these compounds is considered incomplete due to the two Figure 1. Optimized normal (1-N) and tautomer (1-T) forms of
PT sites of compound 2. The first question involves that this compound 1 by the B1B95/TZVP method in nonpolar cyclohexane
experimental work did not provide the adequate informa- and polar acetonitrile solvents.
tion concerning optical properties. The second problem
relates to the absence of the distinct and particular discussions intramolecular HB (O1−H2···O3) were needful in order
on the ESIPT reactions, especially on the more complex to facilitate the discussion about the PT behavior for this
ESIPT processes for the asymmetric compound 2. The third compound. The key structural parameters of 1-N and 1-T
aspect involves the shortage of the in-depth explorations of forms in the S0 and S1 states in two solvents are tabulated in
solvent polarity effect on the ESIPT processes for compounds the Table 1. As seen from Table 1, for the 1-N form, the BL of
1 and 2. Hence, the aim of this work is to shed light on the
detailed ESIPT mechanisms of these compounds and their Table 1. Major Calculated BLs (Å) and BAs (°) of Normal
changes in the different polar solvents in virtue of theoretical and Tautomer Forms for the Compound 1 in the S0 and S1
methods. States Used the DFT/TDDFT/B1B95-TZVP Methods in
Both Nonpolar Cyclohexane and Polar Acetonitrile
2. COMPUTATIONAL DETAILS
Solvents, Respectively
To achieve the useful data derived from the geometric con-
structions, the stable constructions of compounds 1 and 2 in cyclohexane acetonitrile
the ground (S0) and excited (S1) states were optimized using S0 S1 S0 S1
the density functional theory (DFT) and time dependent DFT 1-N O1−H2 0.975 0.986 0.975 0.984
(TDDFT) methods in conjunction with the B1B95 functional65,66 H2−O3 1.977 1.851 1.977 1.878
and TZVP basis set,67−74 as performed in Gaussian09 program.75 δ(O1−H2···O3) 119.5 124.7 119.5 123.6
Moreover, to comply with the previous experiment, the polar- 1-T O1−H2 1.787 1.903 1.815 1.935
izable continuum model (PCM) using the integral equation H2−O3 0.998 0.983 0.994 0.980
formalism variant76−78 with the nonpolar cyclohexane and δ(O1−H2···O3) 125.4 121.5 124.5 120.5
polar acetonitrile solvents was considered when theoretically
computing. The bond lengths (BLs) and angles (BAs) were
not limited in the optimization processes for these compounds. O1−H2 is enlarged from 0.975 (S0) to 0.986 Å (S1), and
Furthermore, the infrared (IR) vibrational frequencies of these the distance of H2···O3 is lessened from 1.977 (S0) to 1.851
compounds were simulated, and it could be confirmed that all Å (S1) in cyclohexane. Moreover, the BA δ (O1−H2···O3) is
optimized constructions were the most stable (no imaginary). increased from 119.5° (S0) to 124.7° (S1), which evidences
Additionally, the vertical excitation energies were calculated that the δ tended to 180° in the S1 state. They indicated
based on the S0 state-optimized geometries. Besides, to expound that the HB (O1−H2···O3) of compound 1 is enhanced in the
the dynamic ESIPT processes of these compounds in two S1 state in nonpolar cyclohexane solvent. A similar trend
different solvents, the potential energy curves (PECs) and appeared in polar acetonitrile solvent: the BL of O1−H2 is
potential energy surfaces (PESs) of the S0 and S1 states were changed from 0.975 (S0) to 0.984 Å (S1); the distance of
constructed, respectively. What is more, the maps of electron H2···O3 is changed from 1.977 (S0) to 1.878 Å (S1); the BA
density difference between the S0 and S1 states and the reduced δ(O1−H2−O3) is changed from 119.5° (S0) to 123.6° (S1).
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Figure 2. RDG isosurfaces for the compound 1: the S0 (1a) and S1 (2a) states in nonpolar cyclohexane; the S0 (1b) and S1 (2b) states in polar
acetonitrile.
That is to say, the HB is strengthened in the S1 state in
both the solvents, which can promote the ESIPT process for
compound 1.
As shown in Figure 2, the intramolecular HB (O1−H2···O3)
between the proton donor (O1 atom) and proton acceptor
(O3 atom) of compound 1 is pictured. It could be plotted
via the RDG versus sign(λ2)ρ and lower panel low-gradient
(s = 0.5 au) isosurfaces, which has been executed by the
Multiwfn package.79 Figure 2(1a,2a,1b,2b) exhibited spikes
3939
Article
of around −0.03 au, wherefore the distinct intramolecular HB
of compound 1 is determined in two solvents, respectively.
3.1.2. IR Vibration Spectra, Electronic Spectra, and
Frontier Molecular Orbitals. First, the IR vibration spectra
of compound 1 in nonpolar cyclohexane and polar acetonitrile
solvents have been simulated and are illustrated in Figure 3.
At present, the detection of IR vibrational spectral shift is the
effective way to confirm the changes of the S1 state HB.80−83
Figure 3 shows that the stretching vibrational frequency
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Figure 3. Calculated IR spectra of the compound 1 in (a) cyclo-

hexane and (b) acetonitrile solvents based on the B1B95/TZVP Figure 4. Theoretical absorption and fluorescence humps for the 1-N
theoretical level. and 1-T forms in (a) cyclohexane and (b) acetonitrile solvents using
the B1B95/TZVP method.

of O1−H2 bond in compound 1 is charged from 3611.1 cm−1

(S0) to 3437.7 cm−1 (S1) in cyclohexane, which exhibits a
large red-shift value of 173.4 cm−1. Analogously, a large red-
shift value of 166.5 cm−1 is produced in the excitation
process [from 3613.3 cm−1 (S0) to 3446.8 cm−1 (S1)] in
acetonitrile. Aforementioned results again manifested that
intramolecular HB of compound 1 is intensified in the S1
state in both the solvents, which can facilitate the ESIPT
reactivity.
Next, we set out to determine whether the theoretical method
chosen is trustworthy. Therefore, the electronic spectra of com-
pound 1 in two solvents were simulated and are plotted in
Figure 4. For nonpolar cyclohexane solvent, the simulative
absorption hump of compound 1 is situated at 420 nm, which
was rather comparable with the experiment (408 nm).55
Furthermore, the simulative double fluorescence humps of
compound 1 are situated at 474 and 578 nm, respectively,
which were agree very well with experiment (434 and 568 nm). Figure 5. MOs (HOMO and LUMO) of the 1-N form and its
In addition, the simulative absorption (422 nm) and double transition energy in nonpolar cyclohexane (left) and polar acetonitrile
fluorescence (499 and 620 nm) humps were in better agree- (right) solvents.
ment with experiment (400, 480, and 590 nm) in polar aceto-
nitrile solvent. It can be significant to conclude that the Additionally, it is noteworthy that the enhancements of
B1B95/TZVP computing method was equal for the probe of electron density on O3 atoms implied the increase of
compound 1. intramolecular HB in two solvents. For the reason that the
Finally, we explored the charge distribution from the S0 to S1 frontier orbital energy gap (Egap) relates to the high chemical
states based on the analysis of the molecular orbitals (MOs) reactivity and low kinetic stability,84 the Egap values of HOMO
(see Figure 5). As plotted in Figure 5, the MOs of the 1-N → LUMO for compound 1 in both the solvents were
form exhibited the obvious π → π* characteristic transition calculated and are displayed in Figure 5. It can be seen that the
from the highest occupied molecular orbital (HOMO) to the Egap values were 3.620 and 3.585 eV in nonpolar cyclohexane
lowest unoccupied molecular orbital (LUMO) in two solvents. and polar acetonitrile solvents, respectively, which clarified that
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the compound 1 possesses the low kinetic stability and high

chemical reactivity in both the solvents.
3.1.3. Analysis of PECs. The main objective of this section
was to elucidate the dynamic ESIPT behaviors of compound 1
in two different polarity solvents. Accordingly, we scanned the
length of O1−H2 bond ranging from 0.975 to 1.975 with a step
size of 0.1 Å to construct the PECs on the S0 and S1 states,
respectively (see Figure 6). As can be noted in Figure 6(1,2),
the high potential barriers (PBs) are produced in the GSIPT
process in corresponding cyclohexane (11.52 kcal/mol) and
acetonitrile (12.74 kcal/mol) solvents, respectively, which testi-
fied that the PT process was difficult to occur in the S0 state in
both the solvents. However, the PBs that have been reduced
to 5.32 (in cyclohexane) and 7.27 kcal/mol (in acetonitrile)
verified that the PT process could happen in the S1 state. What
is more, the PB relationship with the (1) (5.32 kcal/mol) <
(2) (7.27 kcal/mol) in the S1 state denoted that the ESIPT
reaction was more likely to take place in nonpolar cyclohexane
solvent for compound 1.
3.2. 2,2′-((Phenylazanediyl)bis(4,1-phenylene))bis(3-
hydroxy-4H-chromen-4-one) (Compound 2). 3.2.1. Anal-
ysis of Geometric Constructions. On account of the structural
asymmetry of compound 2, we optimized out the four kinds of
stable configurations in the S0 and S1 states for the two solvents
using the B1B95/TZVP method, i.e. 2-N (normal form), 2-T1
(tautomer form: only H5 from O4 to O6), 2-T2 (tautomer
form: only H8 from O7 to O9), and 2-T3 (tautomer form: both
the H5 from O4 to O6 and H8 from O7 to O9), respectively (see
Figure 6. PECs of S0 and S1 states for compound 1 in cyclohexane (1) Figure 7). In addition, the important structural parameters of
and acetonitrile (2) solvents combined with the TDDFT/B1B95/TZVP these forms for compound 2 are recorded in Table 2. As shown
method. The inset presents the corresponding optimized constructions. in Table 2, for the nonpolar cyclohexane solvent, the BLs of
O4−H5 and O7−H8 for the 2-N form both are increased from
S0 (0.976 and 0.976 Å) to S1 (0.982 and 0.981 Å) states, and
the both separations of H5···O6 and H8···O9 are shortened
from S0 (1.961 and 1.956 Å) to S1 (1.892 and 1.911 Å)
accordingly. Moreover, both the BAs δ (O4−H5···O6 and O7−
H8···O9) in the S1 (122.8 and 121.7°) state were closer to 180°
than that in the S0 state (120.1 and 120.2°). It has been eluci-
dated that both the HBs (O4−H5···O6 and O7−H8···O9) of
compound 2 are heightened in the S1 state. The same verdict
could be gated for acetonitrile: the BLs of O4−H5 and O7−H8
from 0.975 and 0.975 Å (S0) changed to 0.979 and 0.980 Å
(S1); the separations of H5···O6 and H8···O9 from 1.977 and
1.970 Å (S0) changed to 1.927 and 1.923 Å (S1); the BAs δ
from 119.5 and 119.7° (S0) changed to 121.3 and 121.5° (S1).
To sum up, both the intramolecular HBs (O4−H5···O6 and
O7−H8···O9) are intensified in the S1 state in two solvents,
which can boost the ESIPT reactions for compound 2.
Furthermore, Figure 8 drew the RDG isosurfaces of com-
Figure 7. Optimized constructions of the 2-N, 2-T1, 2-T2, and 2-T3 pound 2 in the S0 and S1 states in two solvents, for ease of
forms by the B1B95/TZVP method in nonpolar cyclohexane and revelation of the interactions of two intramolecular HBs in the
polar acetonitrile solvents. real space. Evidently, the all spikes of around −0.03 au implied
Table 2. Primary Calculated BLs (Å) and BAs (°) of 2-N, 2-T1, 2-T2, and 2-T3 Constructions in the S0 and S1 States Based on
the DFT/TDDFT/B1B95-TZVP Methods in Cyclohexane and Acetonitrile Solvents, Respectively
2-N 2-T1 2-T2 2-T3
S0 S1 S0 S1 S0 S1 S0 S1
cyclohexane O4−H5 0.976 0.982 1.785 1.905 0.976 0.977 1.785 1.832
H5−O6 1.961 1.892 0.999 0.983 1.961 1.949 0.999 0.995
O7−H8 0.976 0.981 0.976 0.978 1.782 1.909 1.782 1.805
H8−O9 1.956 1.911 1.957 1.943 0.999 0.983 0.999 1.003

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Table 2. continued
2-N 2-T1 2-T2 2-T3
S0 S1 S0 S1 S0 S1 S0 S1
δ(O4−H5···O6) 120.1 122.8 125.4 121.5 120.1 120.3 125.4 125.2
δ(O7−H8···O9) 120.2 121.7 120.2 120.5 125.5 121.3 125.5 122.2
acetonitrile O4−H5 0.975 0.979 1.811 1.939 0.975 0.976 1.810 1.893
H5−O6 1.977 1.927 0.995 0.980 1.977 1.966 0.995 0.985
O7−H8 0.975 0.980 0.975 0.976 1.808 1.941 1.806 1.890
H8−O9 1.970 1.923 1.971 1.961 0.995 0.980 0.996 0.985
δ(O4−H5···O6) 119.5 121.3 124.5 120.3 119.5 119.7 124.6 121.7
δ(O7−H8···O9) 119.7 121.5 119.6 119.8 124.7 120.2 124.7 121.8

Figure 8. RDG isosurfaces for the compound 2: the S0 (1A) and S1 (2A) states in cyclohexane; the S0 (1B) and S1 (2B) states in acetonitrile.

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Figure 9. Calculated IR spectra of compound 2 in (a) cyclohexane Figure 10. Theoretical absorption and fluorescence humps for the
and (b) acetonitrile solvents based on the B1B95/TZVP theoretical compound 2 in (a) nonpolar cyclohexane and (b) polar acetonitrile
level. solvents using the B1B95/TZVP method.

that the intramolecular HB interactions existed in the S0 and S1

states in both the solvents for compound 2.
3.2.2. IR, Electronic Spectra and MOs. The IR vibration
spectra of compound 2 in two solvents are calculated and
shown in Figure 9. As Figure 9 displays, it is seen that the
two red-shift values of 89.1 (O4−H5) and 84.4 cm−1 (O7−H8)
occurred in process of S0 → S1 states in nonpolar cyclohexane
solvent, based on the variations of the stretching vibrational
frequencies of O4−H5 [3609.4 cm−1 (S0) → 3520.3 cm−1 (S1)]
and O7−H8 [3602.9 cm−1 (S0) → 3518.5 cm−1 (S1)]. In addi-
tion, it is also concluded that the two red-shift values of 83.0
(O4−H5) and 81.2 cm−1 (O7−H8) happened from S0 to S1
states in polar acetonitrile solvent combining with the changes
of the stretching vibrational frequencies of O4−H5 [3612.5 cm−1
(S0) → 3529.5 cm−1 (S1)] and O7−H8 [3605.7 cm−1 (S0) → Figure 11. MOs (HOMO and LUMO) of the 2-N form and its transi-
tion energy in cyclohexane (left) and acetonitrile (right) solvents.
3524.5 cm−1 (S1)]. Hence, we could determine that the two
intramolecular HBs (O4−H5···O6 and O7−H8···O9) are
enhanced in the S1 state in both the solvents, which can experiment (429 nm).55 The fluorescence hump of 2-N is
promote the ESIPT reactions for compound 2. situated at 512 nm, which generated a Stokes shift of 83 nm.
Figure 10 depicts the calculative electronic spectra and Besides, the simulative fluorescence humps of 2-T1, 2-T2, and
corresponding experimental values (shown in parentheses) for 2-T3 are situated at 628, 627, and 668 nm, respectively. It is
compound 2, in which Figure 10a,b indicates these in nonpolar worthy to note that emission spectra manifest the visible
cyclohexane and polar acetonitrile solvents, respectively. double fluorescent phenomena for compound 2 in both the
For the cyclohexane solvent, the absorption hump of 2-N is solvents. However, there were no complete data of emission
situated at 447 nm, which was rather comparable with the spectra, which stemmed from the experimental report.55 There
experimental value (415 nm).55 The fluorescence hump of 2-N were two reasons for pursuing this: one was that the difference
is situated at 484 nm, which demonstrated a Stokes shift of between fluorescence humps of 2-T1 and 2-T2 in acetonitrile
37 nm. Additionally, the calculated fluorescence humps of 590, solvent was intensely small; second was that the 2-T3 cannot
587, and 717 nm are attributed to 2-T1, 2-T2, and 2-T3 forms, be formed due to high PEBs in two solvents. As a matter of
respectively. For the acetonitrile solvent, the value of absorp- fact, the reality may be more complicated, and we will put
tion hump of 2-N is situated at 450 nm and was close to forward the in-depth exploration in Section 3.2.3.
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Table 3. Electronic Excitation Energy (nm), the

Corresponding Oscillator Strengths, and the Corresponding
Compositions of the Low-Lying Singlet Excited States of the
Compound 2
transition λ (nm) f composition CI (%)
cyclohexane S0 → S1 447.8 1.1722 H →L 96.5
S0 → S2 398.7 0.3417 H →L+1 97.0
S0 → S3 330.7 0.1123 H −1→L 90.4
S0 → S4 323.4 0.0178 H →L+4 59.4
acetonitrile S0 → S1 450.6 1.1632 H →L 96.7
S0 → S2 399.7 0.3237 H →L+1 97.4
S0 → S3 329.8 0.1169 H −1→L 90.2
S0 → S4 321.9 0.0177 H →L+4 58.8

Figure 13. PESs of (a) S1 and (b) S0 states for compound 2 in

nonpolar cyclohexane solvent.

diminution. Figure 12 presents the perfectly obvious fact that

Figure 12. Electron density difference map between the S0 and S1
states of compound 2 at the TDDFT/B1B95/TZVP level in (a) nonpolar
cyclohexane and (b) polar acetonitrile solvents. The orange zones indicate
electron density loss, whereas the green zones correspond to a gain in
density following photon absorption.
To illustrate the charge distributions for compound 2 after
optical-excitation, the MOs and Egap in two solvents are
described in Figure 11, and the calculated electronic transition
energies, corresponding oscillator strengths (f), and composi-
tions are listed in Table 3. The HOMO and LUMO of 2
compound were observed in two solvents (see Figure 11),
implying that their charge-transfer transitions were π → π* by
nature and accompanying the diminution of electron density
on O4 and O7 atoms and increase of electron density on O6
and O9 atoms. Here, to reveal this phenomenon more
intuitively, the maps of the electron density difference between
the S0 and S1 states for compound 2 are plotted in Figure 12,
in which the green range shows the increase of the electron
density after excitation, and the orange range shows the
3944
the electron density on O6 and O9 was increased after photo-
excitation, while the electron density on O4 and O7 atoms was
decreased. Meanwhile, the Egap values of HOMO → LUMO
for compound 2 in cyclohexane (4.345 eV) and acetonitrile
(4.354 eV) solvents are shown in Figure 11. It is obvious that
compound 2 also has the low kinetic stability and high
chemical reactivity in both the solvents.
3.2.3. Analysis of PESs. As the above discussion shows, we
could forecast that the ESIPT processes can take place for
compound 2 in two solvents. Here, to better shed light on the
ESIPT mechanisms of compound 2 in two solvents, the PESs
as functions of O4−H5 and O7−H8 bonds were structured
by feat of the restricted optimization method in Figures 13
and 14. In addition, we tabulated the relevant PEBs for ESIPT
processes in Tables S2 and S3. It is worth noting that scanning
the PESs along the O4−H5 and O7−H8 BLs can offer tentative
insights into the ESIPT mechanism, but the reaction barrier
does not necessarily coincide with the “true” barrier between
the reactant and the saddle point for the large molecules with
much geometrical freedom. As can be noted in Figure 13b and
Table S2, the PEBs illustrated that both single and double PT
reactions for compound 2 were impracticable in the S0 state on
cyclohexane. For acetonitrile, the PT reactions likewise were
infeasible in the S0 state (see Figure 14b and Table S3).
As Figure 13a displays, the four stable constructions with
O4−H5/O7−H8 lengths are denoted as A (0.982/0.981 Å)
(2-N), B (1.905/0.978 Å) (2-T1), C (0.977/1.909 Å) (2-T2),
DOI: 10.1021/acs.jpca.9b00879
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The Journal of Physical Chemistry A
Figure 14. PESs of (a) S1 and (b) S0 states for compound 2 in polar
acetonitrile solvent.
and D (1.832/1.805 Å) (2-T3), respectively. What is more, the
relative energies of these stable constructions in cyclohexane
solvent are demonstrated in Table 4. Therefore, the conceiv-
able four single-ESIPT processes [shown as I (A → B), II
(A → C), III (B → D), and IV (C → D)] and three double-
ESIPT processes [shown as V (A → B → D), VI (A → C → D),
and VII (A → D)] were presented due to asymmetric config-
uration of compound 2. As seen in Table 4, the relationship of
PE between four stable constructions was EA ≈ EB ≈ EC < ED,
which exhibits that the ESIPT reactions may occur for the
nonpolar cyclohexane solvent. It is clear that the single-ESIPT
processes I (A → B) and II (A → C) are allowed in the S1 state
due to low PEBs (6.26 and 6.62 kcal/mol) (seen in Table S2)
for cyclohexane solvent. In contrast, the high PEBs produced
the following paths to be banned: single-ESIPT processes III
(B → D) (11.68 kcal/mol) and IV (C → D) (12.02 kcal/mol)
and double-ESIPT processes V (A → B → D) (6.26 and
11.68 kcal/mol), VI (A → C → D) (6.62 and 12.02 kcal/mol),
and VII (A → D) (16.45 kcal/mol). Thus, it is concluded that
only single-ESIPT processes (I and II) could take place in
cyclohexane for compound 2, and double-ESIPT processes (V,
VI, and VII) were forbidden in the S1 state because these PBEs
Table 4. Potential Energy (Hartree) of the Stable Constructions in the S0 and S1 States
2-N
S0 S1 S0
cyclohexane 0.00 61.41 11.52
Acetonitrile −6.40 52.09 4.44
Article
were higher than 11 kcal/mol. In addition, the single-ESIPT
processes (I and II) were competing relationships, and process
I had a little advantage over the II. In addition, reverse PT
(RPT) reactions for nonpolar cyclohexane solvent in the S1
state could happen due to the low PBEs among these four stable
constructions of less than 6.10 kcal/mol (see in Table S2).
As seen in Figure 14a, the four minimum points also
appeared on the S1 state PES in polar acetonitrile solvent: A′
(0.979/0.980 Å), B′ (1.939/0.976 Å), C′ (0.976/1.941 Å), and
D′ (1.893/1.890 Å), and the energy-variant sequence was EA′
≈ EB′ ≈ EC′ < ED′. Therefore, the possible kind of PT paths in
S1 state was the same as that in cyclohexane: four single-ESIPT
processes [I′ (A′ → B′), II′ (A′ → C′), III′ (B′ → D′), and IV′
(C′ → D′)] and three double-ESIPT processes [V′ (A′ →
B′ → D′), VI′ (A′ → C′ → D′), and VII′ (A′ → D′)]. Based
on the calculated results from Table S3, it is noteworthy that
only the single-ESIPT processes I′ (6.91 kcal/mol) and II′
(6.90 kcal/mol) could occur in acetonitrile, and their proba-
bility were roughly the same. Moreover, the double-ESIPT
processes (V′, VI′, and VII′) are embargoed in the S1 state
due to these high PBEs. The RPT processes for acetonitrile
solvent in the S1 state could happen due to PBEs of less than
9.08 kcal/mol (seen in Table S3).
Ultimately, it can be significant to conclude that only single-
ESIPT processes could occur for compound 2, and double-
ESIPT processes are prohibited due to higher PBEs, whether
in nonpolar cyclohexane or polar acetonitrile solvents. Further-
more, the single-ESIPT processes (I and II) in nonpolar
cyclohexane were more sensitive than that (I′ and II′) in polar
acetonitrile. Besides, the process I had a little advantage over
the process II in cyclohexane, while the probabilities of processes
I′ and II′ were roughly the same in acetonitrile.
4. CONCLUSIONS
In summary, the ESIPT mechanisms of compounds 1 and 2 in
nonpolar cyclohexane and polar acetonitrile solvents were given a
molecular-level exposition based on theoretical investigation.
Upon the photoexcitation, the intramolecular HBs were inten-
sified in the S1 state for both compounds 1 and 2, which
presents the feasibility of ESIPT reactions in two solvents.
Additionally, the charge redistribution further exposed the
ESIPT trend for these compounds. It is worthy to note that
the ESIPT reaction of compound 1 in the nonpolar cyclohexane
solvent was more susceptible than that in polar acetonitrile
solvent. For asymmetric compound 2, it is concluded that only
single-ESIPT processes [I (6.26 kcal/mol), I′ (6.62 kcal/mol)],
[II (6.91 kcal/mol), and II′ (6.90 kcal/mol)] could occur in
both the solvents due to low PEBs, and double-ESIPT pro-
cesses were prohibitive due to high PBEs. Besides, the single-
ESIPT processes (I and II) in nonpolar cyclohexane were more
susceptible than those (I′ and II′) in polar acetonitrile. In addi-
tion, the process I had a little advantage over the process II in
cyclohexane, while the possibilities of processes I′ and II′ were
roughly the same in acetonitrile. Here, our sincere wish is that
this study not only illustrates the detailed ESIPT mechanisms
of compounds 1 and 2 in two different solvents but also maybe
2-T1 2-T2 2-T3
S1 S0 S1 S0 S1
61.93 11.50 62.18 23.02 73.62
52.39 4.40 52.42 15.25 60.04
3945 DOI: 10.1021/acs.jpca.9b00879
J. Phys. Chem. A 2019, 123, 3937−3948
The Journal of Physical Chemistry A
boosts the relevant utilization and development about these
chromophores in the future.
■
ASSOCIATED CONTENT
*
S Supporting Information
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acs.jpca.9b00879.
Comparing theoretical absorption data for compound 1
in cyclohexane solvent based on different functionals
(B3LYP, CAM-B3LYP, M06, B1B95, PBEPBE,
WB97XD); calculated potential energy barriers (kcal/mol)
among the four stable points on both S0 and S1 state
PESs for compound 2 in nonpolar cyclohexane solvent;
calculated potential energy barriers (kcal/mol) among
the four stable points on both S0 and S1 state PESs for
compound 2 in polar acetonitrile solvent; Cartesian
coordinates of constructions (1-N and 1-T) in S0 and S1
states in nonpolar cyclohexane and polar acetonitrile
solvents; Cartesian coordinates of constructions (2-N,
2-T1, 2-T2, and 2-T3) in S0 and S1 states in nonpolar
cyclohexane and polar acetonitrile solvents (PDF)
■
AUTHOR INFORMATION
Corresponding Author
*E-mail: light_yang@dicp.ac.cn. Phone: +86-411-84379037.
Fax: +86-411-84675584.
ORCID
Yang Yang: 0000-0002-3387-2417
Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS
We sincerely thank the financial support from the National
Natural Science Foundation of China (grants no. 21403226
and 21503226).
■
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3948 DOI: 10.1021/acs.jpca.9b00879

J. Phys. Chem. A 2019, 123, 3937−3948