Boosting the Efficiency of Dye-Sensitized Solar Cells by a Multifunctional Composite Photoanode to 14.13 .

We report a new strategy to fabricate a multifunctional composite photoanode containing TiO2 hollow spheres (TiO2 -HSs), Au nanoparticles (AuNPs) and novel NaYF4 : Yb,Er@NaLuF4 : Eu@SiO2 upconversion nanoparticles (UCNPs). The AuNPs are grown on the photoanode film including TiO2 -HSs and UCNPs by a simple in situ plasmonic treatment. As a result, an impressive power conversion efficiency of 14.13 % is obtained, which is a record for N719 dye-based dye-sensitized solar cells, demonstrating great potential for the solar cells toward commercialization. This obvious enhancement is ascribed to a collaborative mechanism of the TiO2 -HSs exhibiting excellent light-scattering ability, of the UCNPs converting near-infrared photons into visible photons and of the AuNPs presenting outstanding surface plasmon resonance effect. Notably, a steady-state experiment further reveals that the champion cell exhibits 95.33 % retainment in efficiency even after 180 h of measurements, showing good device stability.

Theoretical study on photophysical properties of a series of functional pyrimidine-based organic light-emitting diodes emitters presenting thermally activated delayed fluorescence.

Issue concerning accurate prediction of the reverse intersystem crossing rate (kRISC ) is critical for developing novel efficient thermally activated delayed fluorescence (TADF) materials. In this contribution, the kRISC rates from the lowest excited triplet T1 state to the lowest excited singlet S1 state were evaluated for five donor-π-acceptor-type pyrimidine-based TADF emitters using the semiclassical Marcus theory. Both the singlet-triplet energy difference (ΔEST ) and spin-orbit coupling (V) between the S1 and T1 states were investigated by performing the density functional theory (DFT) and time-dependent density functional theory (TD-DFT) calculations. In addition, their fluorescence emission wavelengths (λem ) were also calculated at the TD-DFT level. The predicted kRISC and λem values are found to reproduce well the available experimental findings. The present results reveal that the kRISC rates of molecules possessing the unsymmetrical diphenyl pyrimidine acceptor core are calculated to be slightly larger than those of their analogues with the symmetrical diphenyl pyrimidine. In addition, introducing two tert-butyl groups into the 2,7-positions of the donor moiety of the latter is also an effective method for increasing kRISC when designing TADF emitters. Such a difference is related to the nature of the T1 excited state. A more remarkable charge-transfer (CT) contribution to the state can achieve a smaller ΔEST , leading to a more efficient RISC process, and consequently a shorter delayed fluorescence lifetime as observed experimentally. © 2019 Wiley Periodicals, Inc.

Theoretical studies on thermally activated delayed fluorescence mechanism of a series of organic light-emitting diodes emitters comprising 2,7-diphenylamino-9,9-dimethylacridine as electron donor.

According to one experimentally reported thermally activated delayed fluorescence (TADF) emitter (AcDPA-2TP), two new molecules (AcDPA-2PP and AcDPA-TPP) have been designed theoretically to probe into the effect of different acceptor strengths on their TADF mechanisms. In this work, the rates of reverse intersystem crossing (kRISC ) of the three targeted molecules were calculated by the semiclassical Marcus rate expression. The present results demonstrate that the kRISC rate of AcDPA-2PP is estimated to be 5.56 × 106 s-1 , about twice larger than that of AcDPA-2TP (2.63 × 106 s-1 ), and especially AcDPA-TPP is found to exhibit the largest kRISC value (6.97 × 106 s-1 ) among the three molecules. Considering that AcDPA-2TP has been observed to be an efficient TADF emitter, our newly designed two molecules AcDPA-2PP and AcDPA-TPP are also expected to be potential TADF materials. © 2018 Wiley Periodicals, Inc.

Theoretical insights into the 1D-charge transport properties in a series of hexaazatrinaphthylene-based discotic molecules.

Discotic liquid crystal (DLC) materials have attracted considerable attention mainly due to their high charge carrier mobilities in quasi-one-dimensional columns. In this article, five hexaazatrinaphthylene-based DLC molecules were investigated theoretically, and their frontier molecular orbital energy levels, crystal structures, and electron/hole drift mobilities were calculated by combination of density functional theory (DFT) and semiclassical Marcus charge transfer theory. The systems studied in this work include three experimentally reported molecules (1, 2, and 3) and two theoretically designed molecules (4 and 5). Compared with the 1-3 compounds, 4 and 5 have three more extended benzene rings in the π-conjugated core. The present results show that the orders of the frontier molecular orbital energy levels and electron drift mobilities agree very well with the experiment. For 4 and 5, the electron/hole reorganization energies are lower than those of compounds 1-3. Furthermore, the calculated electron/hole transfer integral of 5 is the largest among all the five systems, leading to the highest electron and hole mobilities. In addition, the hydrophobicity and solubility were also evaluated by DFT, indicating that compound 5 has good hydrophobicity and good solubility in trichloromethane. As a result, it is expected that compound 5 can be a potential charge transport material in electronic and optoelectronic devices. © 2017 Wiley Periodicals, Inc.

Multi-state nonadiabatic deactivation mechanism of coumarin revealed by ab initio on-the-fly trajectory surface hopping dynamic simulation.

An on-the-fly trajectory surface hopping dynamic simulation has been performed for revealing the multi-state nonadiabatic deactivation mechanism of coumarin. The mechanism involves three adiabatic excited states, S3(ππ*Lb), S2(nπ*, ππ*La) and S1(ππ*La, nπ*), and the ground state S0 at the four state-averaged complete active space self-consistent field, SA4-CASSCF(12,10)/6-31G* level of theory. Upon photoexcitation to the third excited state S3(ππ*Lb) in the Franck-Condon region, 80% sampling trajectories decay to the dark S2(nπ*) state within an average of 5 fs via the conical intersection S3(ππ*Lb)/S2(nπ*), while 20% decay to the S2(ππ*La) state within an average of 11 fs via the conical intersection S3(ππ*Lb)/S2(ππ*La). Then, sampling trajectories via S2(nπ*)/S1(ππ*La) continue with ultrafast decay processes to give a final distribution of quantum yields as follows: 42% stay on the dark S1(nπ*) state, 43.3% go back to the ground S0 state, 12% undergo a ring-opening reaction to the Z-form S0(Z) state, and 2.7% go to the E-form S0(E) state. The lifetimes of the excited states are estimated as follows: the S3 state is about 12 fs on average, the S2 state is about 80 fs, and the S1 state has a fast component of about 160 fs and a slow component of 15 ps. The simulated ultrafast radiationless deactivation pathways of photoexcited coumarin immediately interpret the experimentally observed weak fluorescence emission.

Ultrafast excited-state deactivation of 9-methylhypoxanthine in aqueous solution: A QM/MM MD study.

Photoinduced ultrafast non-adiabatic decay of 9-methylhypoxanthine (9MHPX) in aqueous solution was investigated by ab initio surface-hopping dynamics calculations using a combined quantum mechanical/molecular mechanical approach. The absorption spectra of 9MHPX in aqueous solution were also explored by the hybrid cluster-continuum model at the level of time-dependent density functional theory along with the polarizable continuum model (PCM). The static electronic-structure calculations indicate that the absorption spectra of 9MHPX simulated by TD-B3LYP/PCM and TD-X3LYP/PCM can reproduce very well the experimental findings, with the accuracy of about 0.20 eV. According to dynamics simulations, irradiation of 9MHPX populates the bright excited singlet S1 state, which may undergo an ultrafast non-radiative deactivation to the S0 state. The lifetime of the S1 state of 9MHPX in aqueous solution is predicted to be 115.6 fs, slightly longer than that in the gas phase (88.8 fs), suggesting that the solventwater has no significant influence on the excited-state lifetime of 9MHPX. Such a behavior in 9MHPX is distinctly different from its parent hypoxanthine keto-N9H tautomer in which the excited-state lifetime of the latter in watersolution was remarkably enhanced as compared to the gas phase. The significant difference of the photodynamical behaviors between 9MHPX and keto-N9H can be ascribed to their different hydrogen bond environment in aqueous solution.

A CASSCF/CASPT2 insight into excited-state intramolecular proton transfer of four imidazole derivatives.

Excited-state intramolecular proton transfer (ESIPT) of four imidazole derivatives, 2-(2'-hydroxyphenyl)imidazole (HPI), 2-(2'-hydroxyphenyl)benzimidazole (HPBI), 2-(2'-hydroxyphenyl)-1H-phenanthro[9,10-d]imidazole (HPPI) and 2-(2'-hydroxyphenyl)-1-phenyl-1H-phenanthro[9,10-d]imidazole (HPPPI), were studied by the sophisticated CASSCF/CASPT2 methodology. The state-averaged SA-CASSCF method was used to optimize their geometry structures of S0 and S1 electronic states, and the CASPT2 calculations were used for the calibration of all the single-point energies, including the absorption and emission spectra. A reasonable agreement is found between the theoretical predictions and the available experimental spectral data. The forward ESIPT barriers of four target compounds gradually decrease with the increase of molecular size. On the basis of the present calculations, it is a plausible speculation that the larger the size, the faster is the ESIPT rate, and eventually, HPPPI molecule can undergo a completely barrierless ESIPT to the more stable S1 keto form. Additionally, taking HPI as a representative example, the radiationless decays connecting the S0 and S1 /S0 conical intersection structures were also studied by constructing a linearly interpolated internal coordinate (LIIC) reaction path. The qualitative analysis shows that the LIIC barrier of HPI in the keto form is remarkably lower than that of its enol-form, indicating that the former has a big advantage over the latter in the nonradiative process.

A QM/MM MD insight into photodynamics of hypoxanthine: distinct nonadiabatic decay behaviors between keto-N7H and keto-N9H tautomers in aqueous solution.

Extensive ab initio surface-hopping dynamics simulations have been used to explore the excited-state nonadiabatic decay of two biologically relevant hypoxanthine keto-N7H and keto-N9H tautomers in aqueous solution. QM/MM calculations and QM/MM-based MD simulations predict different hydrogen bonding networks around these nucleobase analogues, which influence their photodynamical properties remarkably. Furthermore, different solvent effects on the conical intersection formation of keto-N7H and keto-N9H were found in excited-state MD simulations, which also change the lifetimes of the excited states. In comparison with the gas-phase situation, the S1 → S0 nonradiative decay of keto-N7H is slightly faster, while this decay process of keto-N9H becomes much slower in water. The presence of π-electron hydrogen bonds in the solvated keto-N7H is considered to facilitate the S1 → S0 nonradiative decay process.

Ab initio study on ultrafast excited-state decay of allopurinol keto-N9H tautomer from gas phase to aqueous solution.

The excited-state decay of the biologically relevant allopurinol keto-N9H tautomer populated at the optically bright S1((1)ππ*) state in the gas phase and in aqueous solution has been explored theoretically. In solution, the hybrid quantum-mechanical/molecular-mechanical simulations were performed, where the QM region (keto-N9H) was treated at the ab initio SA-CASSCF level, while the MM region (water) was described by the TIP3P model. Here we find that there exist four parallel relaxation pathways in the gas phase, but only two of them occur in aqueous solution. In addition, an ultrafast S1 → S0 internal conversion is found in vacuum, with an estimated excited-state lifetime of 104.7 fs, much faster than that in water (242.8 fs), showing reasonable agreement with the available experimental finding in aqueous solution (τ < 200 fs). Calculations indicate that the presence of water solvent plays an important role in the excited-state dynamics of DNA base, showing the pronounced environmental effects on its decay pathways and excited-state lifetimes.

Ab initio insight into ultrafast nonadiabatic decay of hypoxanthine: keto-N7H and keto-N9H tautomers.

Nonadiabatic dynamics simulations at the SA-CASSCF level were performed for the two most stable keto-N7H and keto-N9H tautomers of hypoxanthine in order to obtain deep insight into the lifetime of the optically bright S1((1)ππ*) excited state and the relevant decay mechanisms. Supporting calculations on the ground-state (S0) equilibrium structures and minima on the crossing seams of both tautomers were carried out at the MR-CIS and CASSCF levels. These studies indicate that there are four slightly different kinds of conical intersections in each tautomer, exhibiting a chiral character, each of which dominates a barrierless reaction pathway. Moreover, both tautomers reveal the ultrafast S1→ S0 decay, in which the S1 state of keto-N9H in the gas phase has a lifetime of 85.5 fs, whereas that of keto-N7H has a longer lifetime of 137.7 fs. An excellent agreement is found between the present results and the experimental value of 130 ± 20 fs in aqueous solution (Chen and Kohler, Phys. Chem. Chem. Phys., 2012, 14, 10677-10689).

Liquid Nitrogen Sources Assisting Gram-Scale Production of Single-Atom Catalysts for Electrochemical Carbon Dioxide Reduction.

Developing metal-nitrogen-carbon (M-N-C)-based single-atom electrocatalysts for carbon dioxide reduction reaction (CO2 RR) have captured widespread interest because of their outstanding activity and selectivity. Yet, the loss of nitrogen sources during the synthetic process hinders their further development. Herein, an effective strategy using 1-butyl-3-methylimidazolium tetrafluoroborate ([BMIM][BF4 ]) as a liquid nitrogen source to construct a nickel single-atom electrocatalyst (Ni-SA) with well-defined Ni-N4 sites on a carbon support (denoted as Ni-SA-BB/C) is reported. This is shown to deliver a carbon monoxide faradaic efficiency of >95% over a potential of -0.7 to -1.1 V (vs reversible hydrogen electrode) with excellent durability. Furthermore, the obtained Ni-SA-BB/C catalyst possesses higher nitrogen content than the Ni-SA catalyst prepared by conventional nitrogen sources. Importantly, only thimbleful Ni nanoparticles (Ni-NP) are contained in the large-scale-prepared Ni-SA-BB/C catalyst without acid leaching, and with only a slight decrease in the catalytic activity. Density functional theory calculations indicate a salient difference between Ni-SA and Ni-NP in the catalytic performance toward CO2 RR. This work introduces a simple and amenable manufacturing strategy to large-scale fabrication of nickel single-atom electrocatalysts for CO2 -to-CO conversion.

Ab initio characterization of size dependence of electronic spectra for linear anionic carbon clusters C(n) (-) (n = 4-17).

In this article, we determine the ground-state equilibrium geometries of the linear anionic carbon clusters C n- (n = 4-17) by means of the density functional theory B3LYP, CAM-B3LYP, and coupled cluster CCSD(T) calculations, as well as their electronic spectra obtained by the multireference second-order perturbation theory CASPT2 method. These studies indicate that these linear anions possess doublet ²∏(g) or ²∏(u) ground state, and the even-numbered clusters are generally acetylenic, whereas the odd-numbered ones are essentially cumulenic. The energy differences, electron affinities, and incremental binding energies of C n- chains all exhibit a notable tread of parity alternation, with n-even chains being more stable than n-odd ones. In addition, the predicted vertical excitation energies from the ground state to four low-lying excited states are in reasonably good agreement with the available experimental observations, and the calculations for the higher excited electronic transitions can provide accurate information for the experimentalists and spectroscopists. Interestingly, the absorption wavelengths of the 1²∏(u/g) ← X²∏(g/u) transitions of the n-even clusters show a nonlinear trend of exponential growth, whereas those of the n-odd counterparts are found to obey a linear relationship as a function of the chain size, as shown experimentally. Moreover, the absorption wavelengths of the transitions to the higher excited states of C n- series have the similar linear size dependence as well.

Low-lying electronic states and their nonradiative deactivation of thieno[3,4-b]pyrazine: an ab initio study.

State-averaged complete active space self-consistent field (SA-CASSCF) calculations have been used to locate the four low-lying electronic states of thieno[3,4-b]pyrazine (TP), and their vertical excitation energies and emission energies have been determined by means of the multistate complete active space with second-order perturbation theory (MS-CASPT2) calculations. The present results indicate that the first weak (1)nπ∗ excited state has a C(s)-symmetry structure, unlike two bright (1)ππ∗ excited states in C(2v) symmetry. The predicted vertical excitation energies of the three low-lying excited states in the gas phase are 3.41, 3.92, and 4.13 eV at the restricted-spin coupled-cluster single-double plus perturbative triple excitation [RCCSD(T)] optimized geometry, respectively. On the basis of calculations, a new assignment to the observed spectra of TP was proposed, in which the (1)nπ∗ state should be responsible for the weak absorption centred at 3.54 eV and the two closely spaced (1)ππ∗ states account for the two adjacent absorption bands observed at 3.99 and 4.15 eV. The predicted vertical emission energies lend further support to our assignments. Surface hopping dynamics simulations performed at the SA-CASSCF level suggest that the plausible deactivation mechanism comprises an ultrafast relaxation of the (1)ππ∗ excited states to (1)nπ∗ excited state, followed by a slow conversion to the S(0) ground state via a conical intersection. This internal conversion is accessible, since the MS-CASPT2 predicted energy barrier is ∼0.55 eV, much lower than the Franck-Condon point populated initially under excitation. The dynamical simulations on the low-lying states for 500 fs reveal that the relatively high (1)ππ∗ excited states can be easily trapped in the (1)nπ∗ excited state, which will increase the lifetime of the excited thieno[3,4-b]pyrazine.

An effective strategy for simply varying relative position of two carbazole groups in the thermally activated delayed fluorescence emitters to achieve deep-blue emission.

The development of efficient deep-blue thermally activated delayed fluorescence (TADF) materials is especially important for organic light-emitting devices as displays and lighting sources. However, finding suitable deep-blue TADF emitters is still challenging. Based on an experimentally reported blue-light TADF emitter DCZ-TTR, two new molecules (DCZ1-TTR and DCZ2-TTR) have been designed to investigate the impact of the change of relative position in two carbazole groups on their TADF properties. Density functional theory (DFT) and time-dependent density functional theory (TD-DFT) calculations coupled with the Marcus rate theory have been performed. It is found that the absorption and emission spectra simulated using the BMK functional can reproduce the available experimental data very well. The fluorescence emissions of DCZ1-TTR and DCZ2-TTR are predicted to show clear blue-shifting in cyclohexane with respect to their analogue DCZ-TTR. Especially, the emission wavelength of DCZ2-TTR is calculated to be 435nm, in the deep-blue light range. According to the Marcus rate theory, the rates of reverse intersystem crossing of DCZ1-TTR and DCZ2-TTR are estimated to be two orders of magnitude larger than that of DCZ-TTR, which is more favorable for the occurrence of delayed fluorescence. This strongly suggests that our newly designed two molecules DCZ1-TTR and DCZ2-TTR can be also expected to be potential blue-light or even deep-blue-light TADF emitters. This may be an effective strategy for realizing deep-blue emission by simply varying relative position of two carbazole groups in the TADF molecules. To our best knowledge, this is a novel finding, which may be useful in preparing highly efficient deep-blue TADF-OLED materials.

Electronic spectra of the linear polyyne cations HC(2n)H(+) (n=2-8): An ab initio study.

The B3LYP, CAM-B3LYP, and RCCSD(T) calculations have been used to determine the ground-state geometries of the linear polyyne cations HC(2n)H(+) (n=2-8). The CASSCF method has also been used to optimize the ground and first excited states. The present results indicate that these linear cations generally have an acetylenic structure H-C identical withC-C identical withCcdots, three dots, centeredC identical withC-H(+) with the ground state of X (2)Pi(g) for even-numbered n or X (2)Pi(u) for odd-numbered n. Moreover, the bond length alternation of HC(2n)H(+) is less pronounced than the corresponding one of the neutral polyyne chains HC(2n)H. The CASPT2 approach has been employed to estimate the vertical excitation energies for the dipole-allowed (Acdots, three dots, centeredD) (2)Pi(u/g)<--X (2)Pi(g/u) transitions in HC(2n)H(+) (n=2-8) clusters. The predicted A (2)Pi(u/g)<--X (2)Pi(g/u) transition energies in the gas phase are 2.62, 2.14, 1.81, 1.52, 1.35, 1.22, and 1.10 eV, respectively, in excellent agreement with the corresponding observed values of 2.45, 2.07, 1.75, 1.52, 1.35, 1.20, and 1.08 eV. The present calculations show that the absorption wavelengths for the A (2)Pi(u/g)<--X (2)Pi(g/u) transitions exhibit notably linear size dependence, as shown in previous experimental studies, quite different from the nonlinear lambda-n relationship for origin bands in HC(2n)H.

Strategy for tuning the up-conversion intersystem crossing rates in a series of organic light-emitting diodes emitters relevant for thermally activated delayed fluorescence.

Accurate prediction on the up-conversion intersystem crossing rate (kUISC) is a critical issue for the molecular design of an efficient thermally activated delayed fluorescence (TADF) emitter, and the kUISC rate is considered to be mainly determined by the spin-orbit coupling matrix element (SOCME) and the singlet-triplet energy difference (∆EST). In the present contribution, we strategically designed a series of organic molecules, bearing an isoindole-dione core as the electron acceptor (A) unit and dinitrocarbazolyl, carbazolyl, diphenylcarbazolyl, dicarbazolyl and tercarbazolyl groups as the electron donor (D) units, respectively. Their SOCME and ∆EST values between the S1 and T1 states were calculated by the DFT and TD-DFT methodes, and the kUISC rates were estimated by using the semiclassical Marcus theory. The present studies indicate that as the π-conjugation in the D unit enhances, the ∆EST value gradually decreases, and the kUISC rate gradually increases. The molecule using tercarbazolyl as the D moiety is found to exhibit the largest kUISC in the present computations, as high as 1.22 × 106 s-1, which is of the same order of magnitude as an experimentally observed highly-efficient TADF emitter using a 4-benzoylpyridine as the A unit and the same tercarbazolyl group as the D moiety. The present results sufficiently prove the necessity of introducing strong electron-rich substituent groups when designing highly efficient TADF emitters.

Benzimidazobenzothiazole-based highly-efficient thermally activated delayed fluorescence emitters for organic light-emitting diodes: A quantum-chemical TD-DFT study.

Based upon two thermally activated delayed fluorescence (TADF) emitters 1 and 2, compounds 3-6 have been designed by replacing the carbazol group with the bis(4-biphenyl)amine one (3 and 4) and introducing the electron-withdrawing CF3 group into the acceptor unit of 3 and 4 (5 and 6). It is found that the present calculations predict comparable but relatively large energy differences (approximate 0.5eV) between the lowest singlet S1 and triplet T1 states (∆EST) for the six targeted compounds. In order to explain the highly-efficient TADF behavior observed in compounds 1 and 2, the"triplet reservoir" mechanism has been proposed. In addition, the fluorescence rates of all six compounds are very large, in 107-108 orders of magnitude. According to the present calculations, it is a reasonable assumption that the newly designed compounds 3-6 could be considered as the potential TADF emitters, which needs to be further verified by experimental techniques.

Theoretical studies on electroluminescent mechanism of a series of thermally activated delayed fluorescence emitters possessing asymmetric-triazine-cored triads.

A series of thermally activated delayed fluorescence (TADF) emitters using asymmetric-triazine-cored triad as the electron-accepting unit have been investigated theoretically. Based on two experimentally reported TADF molecules (TPXZ-as-TAZ and oDPXZ-as-TAZ), two new molecules (mDPXZ-as-TAZ and pDPXZ-as-TAZ) have been designed to explore the isomeric effect on their TADF properties. The present results reveal that the absorption and emission spectra calculated by the time-dependent density functional theory (TD-DFT) method at the M06-2X level are match well the available experimental findings, and mDPXZ-as-TAZ and pDPXZ-as-TAZ are found to exhibit the same yellow emission as their analogue oDPXZ-as-TAZ. In addition, the rates of reverse intersystem crossing of mDPXZ-as-TAZ and pDPXZ-as-TAZ estimated by the semiclassical Marcus theory are 2.51 × 106 and 4.57 × 106 s-1, respectively, one order of magnitude larger than that of oDPXZ-as-TAZ (1.27 × 105 s-1), which suggests that our newly designed two molecules mDPXZ-as-TAZ and pDPXZ-as-TAZ can be also considered as potential yellow-light TADF emitters.

The excited-state intramolecular proton transfer in NH-type dye molecules with a seven-membered-ring intramolecular hydrogen bond: A theoretical insight.

Excited-state intramolecular proton transfer (ESIPT) reactions of a series of N(R)H⋯N-type seven-membered-ring hydrogen-bonding compounds were explored by employing density functional theory/time-dependent density functional theory calculations with the PBE0 functional. Our results indicate that the absorption and emission spectra predicted theoretically match very well the experimental findings. Additionally, as the electron-withdrawing strength of R increases, the intramolecular H-bond of the NS1 form gradually enhances, and the forward energy barrier along the ESIPT reaction gradually decreases. For compound 4, its ESIPT reaction is found to be a barrierless process due to the involvement of a strong electron-withdrawing COCF3 group. It is therefore a reasonable presumption that the ESIPT efficiency of these N(R)H⋯N-type seven-membered-ring H-bonding systems can be improved when a strong electron-withdrawing group in R is introduced.

Theoretical insight into the excited-state intramolecular proton transfer mechanisms of three amino-type hydrogen-bonding molecules.

Excited-state intramolecular proton transfer (ESIPT) dynamics of the amino-type hydrogen-bonding compound 2-(2'-aminophenyl)benzothiazole (PBT-NH2) as well as its two derivatives 2-(5'-cyano-2'-aminophenyl)benzothiazole (CN-PBT-NH2) and 2-(5'-cyano-2'-tosylaminophenyl)benzothiazole (CN-PBT-NHTs) were studied by the time-dependent density functional theory (TD-DFT) approach with the B3LYP density functional, and their absorption and emission spectra were also explored at the same level of theory. A good agreement is observed between the theoretical simulations and experimental spectra, indicating that the present calculations are reasonably reliable. In addition, it is also found that the energy barriers of the first excited singlet state of the three targeted molecules along the ESIPT reaction are computed to be 0.38, 0.34 and 0.12eV, respectively, showing the trend of gradual decrease, which implies that the introduction of the electron-withdrawing cyano or tosyl group can facilitate the occurrence of the ESIPT reaction of these amino-type H-bonding systems. Following the ESIPT, both CN-PBT-NH2 and CN-PBT-NHTs dye molecules can undergo the cis-trans isomerization reactions in the ground-state and excited-state potential energy curves along the C2-C3 bond between benzothiazole and phenyl moieties, where the energy barriers of the trans-tautomer→cis-tautomer isomerizations in the ground states are calculated to be 0.83 and 0.34eV, respectively. According to our calculations, it is plausible that there may exist the long-lived trans-tautomer species in the ground states of CN-PBT-NH2 and CN-PBT-NHTs.