Synthesis of π-Conjugated Chiral Aza/Boracyclophanes with a meta and para Substitution.

We herein describe the synthesis of a new class of axially chiral aza/boracyclophanes (BDN1, BXN1, BDB1 and BXB1) using binaphthyls as chiral building blocks and the main-group (B/N) chemistry with tunable electronic effects. All macrocycles substituted with triarylamine donors or triarylborane acceptors are strongly luminescent. These macrocycles showed two distinct meta and para π-conjugation pathways, leading to the formation of quasi figure-of-eight and square-shaped conformations. Interestingly, comparison of such structural models revealed that the former type of macrocycles BXN1 and BXB1 gave higher racemization barriers relative to the other ones. The results reported here may provide a new approach to engineer the optical stability of π-conjugated chiral macrocycles by controlling π-substitution patterns. The ring constraints induced by macrocyclization were also demonstrated to contribute to the configurational persistence as compared with the open-chain analogues p-BTT and m-BTT.

Theoretical Study of the Photocyclization Reaction-Induced Dual Aggregation-Induced Emission Phenomenon.

Photochromic molecules with aggregation-induced emission (AIE) effects are of great value and prospective in various practical applications. To explore its inherent mechanism, the open isomer ap-BBTE and the closed isomer c-BBTE were chosen to perform the theoretical calculation using the quantum mechanics/molecular mechanics model combined with thermal vibration correlation function formalism. The calculations show that the photocyclization (PC) reaction from ap-BBTE to c-BBTE facilitates an improvement in the AIE effect. It is found that the fluorescence quantum yield (ΦF) enhancement of ap-BBTE is attributed to the restriction of the low-frequency rotational motion of the benzothiophene moiety and the high-frequency stretching vibrations of the C-C bond between the benzothiophene and benzylbis(thiadiazole) vinyl groups after aggregation. For c-BBTE, the increase in ΦF upon aggregation is mainly due to the suppression of the high-frequency stretching vibration of the C-C bond between the benzothiophene and the benzobis(thiadiazole) vinyl groups. In addition, the AIE effect was also enhanced from ap-BBTE to c-BBTE, which is consistent with the experimental phenomenon. The corresponding emission spectrum red-shifted from ap-BBTE to c-BBTE in both dilute solution and the crystalline state due to the improved intramolecular conjugation of c-BBTE. Moreover, the PC reaction from ap-BBTE to c-BBTE easily occurs in an excited state with a low energy barrier transition state by forming a C-C bond between benzothiophene groups effectively in dilute solution. Our calculations provide theoretical guidance for the further rational design of efficient AIE luminogens.

Designing Benzodithiophene-Based Small Molecule Donors for Organic Solar Cells by Regulation of Halogenation Effects.

The donors are key components of organic solar cells (OSCs) and play crucial roles in their photovoltaic performance. Herein, we designed two new donors (BTR-γ-Cl and BTR-γ-F) by finely optimizing small molecule donors (BTR-Cl and BTR-F) with a high performance. The optoelectronic properties of the four donors and their interfacial properties with the well-known acceptor Y6 were studied by density functional theory and time-dependent density functional theory. Our calculations show that the studied four donors have large hole mobility and strong interactions with Y6, where the BTR-γ-Cl/Y6 has the largest binding energy. Importantly, the proportion of charge transfer (CT) states increases at the BTR-γ-Cl/Y6 (50%) and BTR-γ-F/Y6 (45%) interfaces. The newly designed donors are more likely to achieve CT states through intermolecular electric field (IEF) and hot exciton mechanisms than the parent molecules; meanwhile, donors containing Cl atoms are more inclined to produce CT states through the direct excitation mechanism than those containing F atoms. Our results not only provided two promising donors but also shed light on the halogenation effects on donors in OSCs, which might be important to design efficient photovoltaic materials.

Theoretical Understanding on the Facilitated Photoisomerization of a Carbonyl Supported Borane System.

Boron compound BOMes2 containing an internal B-O bond undergoes highly efficient photoisomerization, followed by sequential structural transformations, resulting in a rare eight-membered B, O-heterocycle (S. Wang, et al. Org. Lett. 2019, 21, 5285-5289). In this work, the detailed reaction mechanisms of such a unique carbonyl-supported tetracoordinate boron system in the first excited singlet (S1 ) state and the ground (S0 ) state were investigated by using the complete active space self-consistent field and its second-order perturbation (MS-CASPT2//CASSCF) method combined with time-dependent density functional theory (TD-DFT). Moreover, an imine-substituted tetracoordinated organic boron system (BNMes2 ) was selected for comparative study to explore the intrinsic reasons for the difference in reactivity between the two types of compounds. Steric factor was found to influence the photoisomerization activity of BNMes2 and BOMes2 . These results rationalize the experimental observations and can provide helpful insights into understanding the excited-state dynamics of heteroatom-doped tetracoordinate organoboron compounds, which facilitates the rational design of boron-based materials with superior photoresponsive performances.

A moderate intensity ligand works best: a theoretical study on passivation effects of pyridine-based molecules for perovskite solar cells.

Improving battery stability while maintaining high photoelectric conversion efficiency remains the bottleneck in the current development of perovskite solar cells (PSCs). Three π-conjugated pyridine-based molecules, pyridine (Py), bipyridine (Bpy), and terpyridine (Tpy), were adopted to passivate the PSCs in recent experiments (J. Chen, S.-G. Kim, X. Ren, H. S. Jung and N.-G. Park, J. Mater. Chem. A, 2019, 7, 4977-4987; J. Zhang, J. Duan, Q. Zhang, Q. Guo, F. Yan, X. Yang, Y. Duan and Q. Tang, Chem. Eng. J., 2022, 431, 134230), in which Bpy works best in terms of photovoltaic properties and moisture tolerance. In this work, based on density functional theory (DFT) calculations and ab initio molecular dynamics (AIMD) simulations, we demonstrate that Bpy displays the least structural fluctuation when adsorbed on the perovskite surface, enlarges the bandgap suppressing electron-hole recombination, and exhibits remarkable shielding effects against moisture. The appropriate anchoring ability of Bpy retains robust binding strength and preferable charge transfer ability compared to Py at the interfaces between the passivation molecules (PMs) and MAPbI3. In contrast, although Tpy possesses the strongest charge-transfer capability, it introduces midgap states owing to intense electronegativity, providing additional pathways for nonradiative charge relaxation. Besides, Tpy triggers rapid diffusions of water and larger atomic fluctuations, destroying the structures of the perovskite through the removal of lead atoms. Our computational results not only rationalize the experimental observations but also provide valuable guidance at the atomic level to design novel PMs that endow PSCs with outstanding photovoltaic performance as well as stability against moisture.

Cooperative multiple interactions of donor-π-acceptor dyes enhance the efficiency and stability of perovskite solar cells.

Surface passivation by organic dyes has been an effective strategy for simultaneous enhancement of the efficiency and stability of perovskite solar cells. However, lack of in-depth understanding of how subtle structural changes in dyes leads to distinctly different passivation effects is a challenge for screening effective passivation molecules (PMs). In an experiment done by Han et al. (Adv. Energy Mater., 2019, 9, 1803766), three donor-π-acceptor (D-π-A) dyes (SP1, SP2, and SP3) with distinct electron donors have been applied to passivate the perovskite surface, where the efficiency and stability of PSCs are quite different. Herein, we carried out first-principles calculations and ab initio molecular dynamics (AIMD) simulations on the structures and electronic properties of SP1, SP2, SP3, and their passivated perovskite surfaces. Our results showed that SP3 enhances the carrier transfer rate, electric field, and absorption region compared to SP1 and SP2. Moreover, AIMD simulations reveal that the cooperative multiple interactions of O-Pb, S-Pb, and H-I between SP3 and the perovskite surface result in a stronger passivation effect in a humid environment than that of SP1 and SP2. This work is expected to pave the way for screening dye passivation molecules to endow perovskite solar cells with high efficiency and stability.

A theoretical study on the photochemical generation of phenylborylene from phenyldiazidoborane.

Organic borylenes are a kind of highly reactive species, which play important roles in a lot of reactions as vigorous intermediates. In this work, we investigated the photochemical generation mechanisms of phenylborylene (PhB) together with the side product N-phenylnitrenoiminoborane (PhNBN) from phenyldiazidoborane (PhBN6) by extrusion of dinitrogen in the two lowest electronic singlet states (S0 and S1) based on the complete active space self-consistent field (CASSCF) and its second-order perturbation (CASPT2) methods combined with time-dependent density functional theory (TD-DFT) calculations. Our results show that the reaction PhBN6 → PhB + 3N2 involves stepwise N2 extrusion three times and the azido region rearrangement. Moreover, we found that the studied photo-induced processes are kinetically feasible because the highest energy barrier is only 0.36 eV and excitation with light of wavelength 254 nm can provide enough excess energy to overcome these energy barriers. Importantly, we revealed that several conical intersections between S1 and S0 states participate and facilitate the studied photochemical processes. Our results not only clarify the experimental observations, (H. F. Bettinger, J. Am. Chem. Soc. 2006, 128, 2534), but also provide valuable insights into borylene chemistry.

Incorporation of a Boron-Nitrogen Covalent Bond Improves the Charge-Transport and Charge-Transfer Characteristics of Organoboron Small-Molecule Acceptors for Organic Solar Cells.

An organoboron small-molecular acceptor (OSMA) MB←N containing a boron-nitrogen coordination bond (B←N) exhibits good light absorption in organic solar cells (OSCs). In this work, based on MB←N, OSMA MB-N, with the incorporation of a boron-nitrogen covalent bond (B-N), was designed. We have systematically investigated the charge-transport properties and interfacial charge-transfer characteristics of MB-N, along with MB←N, using the density functional theory (DFT) and the time-dependent density functional theory (TD-DFT). Theoretical calculations show that MB-N can simultaneously boost the open-circuit voltage (from 0.78 V to 0.85 V) and the short-circuit current due to its high-lying lowest unoccupied molecular orbital and the reduced energy gap. Moreover, its large dipole shortens stacking and greatly enhances electron mobility by up to 5.91 × 10-3 cm2·V-1·s-1. Notably, the excellent interfacial properties of PTB7-Th/MB-N, owing to more charge transfer states generated through the direct excitation process and the intermolecular electric field mechanism, are expected to improve OSCs performance. Together with the excellent properties of MB-N, we demonstrate a new OSMA and develop a new organoboron building block with B-N units. The computations also shed light on the structure-property relationships and provide in-depth theoretical guidance for the application of organoboron photovoltaic materials.

Suppression of reversible photocyclization reaction induced fluorescence enhancement: a theoretical study.

Aggregation-induced emission (AIE) materials with photocyclization (PC) reactions exhibit rich photophysical and photochemical activities. Understanding the mechanism behind is essential to the design of effective AIE materials. Herein, we employ a polarizable continuum model (PCM) and the hybrid quantum mechanics and molecular mechanics (QM/MM) approach, to study the luminescent properties of PC-typed AIEgens, SIP-2 and DPI, in both solution and crystalline states. The calculated results indicate that the fluorescence quantum yields (ΦF) of SIP-2 and DPI under different environments are mainly related to the competition between the PC reaction and aggregation induced restriction of phenyl ring rotational motions. In solution, SIP-2 and DPI undergo PC reactions to form a C-C bond between the phenyl rings A and B, which provides an important non-radiative decay channel and dramatically reduces the fluorescence intensity. Upon aggregation, the restricted rotational motion of rings A and B blocks the PC reaction and reduces the reorganization energy, which lowers the non-radiative decay rate constant (kIC) and benefits the ΦF. This is consistent with the experimental phenomenon that both SIP-2 and DPI exhibit the AIE effect. In addition, the introduction of the rigid spiro backbone of SIP-2 increases the steric effect, further limiting the phenyl ring rotation and PC reaction, resulting in an increase in the fluorescence intensity. Our calculations not only show the detailed mechanism of PC-typed AIEgens but also provide theoretical guidance for the further rational design of efficient AIEgens.

Atomistic Mechanism of Surface-Defect Passivation: Toward Stable and Efficient Perovskite Solar Cells.

Molecular engineering has been demonstrated to be a predominant strategy for augmenting the long-term stability and passivating adverse defects for perovskite solar cells (PSCs). Here, using density functional theory calculations combined with ab initio molecular dynamics (AIMD) simulations, the passivation effects of bidentate passivation molecules, 2-MP and 2-MDEP, on the iodine vacancy MAPbI3 were comprehensively investigated. We demonstrate that 2-MDEP engenders stronger adsorption and localized charges on Pb atoms because the separated binding sites match with the MAPbI3 lattice. Moreover, the activation barriers for ion migrations are improved by the passivation of 2-MP and 2-MDEP. Furthermore, AIMD simulations verify the improved structural stability and restrained nonradiative recombination after passivation. More importantly, the durable Pb-heteroatom interactions at the interface and stronger hydrophobicity endow 2-MDEP with more remarkable shielding effects against moisture compared to those of 2-MP. This work deepens our understanding of the passivation effects and paves the way for the design of passivation molecules toward the attainment of efficient and stable PSCs.

Understanding of Photo-Induced Reversible Rearrangement from Borepin to Borirane.

The first reversible photoisomerization between a borepin and a borirane was reported in the photo-induced reactions of B(npy)Ar2 (npy=2-(naphthalen-1-yl) pyridine, Ar=phenyl or electron rich aryl; S. Wang, et al. Angew. Chem. Int. Ed. 2019, 58, 6683-6687). In this work, the detailed mechanisms of the unprecedented reversible photoisomerization between the borepin (compound a) and the borirane (compound b) of B(npy)Ph2 in the first excited singlet (S1 ) state and the ground (S0 ) state were studied by carrying out calculations with the complete active space self-consistent field (CASSCF) and its second-order perturbation (CASPT2) methods combined with time-dependent density functional theory (TD-DFT). The calculation results show that photoexcitation of a-S0 at 365 nm and b-S0 at 450 nm populate their S1 state with evident charge transfer characteristics. The photoisomerization is triggered in the S1 state and ends in the S0 state, at which the intersection points in a (S1 /S0 )x intersection seam participate in and promote phenyl migration and ring-closure processes. Furthermore, we reveal that the not large energy difference (less than 0.6 eV) and similar conjugation properties of π electrons between a-S0 and b-S0 are responsible for their unique photo-reversible reactivity, compared with those of the isomers of the thermally reversible compound B(ppy)Mes2 . Our results contribute to an understanding of the excited-state reactivity of organoboron compounds and will be useful to support the design of new boron-based photo-responsive materials.

Theoretical insights into photo-induced isomerization mechanisms of phenylsulfinyl radical PhSO˙.

Sulfinyl radicals (R-SO˙) play important roles in lots of reactions, while the isomer oxathiyl radicals (R-OS˙) and the isomerization between them are rarely observed due to the poor stability of R-OS˙. In this work, the complete active space self-consistent field (CASSCF) and its multi-state second order perturbation (MS-CASPT2) methods were employed to study the photo-induced reaction mechanisms of phenylsulfinyl radical PhSO˙ 1 and its isomer phenoxathiyl radical PhOS˙ 2. Our results show that 1 and 2 have similar singly occupied molecular orbitals in the ground state but different properties in the excited state, which determine their diverse behaviors after irradiation. Radical 1 can generate 2 by light irradiation, but 2 produces isomerization product 3 (2-hydroxyphenylthiyl radical) and ring-opening product 4 (acyclic thioketoketene radical) in two paths via S atom migration intermediate Int1 (2-carbonylcyclohexadienthiyl radical). The former path involves consequent hydrogen shift reactions with a strongly exothermic process while the latter path involves both ring-expansion and ring-opening processes with a high barrier, resulting in a structural and energetic preference for the former path. Moreover, we revealed several conical intersections that participate in the reactions and facilitate the photochemical processes. Our calculations not only remain consistent with and clarify the experimental observations (X. Zeng, et al., J. Am. Chem. Soc., 2018, 140(31), 9972-9978) but also enrich the knowledge of sulfinyl radicals and isomer oxathiyl radicals.

Theoretical Study of Non-Fullerene Acceptors Using End-Capped Groups with Different Electron-Withdrawing Abilities toward Efficient Organic Solar Cells.

Acceptors in organic solar cells (OSCs) are of paramount importance. On the basis of the well-known non-fullerene acceptor Y6, six acceptors (Y6-COH, Y6-COOH, Y6-CN, Y6-SO2H, Y6-CF3, and Y6-NO2) were designed by end-capped manipulation. The effects of end-capped engineering on electronic properties, optical properties, and interfacial charge-transfer states were systematically studied by density functional theory, time-dependent density functional theory, and molecular dynamics. The designed acceptors possess suitable energy levels and improved optical properties. More importantly, the electron mobility of the new acceptors was greatly enhanced, even more than 20 times that of the parent molecule. Among them, Y6-NO2 with the lowest-lying frontier molecular orbitals and the largest red-shifted absorption was selected to construct interfaces with the donor PM6. PM6/Y6-NO2 exhibits stronger interfacial interactions and enhanced charge-transfer characteristics compared with PM6/Y6. This work not only enhances the understanding of the structure-property relationship for acceptors but also offers a set of promising acceptors for high-performance OSCs.

Theoretical design of asymmetric A-D1A'D2-A type non-fullerene acceptors for organic solar cells.

The acceptor in organic solar cells (OSCs) is of paramount importance for achieving a high photovoltaic performance. Based on the well-known non-fullerene acceptor Y6, we designed a set of asymmetric A-D1A'D2-A type new acceptors Y6-C, Y6-N, Y6-O, Y6-Se, and Y6-Si by substituting the two S atoms of one thieno[3,2-b]thiophene unit with C, N, O, Se, and Si atoms, respectively. The electronic, optical, and crystal properties of Y6 and the designed acceptors, as well as the interfacial charge-transfer (CT) mechanisms between the donor PM6 and the investigated acceptors have been systematically studied. It is found that the newly designed asymmetric acceptors possess suitable energy levels and strong interactions with the donor PM6. Importantly, the newly designed acceptors exhibit enhanced light harvesting ability and more CT states with larger oscillator strengths in the 40 lowest excited states. Among the multiple CT mechanisms, the direct excitation of CT states is found to be more favored in the case of PM6/newly designed acceptors than that of PM6/Y6. This work not only offers a set of promising acceptors superior to Y6, but also demonstrates that designing acceptors with asymmetric structure could be an effective strategy to improve the performance of OSCs.

Mechanistic Investigation on Chemiluminescent Formaldehyde Probes.

A first-generation pair of chemiluminescent formaldehyde (FA) probes (CFAP540 and CFAP700) was reported recently. CFAP540 and CFAP700, with high selectivity and sensitivity to FA, are, respectively, suitable in cell and in vivo. Experimentalists have confirmed that both probes utilize a general 2-aza-Cope FA-reactive trigger and a chemiluminogenic phenoxydioxetane scaffold. The mechanism and detailed process of CFAP chemiluminescence (CL) remain largely unknown. In the present paper, (time-dependent) density functional theory calculations are performed on the entire reaction process of CFAP540 with FA to produce CL. The calculations elucidated the CL-producing process: FA initiates the decomposition of CFAP540 by dehydration condensation, and a phenoxy 1,2-dioxetane is formed through a series of reactions of aza-Cope rearrangement, hydrolysis of imine, and ß-elimination of alkoxyl group. Afterwards, the produced phenoxy 1,2-dioxetane decomposes to produce the m-oxybenzoate derivative in the first singlet state (S1 ) via two crossings between potential energy surfaces of the ground state (S0 ) and S1 state. This m-oxybenzoate derivative was assigned as the light emitter of the CFAP540 CL. The CL-producing process and assignment of the light emitter of CFAP700 CL are similar with the corresponding ones of CFAP540. By analyzing the D-π-A architecture of the light emitters of CFAP540 and CFAP700, a series of CFAPs is theoretically designed and a scheme to modulate their CL from visible to near-infrared region is proposed by adjusting the length and structure of the π-bridge.

Theoretical study on the photochemistry of furoylazides: Curtius rearrangement and subsequent reactions.

Organic azides are an efficient source of nitrenes, which serve as vigorous intermediates in many useful organic reactions. In this work, the complete active space self-consistent field (CASSCF) and its second-order perturbation (CASPT2) methods were employed to study the photochemistry of 2-furoylazide 1 and 3-furoylazide 5, including the Curtius rearrangement to two furylisocyanates (3 and 7) and subsequent reactions to the final product cyanoacrolein 9. Our calculations show that the photoinduced Curtius rearrangement of the two furoylazides takes place through similar stepwise mechanisms via two bistable furoylnitrenes 2 and 6. However, the decarbonylation and ring-opening process of 7 to 9 prefers a stepwise mechanism involving the 3-furoylnitrene intermediate 8, while 3 to 9 goes in a concerted asynchronous way without the corresponding 2-furoylnitrene intermediate 4. Importantly, we revealed that several conical intersections play key roles in the photochemistry of furoylazides. Our results are not only consistent and also make clear the experimental observations (X. Zeng, et al., J. Am. Chem. Soc., 2018, 140, 10-13), but additionally provide important information on the chemistry of furoylazides and nitrenes.

End-capped group manipulation of indacenodithienothiophene-based non-fullerene small molecule acceptors for efficient organic solar cells.

As the key component of organic solar cells (OSCs), the acceptor plays key roles in determining the power conversion efficiency (PCE). Based on the famous non-fullerene acceptor ITIC, a series of acceptors (A1-A5) were designed by introducing fused-ring units (phenanthrene, pyrene, benzopyrazine, dibenzo[a,c]phenazine, and phenanthro[4,5-abc]phenazine) as the end groups. Theoretical calculations showed that A1-A5 display improved solubility and redshifted absorption spectra compared with ITIC. More importantly, the newly designed acceptors exhibit much higher electron mobility, where the electron mobility of A5_h (similar to A5 but with the same hexyl side chain as ITIC) is about four orders of magnitude larger than that of ITIC. The computed binding energies of the donor PBDB-TF with the acceptor ITIC and A5_h are -2.52 eV and -3.75 eV, indicating much stronger interface interactions in PBDB-TF/A5_h. In terms of charge-transfer (CT) mechanism, we found that both PBDB-TF/ITIC and PBDB-TF/A5_h can generate CT states through direct excitation and hot excitons, meanwhile there exist more opportunities of producing CT states via the intermolecular electric field (IEF) mechanism in PBDB-TF/A5_h. Our results not only offer a set of promising ITIC-based acceptors, but also provide new insights into the donor/acceptor interface properties, which are closely related to the PCE of OSCs.

Molecular Engineering of Hexaazatriphenylene Derivatives toward More Efficient Electron-Transporting Materials for Inverted Perovskite Solar Cells.

The electron-transporting material (ETM) in inverted perovskite solar cells (PSCs) plays important role in reducing hysteresis and realizing simple processing procedures, while the improvement of power conversion efficiency is limited by low electron mobility and weak perovskite/ETM interface interaction. In this work, three new ETMs (HAT-1, HAT-2, and HAT-3) were designed by introducing methoxyphenyl, imide, and naphthalene groups into the hexaazatriphenylene (HAT) skeleton, based on the ETM HATNASOC7 synthesized experimentally [Jen; Angew. Chem., Int. Ed. 2016, 55, 8999]. Theoretical calculations showed that the electron mobilities of HAT-1, HAT-2, and HAT-3 are 2.98, 3.79, and 13.21 times that of HATNASOC7, which is attributed to the increased C···C and O···H interactions in the newly designed ETMs. More importantly, the evidently decreased perovskite/ETM interface distances and the significantly increased adsorption energies revealed that the interface interactions were markedly enhanced with the newly designed ETMs by forming additional Pb···O interactions, which promote the electron injection. The deep understanding of perovskite/ETM interface properties sheds new light on the complex factors determining the PSC function and paves the way for the rational design of highly efficient and stable components for PSCs.

Theoretical Study on Photoisomerization Mechanisms of Diphenyl-Substituted N,C-Chelate Organoboron Compounds.

N,C-chelate organoboron compounds are widely employed as photoresponsive and optoelectronic materials due to their efficient photochromic reactivity. It was found in experiments that two diphenyl-substituted organoboron compounds, namely B(ppy)Ph2 (ppy=2-phenylpyridyl) and B(iba)Ph2 (iba=N-isopropylbenzylideneamine), show distinct photochemical reactivity. B(ppy)Ph2 is inert on irradiation, whereas B(iba)Ph2 undergoes photoinduced transformations, yielding BN-cyclohepta-1,3,5-triene via a borirane intermediate. In this work, the complete active space self-consistent field and its second-order perturbation (CASPT2//CASSCF) methods were used to investigate the photoinduced reaction mechanisms of B(ppy)Ph2 and B(iba)Ph2 . The calculations showed that the two compounds isomerize to borirane in the same way by passing a transition state in the S1 state and a conical intersection between the S1 and S0 states. The energy barriers in the S1 state of 0.54 and 0.26 eV for B(ppy)Ph2 and B(iba)Ph2 , respectively, were explained by analyzing the charge distributions of minima in S0 and S1 states. The results provide helpful insights into the excited-state dynamics of organoboron compounds, which could assist in rational design of boron-based photoresponsive materials.

Insights into the Photoinduced Isomerization Mechanisms of a N,C-Chelate Organoboron Compound: A Theoretical Study.

As the first discovered organoboron compound with photochromic property, B(ppy)Mes2 (ppy=2-phenylpyridine, Mes=mesityl) displays rich photochemistry that constitutes a solid foundation for wide applications in optoelectronic fields. In this work, we investigated the B(ppy)Mes2 to borirane isomerization mechanisms in the three lowest electronic states (S0 , S1 , and T1 ) based on the complete active space self-consistent field (CASSCF) and its second-order perturbation (CASPT2) methods combined with time-dependent density functional theory (TD-DFT) calculations. Our results show that the photoisomerization in the S1 state is dominant, which is initiated by the cleavage of the B-Cppy bond. After overcoming a barrier of 0.5 eV, the reaction pathway leads to a conical intersection between the S1 and S0 states (S1 /S0 )x , from which the decay path may go back to the reactant B(ppy)Mes2 via a closed-shell intermediate (Int1-S0 ) or to the product borirane via a biradical intermediate (Int2-S0 ). Although triplet states are probably involved in the photoinduced process, the possibility of the photoisomerization in T1 state is very small owing to the weakly allowed S1 →T1 intersystem crossing and the high energy barrier (0.77 eV). In addition, we found the photoisomerization is thermally reversible, which is consistent with the experimental observations.