Enhancing Built-in Electric Field via Molecular Dipole Control in Conjugated Microporous Polymers for Boosting Charge Separation.

The built-in electric field (BEF) has been considered as the key kinetic factor for facilitating efficient photoinduced carrier separation and migration of polymeric photocatalysts. Enhancing the BEF of the polymers could enable a directional migration of the photogenerated carriers to accelerate photogenerated charge separation and thus boost photocatalytic performances. However, achieving this approach remains a formidable challenge, which has never been realized in conjugated microporous polymers (CMPs). Herein, we developed a molecular dipole control strategy to modulate the BEF in CMPs by varying the nature of the core. As a result, a series of CMPs with a tunable BEF were designed and prepared via FeCl3-mediated coupling of bicarbazole with different acceptor cores. The optimized CbzCMP-9 featured the strongest BEF induced by its high molecular dipole, which grants it with a powerful driving force to accelerate exciton dissociation into electron-hole pairs and facilitates charge transfer along the backbone of CMPs to the surface, resulting in a remarkable photocatalytic performance toward thiocyano chromones and C-3 thiocyanation of indoles (up to 95 and 98% yields, respectively) and prominently surpassing many other reported photocatalysts. In brief, the proposed strategy highlights that enhancing the BEF by modulating molecular dipole can lead to a dramatic improvement in photocatalytic performance, which is expected to be employed for constructing other photocatalytic systems with high performance.

Modulating Carrier Transfer over Carbazolic Conjugated Microporous Polymers via Donor Structural Design for Functionalization of Thiophenols.

Developing photocatalysts to steer conversion of solar energy toward high-value-added fine chemicals represents a potentially viable approach to address the energy crisis and environmental issues. However, enablement of this conversion is usually impeded by the sluggish kinetic process for proton-coupled electron transfer and rapid recombination of photogenerated excitons. Herein, we report a simple and general structural expansion strategy to facilitate charge transfer in conjugated microporous polymers (CMPs) via engineering the donor surrounding the trifluoromethylphenyl core. The resulting CMPs combine high surface area, strong light-harvesting capabilities, and tunable optical properties endowed by extended π-conjugation; the optimized compound CbzCMP-5 generated from 9,9',9″-(2-(trifluoromethyl)benzene-1,3,5-triyl)tris(9H-carbazole) remarkably enhanced the photogenerated carrier transfer efficiency, enabling the functionalization of thiophenols toward thiocarbamates and 3-sulfenylindoles with high photocatalytic efficiency. Most importantly, the in-depth insights into the carrier-transfer processes open up new prospects on further optimization and rational design of photoactive polymers for efficient charge-transfer-mediated reactions.

Correlation between the structure and skin permeability of compounds.

A three-descriptor quantitative structure-activity/toxicity relationship (QSAR/QSTR) model was developed for the skin permeability of a sufficiently large data set consisting of 274 compounds, by applying support vector machine (SVM) together with genetic algorithm. The optimal SVM model possesses the coefficient of determination R2 of 0.946 and root mean square (rms) error of 0.253 for the training set of 139 compounds; and a R2 of 0.872 and rms of 0.302 for the test set of 135 compounds. Compared with other models reported in the literature, our SVM model shows better statistical performance in a model that deals with more samples in the test set. Therefore, applying a SVM algorithm to develop a nonlinear QSAR model for skin permeability was achieved.

Engineering the Interconnecting Position of Star-Shaped Donor-π-Acceptor Molecules Based on Triazine, Spirofluorene, and Triphenylamine Moieties for Color Tuning from Deep Blue to Green.

Pi-conjugated organic molecules featuring the donor-bridge-acceptor (D-π-A) structure have been widely used in semiconducting materials owing to their rigid structure, good thermal stability, excellent charge transfer, and high emission efficiency. To investigate the effect of the D-π-A molecular structure on the photophysical properties, in this contribution, three star-shaped D-π-A isomers based on the 2,4,6-triphenyl-1,3,5-triazine, spirofluorene, and triphenylamine moieties, that is, p-TFTPA, mp-TFTPA, and m-TFTPA, were synthesized by elaborately engineering the interconnecting position in the building-block units. The optophysical properties of these compounds were systematically explored by experiments and theory calculations. Definitively, changing the interconnecting position in these molecules played a significant role in the degree of π conjugation, which resulted in tunable emission colors from deep blue to green. Moreover, these isomers were employed as emissive dopants in organic light-emitting diodes. The highest external quantum efficiency of 2.3 % and current efficiency of 6.2 cd A(-1) were achieved by using the p-TFTPA based device. This research demonstrates a feasible way to realize blue emitters by engineering D-π-A conjugation.