Chinese Journal of Chemistry最新文献

Given the crucial role of film morphology in determining the photovoltaic parameters of organic solar cells (OSCs), solvent or solid additives have been widely used to realize fine-tuned film morphological features to further improve the performance of OSCs. However, most high-performance OSCs are processed only using single component additive, either solvent additive or solid additive. Herein, a simple molecular building block, namely thieno[3,4-b]thiophene (TT), was utilized as the solid additive to coordinate with the widely used solvent additive, 1-chloronaphthalene (CN), to modulate the film morphology. Systematical investigations revealed that the addition of TT could prevent the excessive aggregation to form a delicate nanoscale phase separation, leading to enhanced charge transport and suppressed charge recombination, as well as superior photovoltaic performance. Consequently, the PM6:Y6 based OSCs with the addition of hybrid additive of CN + TT demonstrated the optimal PCE of 18.52%, with a notable FF of 79.6%. More impressively, the PM6:Y6:PC₇₁BM based ternary OSCs treated with the hybrid additives delivered a remarkable efficiency of 19.05%, which ranks among the best values of Y6-based OSCs reported so far. This work highlights the importance of the hybrid additive strategy in regulating the active layer morphology towards significantly improved performance.

Chiral α-tertiary aminonitriles are valuable synthetic intermediates. They are also found in various structures of biologically active molecules. Therefore, numerous reports of catalytic asymmetric synthesis of chiral α-aminonitriles continuously emerged during the past few decades. Great strides have been made for the synthesis of chiral α-aryl and α-branched alkyl aminonitriles. However, efficient methods for catalytic asymmetric synthesis of chiral α-linear alkyl aminonitriles remain limited. We herein report a new synthetic approach to chiral α-tertiary alkyl aminonitriles via catalytic asymmetric isomerization of cyanoketimines. The synthetic value of this method was illustrated by application to a concise catalytic asymmetric synthesis of vildagliptin.

The difunctionalization of bicyclo[1.1.0]butanes is an under-explored transformation that accesses to moieties that are otherwise difficult to prepare. Herein, a new oxidative radical alkylarylation of N-aryl bicyclobutyl amides with C(sp³)−H feedstocks is achieved in an atom-economic and photocatalyst- and light-free manner. This protocol follows a sequential C(sp³)–H/C(sp²)–H functionalization, providing an efficient route for diversity-oriented synthesis of functionalized 3-spirocyclobutyl oxindoles. In particular, a wide range of C(sp³)−H feedstocks, including ether, alcohol, amine, thioether, polychlorinated methane, silane, acetone, acetonitrile, toluene, and alkane are all suitable for the C(sp³)−H functionalization, demonstrating the broad applicability of this transformation.

How to obtain organic electro-optic materials with large electro-optic coefficients, high glass transition temperature, and good optical transparency remains a challenge in this field. To solve this problem, we introduce groups that can undergo Huisgen cycloaddition reactions into the donor and electron bridge of chromophores with large hyperpolarizability using tetrahydroquinoline as the donor. Binary cross-linkable chromophores TLD1-2 with CF₃-TCF as the acceptor and chromophores TLD3-4 with 5Fph-TCF as the acceptor were synthesized. After poling and crosslinking, the T_g of TLD1/TLD2 and TLD3/TLD4 were raised to 152 and 174 °C, respectively. The electro-optical coefficients of chromophores TLD1/TLD2 and TLD3/TLD4 were as high as 312 pm/V and 287 pm/V, respectively. The long-term alignment stability test showed that after being left at 85 °C for 500 h, the cross-linked film TLD3/TLD4 can still maintain more than 98% of the original electro-optical coefficient value, which is higher than that of TLD1/TLD2 (93%). The chromophore TLD3-4 exhibited much blue-shifted maximum absorption wavelengths (~40 nm) compared to TLD1-2 which was beneficial for reducing optical loss in the device. The combination of high electro-optic coefficient, strong stability, and excellent optical transparency makes the TLD series of binary cross-linked materials very promising for practical high-performance electro-optic devices.

Considering their oriented crystalline structure and high luminescent efficiency, the exploration of multi-component organic cocrystal systems with tunable supramolecular nanostructures and potential RGB light emission has emerged as a captivating but challenging subject. Here, we propose a straightforward synthetic strategy to precisely govern the assembly, structure and structure-property relationship of organic cocrystals. By employing the single-crystalline template-assisted epitaxial growth (SCT-EG) method, the two-dimensional (2D) highly-aligned cocrystal nanomeshes are firstly developed to afford an exceptional RGB trichromatic system, triggering cross-modulation white light emission (WLE) with remarkable stability and regeneration capacity over six months. The transformation from random 1D microstructures to uniformly-oriented 2D nanomeshes can be attributed to the regulatory competitive intermolecular π-π, CT interactions, and partial H bond interactions among cocrystals. Moreover, the successful construction of 2D RGB trichromatic cocrystal nanomeshes system holds promise to generate full-color display, which can function as multicolor inks for photonic dynamic recognition, information encryption, and decryption.