Nikolaev Institute of Inorganic Chemistry, Siberian Branch of the Russian Academy of Sciences, 3 Lavrentiev Ave., 630090 Novosibirsk, Russia.
Department of Natural Sciences, National Research University-Novosibirsk State University, 630090 Novosibirsk, Russia.
Molecules. 2022 Jun 16;27(12):3857. doi: 10.3390/molecules27123857.
We report synthesis, crystal structure, and photophysical properties of novel 1,3-phosphinoamines based on 4-amino-2,1,3-benzothiadiazole (NH-): PhPCH(Ph)NH- () and PhP(E)CH(Ph)NH-, (E = O ( and ·thf), S (), Se ()). Chalcogenides - exhibit bright emissions with a major band at 519-536 nm and a minor band at 840 nm. According to TD-DFT calculations, the first band is attributed to fluorescence, while the second band corresponds to phosphorescence. In the solid state, room temperature quantum yield reaches 93% in the case of the sulphide. The compounds under study feature effects of the molecular environment on the luminescent properties, which manifest themselves in fluorosolvatochromism as well as in a luminescent response to changes in crystal packing and in contributions to aggregation effects. Specifically, transformation of solid ·thf to solvate-free either by aging or by grinding causes crystal packing changes, and, as a result, a hypsochromic shift of the emission band. Polystyrene films doped with reveal a bathochromic shift upon increasing the mass fraction from 0.2 to 3.3%, which is caused by molecular aggregation effects.
我们报告了基于 4-氨基-2,1,3-苯并噻二唑 (NH-)的新型 1,3-膦胺的合成、晶体结构和光物理性质：PhPCH(Ph)NH-()和 PhP(E)CH(Ph)NH-，(E = O()和·thf，S()，Se())。这些硫属元素化合物表现出明亮的发射，主要带位于 519-536nm，次要带位于 840nm。根据 TD-DFT 计算，第一个带归因于荧光，而第二个带对应于磷光。在固态下，室温量子产率在硫化物的情况下达到 93%。研究中的化合物具有分子环境对发光性质的影响，这表现在荧光溶剂化效应以及对晶体堆积变化的发光响应以及对聚集效应的贡献。具体而言，通过老化或研磨将固体·thf 转化为无溶剂的，会导致晶体堆积发生变化，从而导致发射带的蓝移。掺杂有 的聚苯乙烯薄膜在质量分数从 0.2%增加到 3.3%时会发生红移，这是由分子聚集效应引起的。
