Kononevich Yuriy N, Temnikov Maxim N, Korlyukov Alexander A, Volodin Alexander D, Dorovatovskii Pavel V, Sazhnikov Viacheslav A, Safonov Andrey A, Ionov Dmitriy S, Ivanov Anatoly A, Surin Nikolay M, Svidchenko Evgeniya A, Muzafarov Aziz M
A.N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, 119991, Moscow, Russian Federation.
Pirogov Russian National Research Medical University, 117997, Moscow, Russian Federation.
Chempluschem. 2020 Jun;85(6):1111-1119. doi: 10.1002/cplu.201900732. Epub 2020 Apr 1.
Four tetrahedral silicon-centered derivatives of dibenzoylmethanatoboron difluoride (DBMBF ) were synthesized and characterized. Their structural and optical features both in solution and the solid state were investigated by using X-ray crystallography, steady-state and time-dependent spectroscopy, and DFT-based calculations. In dilute solutions, the molar absorption coefficient increases from 40500 to 175200 M cm as the number of DBMBF fragments in a molecule increases from one to four, while, in contrast, the nonradiative rate constant of fluorescence decay decreases from 0.49 to 0.34. In the solid state, absorption and emission spectra depend on the degree of crystallinity and microcrystal size. The tris-DBMBF derivative forms fully overlapping dimeric structures that exhibit excimer-like fluorescence, which is accurately predicted by the quantum-chemical calculations. The mono-DBMBF derivative exhibits fully reverse mechanofluorochromic behavior.
合成并表征了二苯甲酰甲烷基二氟化硼（DBMBF）的四种以硅为中心的四面体衍生物。通过X射线晶体学、稳态和时间相关光谱以及基于密度泛函理论（DFT）的计算，研究了它们在溶液和固态中的结构和光学特性。在稀溶液中，随着分子中DBMBF片段的数量从一个增加到四个，摩尔吸收系数从40500增加到175200 M⁻¹ cm⁻¹，而荧光衰减的非辐射速率常数则从0.49降低到0.34。在固态中，吸收光谱和发射光谱取决于结晶度和微晶尺寸。三-DBMBF衍生物形成完全重叠的二聚体结构，表现出类激基缔合物荧光，这可以通过量子化学计算准确预测。单-DBMBF衍生物表现出完全相反的机械荧光变色行为。
