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Tetrahedral Silicon‐Centered Dibenzoylmethanatoboron Difluorides: Synthesis, Crystal Structure, and Photophysical Behavior in Solution and the Solid State
Author(s) -
Kovich 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.
Publication year - 2020
Publication title -
chempluschem
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.801
H-Index - 61
ISSN - 2192-6506
DOI - 10.1002/cplu.201900732
Subject(s) - difluoride , fluorescence , crystallinity , molecule , crystallography , absorption (acoustics) , crystal structure , chemistry , derivative (finance) , absorption spectroscopy , spectroscopy , materials science , photochemistry , inorganic chemistry , organic chemistry , optics , physics , financial economics , economics , quantum mechanics , composite material
Four tetrahedral silicon‐centered derivatives of dibenzoylmethanatoboron difluoride (DBMBF 2 ) 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 −1 cm −1 as the number of DBMBF 2 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 2 derivative forms fully overlapping dimeric structures that exhibit excimer‐like fluorescence, which is accurately predicted by the quantum‐chemical calculations. The mono‐DBMBF 2 derivative exhibits fully reverse mechanofluorochromic behavior.