Synthesis and photophysical properties of halogenated derivatives of (dibenzoylmethanato)boron difluoride

• Published in: Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy Vol. 175; pp. 177 - 184
• Main Authors: Kononevich, Yuriy N., Surin, Nikolay M., Sazhnikov, Viacheslav A., Svidchenko, Evgeniya A., Aristarkhov, Vladimir M., Safonov, Andrei A., Bagaturyants, Alexander A., Alfimov, Mikhail V., Muzafarov, Aziz M.
• Format: Journal Article
• Language: English
• Published: England Elsevier B.V 15.03.2017
• Subjects: DFT calculations; Exciplex; Fluorescence; Halogenated (dibenzoylmethanato)boron difluorides; Exciplex; Fluorescence; Halogenated (dibenzoylmethanato)boron difluorides; DFT calculations
• ISSN: 1386-1425; 1873-3557
• DOI: 10.1016/j.saa.2016.12.025

A series of (dibenzoylmethanato)boron difluoride (BF2DBM) derivatives with a halogen atom in one of the phenyl rings at the para-position were synthesized and used to elucidate the effects of changing the attached halogen atom on the photophysical properties of BF2DBM. The room-temperature absorption and fluorescence maxima of fluoro-, chloro-, bromo- and iodo-substituted derivatives of BF2DBM in THF are red-shifted by about 2–10nm relative to the corresponding peaks of the parent BF2DBM. The fluorescence quantum yields of the halogenated BF2DBMs (except the iodinated derivative) are larger than that of the unsubstituted BF2DBM. All the synthesized compounds are able to form fluorescent exciplexes with benzene and toluene (emission maxima at λem=433 and 445nm, respectively). The conformational structure and electronic spectral properties of halogenated BF2DBMs have been modeled by DFT/TDDFT calculations at the PBE0/SVP level of theory. The structure and fluorescence spectra of exciplexes were calculated using the CIS method with empirical dispersion correction. [Display omitted] •A series of halogenated in the para-position DBMBF2 derivatives were synthesized.•The absorption and fluorescence of the Hal-DBMBF2 derivatives are measured.•The fluorescence QY of the Hal-DBMBF2 (except I-DBMBF2) is larger than of DBMBF2.•All Hal-DBMBF2 are able to form fluorescent exciplexes with benzene and toluene.