Essential differences in the luminescence properties of dibenzoylmethanatoboron difluoride (1) bulk and microcrystals were detected. Analysis of the spectral data showed that in every case the fluorescence spectrum of 1 consisted of three components: monomer fluorescence, excimer fluorescence, and fluorescence related with interdimer interaction. Evolution of luminescence spectra observed with decrease of the crystal size are bound with decrease of monomer fluorescence intensity and considerable growth of intensity of fluorescence related to interdimer interaction. The presence of reversible luminescence thermochromism was discovered for 1: lowering the temperature from 300 to 77 K resulted in essential hypsochromic shift of the luminescence band maximum ( approximately 60 nm) connected with considerable decrease of the distances between the planes of the neighboring molecules ( approximately 0.1 Angstrom) that lead to the weakening of interdimer interaction and intensification of monomer luminescence.

Reversible luminescence thermochromism of dibenzoyl(methanato)boron difluoride was found. A substantial hypsochromic shift of the luminescence band maximum (60 nm) with a temperature decrease from 300 to 77 K was observed, and the luminescence color changed from green to blue. A considerable decrease (by 0.386 Å) in the unit cell parameters along the c axis was detected by X ray diffractometry when the temperature of the crystal decreased from 293 to 123 K. Shortening of the distances between the planes of adjacent molecules (stacking factor) weakens the interaction between the dimers and enhances the monomeric and excimeric luminescence.Development and synthesis of reversible luminescent thermochromes are urgent from both practical and theo retical standpoints. 1,2 One of the promising lines of search for new luminescent thermochromes is a study of mo lecular organized organic systems, including dimers, tri mers, and aggregates of conjugated molecules, whose supramolecular architecture produces different intermo lecular interactions: dimeric (excimeric), interdimeric, and stacking interactions. 3,4Continuing our works on studying the interrelation of the structure and luminescence and photochemical prop erties of boron difluoride β diketonates, 5-7 in this work we studied a change in the luminescence of dibenzo yl(methanato)boron difluoride (1) at different tempera tures and revealed reversible luminescence thermo chromism of this compound, namely, a substantial hypso chromic shift of the fluorescence band maximum (60 nm) and a change in the luminescence color from green to blue when the temperature decreases from 300 to 77 K. ExperimentalCompound 1 was synthesized according to a previously pub lished procedure. 8 Crystals were prepared by recrystallization from an acetonitrile-toluene (1 : 1) mixture. Fluorescence spec tra of solutions were obtained on a Shimadzu RF 5000 in strument. Luminescence spectra of crystalline compounds at 77-300 K were recorded on an SDL 1 spectrometer, using a DRSh 250 lamp as an excitation source and an UFS 6 filter (λ exc = 365 nm). To measure a temperature dependence of the luminescence spectra, a sample was placed in a quartz Dewar flask above the liquid nitrogen surface. The temperature of the sample was measured by a platinum thermocouple. The X ray diffraction study of compound 1 was carried out at 293, 203, and 123 K in a SMART 1000 CCD Bruker system using Мо Кα radiation. Results and DiscussionAs can be seen from the data in Fig. 1, a decrease in the temperature of the crystal from 300 to 77 K produces a substantial hypsochromic shift of the fluorescence band maximum of compound 1 (60 nm). For a more detailed analysis of the evolution of the luminescence spectra with a temperature change, the spectra were deconvoluted by the Gaussian expansion using the Origin 6.1 program; the results of deconvolution are presented in Fig. 1.It turned out that the fluorescence spectrum of com pound 1 at each temperature consists of three compo nents with maxima at 470, 500, and 560 nm, and o...

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The crystal structure, luminescence properties of 2,2-difluoro-4,6-(4-methylphenyl)-1,3,2-dioxaborine (СH 3 C 6 H 4 COCHCOC 6 H 4 CH 3 BF 2 ) crystals and solutions at different concentrations are examined at T 296 K and 156 K.Keywords: boron difluoride β-diketonate, 2,2-difluoro-4,6-(4-methylphenyl)-1,3,2-dioxaborine, crystal structure, luminescence, H and J aggregates, quantum chemical simulation.Boron difluoride β-diketonates exhibit strong luminescence in both solutions and the crystalline state [1]. These compounds are employed in molecular electronics for they possess nonlinear optical properties [2], two-photon absorption [3,4], and photoconductivity [5].2,2-Difluoro-4,6-(4-methylphenyl)-1,3,2-dioxaborine (СH 3 C 6 H 4 COCHCOC 6 H 4 CH 3 BF 2 ) (1) belongs to boron difluoride dibenzoylmethanates bearing substituents in the phenyl rings. We have previously studied the spectral luminescent properties of solid boron difluoride dibenzoylmethanate (C 6 H 5 COCHCOC 6 H 5 BF 2 ) and its solutions [6]. The introduction of a methyl substituent, as exemplified by boron difluoride benzoylacetonate [7], strongly influences the supramolecular structure of the crystal, its luminescence properties being significantly affected. This contribution reports the effect of the crystal structure of 1 on its spectral luminescence properties as well as the evolution of spectral properties with an increase in the solution concentration. EXPERIMENTALCompound 1 was prepared by acylation of toluene with mixed anhydride of trifluoroacetic and malonic acids [8] (Scheme 1). X-ray quality crystals of 1 were obtained by recrystallization from toluene on slow cooling of the solution.Luminescence spectra of the crystals were recorded on a SDL-1 spectrometer (LOMO) at 300 K and 77 K, excitation source DRSh-250 lamp, UFS-6 filter (λ ex = 365 nm); excitation spectra and luminescence spectra of the solutions and crystals at 300 K were measured on a Shimadzu-RF5301 spectrofluorophotometer. Time-resolved luminescence spectra were recorded on a FluoTime 200 spectrometer (PicoQuant). A crystal with the dimensions of 10×1.35×0.6 mm was used for the time-resolved spectroscopic examination of compound 1. Complete X-ray structural investigation was carried out with a SMART-1000 CCD diffractometer (Bruker) at temperatures of 296(2) K and 156(2) K. Data collection for the crystal was carried out by ω-scanning in three sets of 906