Photophysics and stability of cyano-substituted boradiazaindacene dyes.
The solvatochromic photophysical properties of two fluorescent, cyano-substituted BODIPY dyes-8-(4-bromophenyl)-3,4,4,5-tetracyano-4-bora-3a,4a-diaza-s-indacene (4CN) and 8-(4-bromophenyl)-3,5-dicyano-4,4-difluoro-4-bora-3a,4a-diaza-s-indacene (2CN)-have been studied in various solvents by UV-vis spectrophotometry and steady-state and time-resolved fluorometry. These two BODIPY analogues have comparable photophysical properties, implying that displacement of F by CN at boron has a negligible effect. Both compounds have high fluorescence quantum yields Phi(f) (0.65-0.90 for 4CN and 0.63-0.88 for 2CN) in the solvents studied and display mono-exponential fluorescence decay profiles in nonprotic solvents. A new, generalized treatment of the solvent effect based on four mutually independent, empirical solvent scales (dipolarity, polarizability, acidity, and basicity of the medium) indicates that solvent polarizability and, to a lesser degree, solvent (di)polarity are crucial factors causing the solvent-dependent shifts of the UV-vis absorption and fluorescence emission. The rate constants of radiative deactivation (k(f)) are nearly independent of the nonprotic solvent [k(f) = (1.4 +/- 0.1) x 10(8) s(-1) for 4CN and (1.5 +/- 0.2) x 10(8) s(-1) for 2CN]. Both compounds undergo a color change in polar aprotic solvents (acetone, acetonitrile, and N,N-dimethylformamide), which can be stopped by addition of HClO(4). The kinetics of this color change indicates that the decomposition of these cyano-substituted BODIPY compounds is complex.
Cieślik-Boczula
Katarzyna
K
Faculty of Chemistry, University of Wroclaw, F. Joliot-Curie 14, 50-383 Wrocław, Poland.
Burgess
Kevin
K
Li
Lingling
L
Nguyen
Binh
B
Pandey
Lesley
L
De Borggraeve
Wim M
WM
Van der Auweraer
Mark
M
Boens
Noël
N
D015082:2,2'-Dipyridyl / Q000031:analogs & derivatives* / Q000138:chemical synthesis / Q000737:chemistry; D001880:Boranes / Q000138:chemical synthesis / Q000737:chemistry*; D004396:Coloring Agents / Q000138:chemical synthesis / Q000737:chemistry*; D015394:Molecular Structure; D009570:Nitriles / Q000138:chemical synthesis / Q000737:chemistry*; D010777:Photochemistry; D012997:Solvents / Q000737:chemistry; D013057:Spectrum Analysis
D001880:Boranes; D004396:Coloring Agents; D009570:Nitriles; D012997:Solvents; C476083:boradiazaindacene; D015082:2,2'-Dipyridyl