TY - JOUR A1 - Kollmannsberger, M. A1 - Rurack, Knut A1 - Resch-Genger, Ute A1 - Daub, J. T1 - Ultrafast charge transfer in amino-substituted boron dipyrromethene dyes and Its inhibition by cation complexation - a new design concept for highly sensitive fluorescent probes N2 - The photophysical behavior of a newly synthesized aza crown-substituted boron-dipyrromethene (BDP) dye and its dimethylamino analogue were investigated with steady-state and time-resolved fluorometry and compared to a reference compound. In solvents more polar than hexane, excitation of the dyes leads to a fast charge transfer from the locally excited (LE) state to a weakly emissive charge-transfer (CT) state. The donor-substituted compounds show dual emission from the LE and CT state, both fluorescence quantum yields being low. The rate constant of excited-state charge separation, calculated from the global analysis of time-resolved emission data, was determined to 1.6 × 1011 s-1 in 1,4-dioxane. The crowned compound forms 1:1-complexes with various alkali and alkaline-earth metal ions, which exist as two conformers in solution. In these complexes, coordination of the cation to the nitrogen donor atom of the crown inhibits the charge-transfer process, leading to a cation-dependent enhancement of the LE emission and the fluorescence lifetimes by factors >103. This efficient "switching on" of the fluorescence renders the crowned BDP dye an extremely sensitive fluorescent probe for metal ions. PY - 1998 DO - https://doi.org/10.1021/jp982701c SN - 1089-5639 SN - 1520-5215 VL - 102 IS - 50 SP - 10211 EP - 10220 PB - Soc. CY - Washington, DC AN - OPUS4-2095 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER -