4-4-difluoro-4-bora-3a-4a-diaza-s-indacene and chlorin

We report here the synthesis and characterization of BODIPY-chlorin arrays containing a chlorin subunit, with tunable deep-red (641-685 nm) emission, and one or two BODIPY moieties, absorbing at 504 nm. Two types of arrays were examined: one where BODIPY moieties are attached through a phenylacetylene linker at the 13- or 3,13-positions of chlorin, and a second type where BODIPY is attached at the 10-position of chlorin through an amide linker. Each of the examined arrays exhibits an efficient (≥0.80) energy transfer from BODIPY to the chlorin moiety in both toluene and DMF and exhibits intense fluorescence of chlorin upon excitation of BODIPY at ∼500 nm. Therefore, the effective Stokes shift in such arrays is in the range of 140-180 nm. Dyads with BODIPY attached at the 10-position of chlorin exhibit a bright fluorescence in a range of solvents with different polarities (i.e., toluene, MeOH, DMF, and DMSO). In contrast to this, some of the arrays in which BODIPY is attached at the 3- or at both 3,13-positons of chlorin exhibit significant reduction of fluorescence in polar solvents. Overall, dyads where BODIPY is attached at the 10-position of chlorin exhibit ∼5-fold brighter fluorescence than corresponding chlorin monomers, upon excitation at 500 nm.

Topics: Boron Compounds; Fluorescence; Molecular Structure; Porphyrins; Quantum Theory