Synthesis and studies of covalently linked meso-furyl boron-dipyrromethene-ferrocene conjugates

Four meso-furyl BODIPY-ferrocene conjugates 1-4 in which one or more ferrocene groups were connected directly to BODIPY core or meso-furyl group were synthesized by coupling of appropriate bromo meso-furyl BODIPYs with alpha-ethynylferrocene under mild Pd(0) coupling conditions. The compounds were characterized by HR-MS mass, NMR, absorption, electrochemistry and fluorescence techniques. The absorption studies of compounds 1-4 showed charge transfer band in addition to BODIPY absorption bands indicating that the BODIPY and ferrocene moieties interact within the conjugates. On the other hand, the charge transfer band is absent in meso-phenyl BODIPY-ferrocene conjugate due to the orthogonal arrangement of ferrocene appended meso-phenyl group with BODIPY core which prevents the interaction between the two moieties. The electrochemical studies showed strong oxidation due to ferrocene moiety and reduction due to meso-furyl BODIPY unit. The compounds 3 and 4 which contain two and three ferrocenyl groups respectively were oxidized at the same potential with two and three electrons involved in the redox process. The compounds 1-4 are weakly fluorescent due to electron transfer from ferrocene unit to BODIPY unit. However, the fluorescence can be restored by oxidizing the ferrocene to ferrocenium ion which prevents the electron transfer between the two moieties. The computational studies support the experimental results. (C) 2011 Elsevier B. V. All rights reserved.