1225375-30-3Relevant academic research and scientific papers
β,meso-Acetylenyl-bridged, asymmetrical, porphyrin dyads - synthesis, spectral, electrochemical and computational studies
Yedukondalu, Meesala,Maity, Dilip K.,Ravikanth, Mangalampalli
experimental part, p. 1544 - 1561 (2010/06/15)
The first: examples of β,meso-acetylenyl-bridged, asymmetrical, covalently linked, porphyrin, dyads, containing two different subunits, such as ZnN4P-N3OP (1), ZnN4P-N3SP (2), ZnN4P-N2SOP (4) and ZnN4P-N2S 2P (6), were synthesized by the coupling of a β-acetylenyl, ZnN4 porphyrin with a mesobromoheteroporphyrin under mild, Pd°-catalyzed, coupling conditions. The dyads containing different types of metalfree subunits, such as N4P-N3SP (3), N 4P-N2SOP (5) and N4PN2S2P (7), were synthesized by the demetallation of the corresponding dyads. The seven β.meso-acetylenyl dyads 1-7 were characterized, by NMR, MS, absorption, fluorescence and electrochemical techniques. The NMR, absorption and electrochemical studies support an electronic interaction be tween the subunits in all seven dyads. The steady-state fluorescence studies on dyads 1-7 support an efficient energy transfer from the donor (ZnN4 or N4) subunit to the acceptor heteroporphyrin subunit upon excitation of the ZnN 4/N4 subunit. First-principle-based, quantum-chemical studies carried, out on dyads 1, 2, 4 and 6 further support an electronic interaction between the donor and acceptor subunits. The computational studies also predict significant tuning of the electronic energy levels in these dyads with the modification of the porphyrin core of the acceptor groups. The calculations support the experimental results of efficient donor→acceptor energy transfer in these dyads.
