Physicochemical and photophysical studies on porphyrin-based donor-acceptor systems: effect of redox potentials on ultrafast electron-transfer dynamics.

We report new polychromophoric complexes, where different porphyrin (P) derivatives are covalently coupled to a redox active Mo center, MoL*(NO)Cl(X) (L* is the face-capping tridentate ligand tris(3,5-dimethylpyrazolyl) hydroborate and X is a phenoxide/pyridyl/amido derivative of porphyrin). The luminescence quantum yields of the bichromophoric systems (1, 2, and 5) were found to be an order of magnitude less than those of their respective porphyrin precursors. Transient absorption measurements revealed the formation of the porphyrin radical cation species (P(.)(+)) and photoinduced electron transfer from the porphyrin moiety to the respective Mo center in 1, 2, and 5. Electrochemical studies showed that the reduction potentials of the acceptor Mo centers in a newly synthesized pyridyl derivative (2; E(1/2)[Mo(I/0)] = approximately -1.4 V vs Ag/AgCl) and previously reported phenoxy- (1; E(1/2)[Mo(II/I)] = approximately -0.3 V vs Ag/AgCl) and amido- (3; E(1/2)[Mo(II/I)] = approximately -0.82 V vs Ag/AgCl) derivatives were varied over a wide range. Thus, studies with these complexes permitted us to correlate the probable effect of this potential gradient on the electron-transfer dynamics. Time-resolved absorption studies, following excitation at the Soret band of the porphyrin fragment in complexes 1, 2, and 5, established that forward electron transfer took place biexponentially from both S2 and S1 states of the porphyrin center to the Mo moiety with time constants 150-250 fs and 8-20 ps, respectively. In the case of MoL*(NO)ClX (where X is pyridine derivative 2), the high reduction potential for the MoI/0 couple allowed electron transfer solely from the S2 state of the porphyrin center. Time constants for the charge recombination process for all complexes were found to be 150-300 ps. Further, electrochemical and EPR studies with the trichromophoric complexes (3 and 4) revealed that the orthogonal orientation of the peripheral phenoxy/pyridyl rings negated the possibility of any electronic interaction between two paramagnetic Mo centers in the ground state and thereby the spin exchange, which otherwise was observed for related Mo complexes when two Mo centers are separated by a polyene system with comparable or larger separation distances.