Supramolecular interaction of PCBM with porphyrins in solution: Photophysical insights

This work reports the self-assembly between [6,6]-phenyl C₇₁ butyric acid methyl ester (PCBM) and 2,3,7,8,12,13,17,18-octaethyl-21H,23H porphyrin (1)(and/2,3,7,8,12,13,17,18-octaethyl-21H,23H porphyrin Zn(II) (2) in toluene. Ground state intermolecular interaction is evidenced from absorption spectrophotometric measurements. New absorption bands are observed in the visible region which may be identified due to charge transfer (CT). Several important physicochemical factors are enumerated for PCBM-1 and PCBM-2 systems. Fluorescence investigations elicit complex formation of PCBM with porphyrins (with both 1 and 2) and reveal considerable magnitude of binding constant (K) for PCBM-2 system, i.e., K_PCBM-2 = 80,435 dm³⋅mol^-1 compared to PCBM-1 system, i.e., K_PCM-1 = 12,600 dm^3·mol^-1 as well as highly ratio of selectivity in binding (K_PCBM-2/K_PCBM-1 ∼ 6.4). Time resolved fluorescence experiments reveal that photoexcited decay from the excited singlet state of porphyrins (i.e., 1* and 2*) by PCBM is statically controlled compared to dynamic path. Magnitude of solvent reorganization energy indicates possibility of faster charge recombination in case of PCBM-2 system. Both ¹H and ¹³C NMR measurements provide substantial support behind complexation of PCBM with porphyrins (both 1 and 2) in solution. Ab initio calculations in vacuo support the trend in K for PCBM-1 and PCBM-2 systems and establish the proper orientation of PCBM towards 1 (and/ 2) during complexation. Transient absorption measurements establish two different mode of energy transfer pathway from porphyrin to PCBM in toluene.