Structural, optical, and photophysical properties of nickel(II) alkylthioporphyrins: insights from experimental and...

The ground- and excited-state properties of a Ni(II) porphyrin bearing peripheral alkylthio group, NiOMTP (OMTP = 2,3,7,8,12,13,17,18-octakis methylthio porphyrinate) have been investigated by steady-state and time-resolved absorption spectrometry and DFT/TDDFT theoretical methods. Several conformations corresponding to different deformations of the porphyrin core and to different orientations of the alkylthio groups have been theoretically explored. The nearly degenerate, purely ruffled D(2d) and hybrid (ruffled with a modest degree of saddling) D(2) conformations, both characterized by an up-down (ud) orientation of the vicinal methylthio groups are by far the preferred conformations in the "gas phase". In contrast to NiOEP, it is the orientation of the peripheral substituents rather than the type and degree of distortions of the porphyrin core that determines the stability of the NiOMTP conformers. The ground-state electronic absorption spectra of NiOMTP exhibit significant changes compared to its parent NiP and beta-alkylated analogues, such as NiOEP, resulting in a considerable red shift of the B and the Q bands, intensification and broadening of the Q band, and additional weak absorptions in the region between the Q and B bands. These spectral changes can be understood in terms of the electronic effects of the methylthio groups with nonplanar distortions of the porphyrin ring playing a very minor role. Transient absorption measurements with sub-picosecond resolution performed in toluene and TDDFT calculations reveal that following photoexcitation, NiOMTP deactivates by the pathway 1(pi,pi) --> 3(d(z2),d(x2-y2))--> ground state. The (d,d) state exhibits complex spectral evolution over ca. 8 ps, interpreted in terms of vibrational relaxation and cooling. The cold ligand-field excited state decays with a lifetime of 320 ps. At variance with the highly distorted nickel porphyrins but similar to the planar analogues, the (d,d) spectrum of NiOMTP has transient absorption bands immediately to the red of the bleaching of the ground-state Q and B bands.