Structural factors determining photophysical properties of directly linked zinc(II) porphyrin dimers: Linking position, dihedral angle, and linkage length

We have investigated the relationship between the photophysical properties and structures of a series of directly linked zinc(II) porphyrin dimers (mmZ2, mbZ2, and bbZ2) using time-resolved spectroscopic measurements and theoretical calculations. Their unique characters such as CT nature and torsional motion are caused by interporphyrin interactions and steric effects, respectively, which can be fully understood in terms of three structural factors: linking position, dihedral angle, and linkage length. The orthogonal geometry and heterolinking of mmZ2 and mbZ2 induce the localized MOs and electron unbalance in the constituent porphyrin units, respectively, and consequently lead to distinct CT characters in spite of their different origin. On the other hand, a small interporphyrin steric hindrance in bbZ2 makes a torsional motion possible around the direct β-β′ linkage in the excited state, which is correlated with the solvent dependence of the fast S₁fluorescence decay component. On the basis of this work, we can gain further insight into the effect of individual structural factors on the photophysical properties, which provides a firm basis for further understanding of the photophysical properties mainly determined by the structural factors in multiporphyrin systems.