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Novel perylene imide derivatives with both electron-donating and bulky substituents have been synthesized for dye-sensitized solar cells. The power conversion efficiency reached 2.6%, which is the highest value among perylene-sensitized TiO2 solar cells.

For development of the molecular solar-energy conversion systems, it is crucial to investigate how both the molecular geometry and electronic structure of electron donor-bridge-acceptor (D-B-A) molecules contribute to the electronic coupling for the charge-separation (CS) and charge-recombination (CR) processes. In a D-B-A system of a porphyrin-fullerene dyad (ZnP-C(60)) bridged by a diphenyldisilane spacer, we have characterized one specific folded molecular conformation in the CS state among several existing conformations using the time-resolved electron paramagnetic resonance (TREPR) method at low temperature. To determine the molecular conformation and spin-spin exchange coupling of the CS state, we have considered (1) the electron spin polarization transfer from the excited triplet state of the C(60) moiety to the CS state and (2) the sublevel-selective spin relaxations and CR in the CS state. In the CS state of this conformation, although the ZnP cation and C(60) anion radicals are in close proximity, direct overlap between their singly occupied molecular orbitals is small, resulting in detection of the long-lived CS state which has a totally different conformation from the optically detected, charge-transfer (CT) complex. It has been demonstrated that, among several folded and extended molecular conformations created by the flexibility of the -Si-Si- bridge, the EPR conformation can play a role on the prevention of the energy-wasting CR.

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