AB INITIO AND DFT THEORETICAL INVESTIGATIONS ON NOVEL PORPHYRIN–FULLERENE SUPRAMOLECULAR DYADS FOR PHOTOVOLTAIC DEVICES

Abstract

The conformational stability and electronic structures of novel H 2 -(1) and Zntetraphenylporphyrin-[60]fullerene (2) dyads, in which the [60]fullerene is directly linked to the tetrapyrrolic rings by ethynylenephenylene subunits, have been studied by ab initio and density functional theory calculations. From the investigation on frontier molecular orbitals, it was found that the lowest unoccupied molecular orbital state of these supramolecules is localized on the fullerene and that the highest occupied molecular orbital state is localized on the porphyrin moiety. Molecular electrostatic potential maps clearly demonstrate the electron transfer phenomena from the porphyrin moiety to the fullerene in dyads 1 and 2.Keywords: H 2 -(1) and Zn-tetraphenylporphyrin-[60]fullerene (2) dyads; ab initio and density functional theory calculations; HOMO-LUMO energy gap; molecular electrostatic potential maps. * Corresponding author. 1055 J. Theor. Comput. Chem. 2008.07:1055-1069. Downloaded from www.worldscientific.com by NANYANG TECHNOLOGICAL UNIVERSITY on 08/23/15. For personal use only.

Synthesis and Spectroscopic and Electrochemical Properties of an Axially Symmetric Fullerene–Porphyrin Dyad with a Rigid Pyrrolo[3,4-c]pyrrole Spacer

“…According to the calculations, the HOMO of molecule 2 is located mostly on the porphyrin moiety, while the LUMO is located on the fullerene cage (Figure ). This is typical for fullerene–porphyrin dyads and is the precondition for generating a charge-separated state. The simple approach for the estimation of the ability of a molecule to form a long-lived CS state is based on the frontier molecular orbital description of photoinduced electron transfer .…”

“…All solutions were purged prior to electrochemical measurements using argon gas. CVA curves were recorded under an argon atmosphere at various potential sweep rates (10,20,30,50, and 70 mV/s) for compounds 3a−e, 4a−c, and 5 (see the Supporting Information). In most cases, potentials are referenced to a Ag/AgCl electrode.…”