Theoretical study of one- and two-photon absorption properties of expanded donor-acceptor calix[4]arenes

Two types of donor(D)-acceptor(A) calix[4]arenes have been theoretically studied using DFT//B3LYP/6-31G(d) method and ZINDO/CISD method. The calculations show that the substitution of C equivalent to C by the conjugation bridge C=C and N=N plays an important part in altering one-photon absorption (OPA) and two-photon absorption (TPA) properties. The maximum OPA wavelengths of all studied compounds are less than 400 nm, which means high transparency. The geometry of the calixarenes strongly influences the TPA properties of the studied compounds. In addition, the nitro derivatives have a wider TPA response range than other non-nitro derivatives. The tetrasubstituted calix[4]arenes (type B calixarenes) have a larger TPA cross-section values than the bisubstituted calix[4]arenes (type A calixarenes). Copyright (C) 2009 John Wiley & Sons, Ltd.