Quadratic and cubic nonlinear optical properties of salts of diquat-based chromophores with diphenylamino substituents

Coe, Benjamin J. and Fielden, John and Foxon, Simon P. and Helliwell, Madeleine and Brunschwig, Bruce S. and Asselberghs, Inge and Clays, Koen and Olesiak, Joanna and Matczyszyn, Katarzyna and Samoc, Marek (2010) Quadratic and cubic nonlinear optical properties of salts of diquat-based chromophores with diphenylamino substituents. Journal of Physical Chemistry A, 114 (45). pp. 12028-12041. ISSN 1089-5639

Abstract

A series of chromophoric salts has been prepared in which 4-(diphenylamino)phenyl (Dpap) electron donor groups are connected to electron-accepting diquaternized 2,2′-bipyridyl (diquat) units. The main aim is to combine large quadratic and cubic nonlinear optical (NLO) effects in potentially redox-switchable molecules with 2D structures. The chromophores have been characterized as their PF6− salts by using various techniques including electronic absorption spectroscopy and cyclic voltammetry. The visible absorption spectra are dominated by intense π → π* intramolecular charge-transfer (ICT) bands, and all of the compounds show two reversible or quasireversible diquat-based reductions and partially reversible Dpap oxidations. Single crystal X-ray structures have been obtained for one salt and for the precursor compound (E)-4-(diphenylamino)cinnamaldehyde, both of which adopt centrosymmetric space groups. First hyperpolarizabilities β have been measured by using hyper-Rayleigh scattering (HRS) with a 800 nm laser, and Stark (electroabsorption) spectroscopy of the ICT bands affords estimated static first hyperpolarizabilities β0. The directly and indirectly derived β values are large and generally increased substantially for the bis-Dpap derivatives when compared with their monosubstituted analogues. Polarized HRS studies show that the NLO responses of the disubstituted species are dominated by “off-diagonal” βzyy components. Lengthening the diquaternizing alkyl unit lowers the electron-acceptor strength and therefore increases the ICT energies and decreases the E1/2 values for diquat reduction. However, compensating increases in the ICT intensity prevent significant decreases in the Stark-based β0 responses. Cubic NLO properties have been measured by using the Z-scan technique over a wavelength range of 520−1600 nm, revealing relatively high two-photon absorption cross-sections of up to 730 GM at 620 nm for one of the disubstituted chromophores.