Tunable Chiral Second-Order Nonlinear Optical Chromophores Based on Helquat Dications

0478612 - ÚOCHB 2018 RIV US eng J - Článek v odborném periodiku
Buckley, L. E. R. - Coe, B. J. - Rusanova, D. - Joshi, Vishwas - Sánchez, S. - Jirásek, Michael - Vávra, Jan - Khobragade, Dushant - Severa, Lukáš - Císařová, I. - Šaman, David - Pohl, Radek - Clays, K. - Depotter, G. - Brunschwig, B. S. - Teplý, Filip
Tunable Chiral Second-Order Nonlinear Optical Chromophores Based on Helquat Dications.
Journal of Physical Chemistry A. Roč. 121, č. 31 (2017), s. 5842-5855. ISSN 1089-5639. E-ISSN 1520-5215
Grant CEP: GA ČR GA13-19213S; GA MZd(CZ) NV16-31156A
Grant ostatní: AV ČR(CZ) M200551208
Institucionální podpora: RVO:61388963
Klíčová slova: hyper-Rayleigh scattering * excited states * derivatives
Obor OECD: Physical chemistry
Impakt faktor: 2.836, rok: 2017

Fourteen new dipolar cations have been synthesized, containing methoxy or tertiary amino electron donor groups attached to helquat (Hq) acceptors. These Hq derivatives have been characterized as their TfO- salts by using various techniques including NMR and electronic absorption spectroscopies. UV-vis spectra show intense, relatively low energy absorptions with lambda(max) approximate to 400-600 nm, attributable to intramolecular charge-transfer (ICT) excitations. Single-crystal X-ray structures have been solved for two of the chromophores, one as its PF6- salt, revealing centrosymmetric packing arrangements (space groups Pbca and P (1) over bar). Molecular quadratic nonlinear optical (NLO) responses have been determined directly by using hyper-Rayleigh scattering (HRS) with a 800 nm laser, and indirectly via Stark (electroabsorption) spectroscopy for the low energy absorption bands. The obtained static first hyperpolarizabilities beta(0) range from moderate to large: (9-140) X 10(-30) esu from HRS in MeCN and (44-580) X 10(-30) esu from the Stark data in PrCN. The magnitude of beta(0) increases upon either extending the pi-conjugation length or replacing a methoxy with a tertiary amino electron donor substituent. Density functional theory (DFT) and time dependent DFT calculations on selected tertiary amino chromophores confirm that the low energy absorptions have ICT character. Relatively good agreement between the simulated and experimental UV-vis absorption spectra is achieved by using the CAM-B3LYP functional with the 6-311G(d) basis set. The beta(tot) values predicted by using DFT at the same level of theory are large ((472-1443) X 10(-30) esu in MeCN). Both the theoretical and experimental results show that para-conjugation between Hq and electron donor fragments is optimal, and enlarging the Hq unit is inconsequential with respect to the molecular quadratic NLO response.
Trvalý link: http://hdl.handle.net/11104/0274677