Quantum chemical design for enhanced second-order NLO response of terpyridine-substituted hexamolybdates

Abstract

Abstract A dramatic increase in the second‐order nonlinear optical (NLO) response of terpyridine‐substituted hexamolybdates has been observed from 886.55 × 10 –30 esu (system 1 ) to 4622.92 × 10 –30 esu (system 7 ). The dipole polarizabilities and second‐order nonlinear optical (NLO) properties of terpyridine derivatives of hexamolybdates have been investigated by using time‐dependent density functional theory (TDDFT). The quantum mechanical design suggests that [Mo 6 O 18 (N 4 C 25 H 14 (CF 3 ) 2 (CN) 2 )] 2– (system 7 ) is the best choice among all studied systems to improve nonlinearity. The electron‐withdrawing ability of electron‐acceptor groups (F, Cl, Br, I, CF 3 , and CN) at the end of the terpyridine ligand directs the charge transfer (CT) from the POM cluster to the terpyridine segment along the z axis, which leads to an efficient second‐order NLO molecular design. These small changes in molecular composition by substitution may have disproportionately huge effects on the NLO properties, which can be attributed to the so‐called “butterfly effect”.

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