First Hyperpolarizabilities of Intramolecular Charge-Transfer Architectures Based on Acenaphthene Derivatives in Gas, Solution, and Solid States.

Constructing charge transfer (CT) systems and packing arrangement are common and effective methods to control the efficiency of nonlinear optical (NLO) materials. Apart from the traditional through-bond CT (TBCT) systems, through-space CT (TSCT) also leads to distinctive optical and electronic properties. Meanwhile, corresponding theoretical investigations of the aggregation effect are highly desired. In this work, some TSCT and model compounds incorporating acenaphthene as a scaffold and triphenylamine (TPA) as the donor are theoretically performed to systematically reveal the effect of both solvent and solid environments on their static first hyperpolarizabilities (β tot ) by using the polarizable continuum model (PCM) and the combined quantum mechanics and molecular mechanics (QM/MM) method. Results indicate that the dichloromethane solvent effect within the PCM approach causes an almost 2 times increase of the β tot values. Besides, the different packing modes and intermolecular interactions have remarkable influence on the second-order NLO properties. For the case of TPA-ace-CN in the crystal state, the parallel arrangement will lead to large NLO responses (4.9 × 10 -30 esu) compared to the correspondingly isolated molecule (3.4 × 10 -30 esu). However, for the TPA-ace-TRZ compound with the TSCT architecture, selection of the molecular arrangement may make the aggregate ineffective due to the offset of the through-space dipole and charge transfer between D-A groups, which lead to the β tot values decreasing from 15.2 × 10 -30 to 7.7 × 10 -30 esu. We believe that our calculation will serve as a guide for the exploration of more efficient NLO materials wherein the molecules are oriented in their most favorable arrangements.