A Series of Novel Derivatives with Giant Second Hyperpolarizabilities, Based on Radiaannulenes, Tetrathiafulvalene, Nickel Dithiolene, and Their Lithiated Analogues

Abstract

The main goal of this study was the design/ recognition of a series of derivatives with exceptionally large hyperpolarizabilities, the understanding of the mechanism through which these properties are derived, and the generalization of the resulting findings. Thus, we have studied the structure, a series of properties involving the excitation energies and the diradical character, but mainly the (hyper)polarizabilities of some oligomers of radiaannulene-tetrathiafulvalene (RA-TTF), radiaannulene-bis(ethylene-1,2dithiolato)nickel (RA-NiBDT), and their lithiated analogues. The employed methodology involves MP2 and DFT techniques, approaches for the computation of static and frequency-dependent properties, and techniques for the calculation of electronic and vibrational contributions. The polarizability has been partitioned be employing the fractional occupational Hirshfeld iterative method. Indices for the calculation of the diradical character of the NiBDT oligomers have been employed. We have found that (i) oligomerization increases γ zzzz (second hyperpolarizability), (ii) substitution of TTF with NiBDT leads to a very large increase of γ zzzz , and (iii) lithiation leads to extremely large nonlinearities. The importance of NiBDT and lithium as building blocks for the production of NLO materials is highlighted.

Design of Hückel–Möbius Topological Switches with High Nonlinear Optical Properties

“…For this purpose, it has been well-established in the literature that the computational theoryaided design can be a useful tool to optimize the molecular electro-optic performance. [28][29][30][31][32][33][34][35][36][37][38][39][40][41][42][43][44] Recently, several works [45][46][47][48][49][50][51][52][53][54][55] have evaluated the NLOP of Hückel and Möbius topologies. For instance, the present authors studied the electronic and vibrational contributions to static and dynamic NLOP of the Hückel-Möbius switch of the bianthraquinodimethane modified [16] annulene 56,57 and A,D-di-p-benzi [28]hexaphyrin(1.1.1.1.1.1).…”

A Computational Strategy for the Design of Photochromic Derivatives Based on Diarylethene and Nickel Dithiolene with Large Contrast in Nonlinear Optical Properties

“…Most of the presented here results have been computed by using the (U)­CAM-B3LYP functional with the 6-31G* basis set for H, C, Ο, F, and S, atoms. , The quasi-relativistic, effective core potential ECP28MWB­(SDD) has been employed for Ni . A detailed study on the performance of CAM-B3LYP/6-31G*, for NiBDT derivatives, has been reported . The satisfactory performance of the procedure we employ has been confirmed by comparing the DFT results with the more rigorous CASSCF/CASPT2 [complete active space multiconfiguration SCF/CAS second order perturbation theory] and CCSD­(T) [coupled-cluster with single, double and perturbative triple excitations (CCSD­(T))] ones .…”

Sonogashira-Like Coupling Reactions with Phosphine–Gold(I) Alkynyl Complexes

“…25 A recent theoretical study has also shown that such compounds are interesting for their nonlinear optical properties. 26 The first synthesis 23b (Scheme 11) did not involve gold(I) alkynyl complexes. Instead, the trimethylsilyl groups of TEE 22 were removed selectively using K 2 CO 3 in MeOH and THF,…”