Design of nickel donor–acceptor dithiolenes for 2nd order nonlinear optics: an experimental and computational study

Abstract

This study, concerning the influence on the NLO properties of a remote functionality in the donor of D–Ni–A dithiolenes 1–4, allows to point out the relationship between NLO properties and the donor capability in modulating the low-energy absorption.

Annulation of a 1,3-dithiole ring to a sterically hindered o-quinone core. Novel ditopic redox-active ligands

“…Gem-dithiolates are comparatively less studied than related dithiocarboxylates [20][21][22][23]. There are some reports in the literature regarding their application as ligands for the preparation of complexes exhibiting non-linear optical activity as well as possessing extraordinary magnetic properties [24]. The simplest structures that were classified both as gem-dithiolate and dithiocarboxilate are trithiocarbonate salts.…”

Progress and perspectives on strategies to control photochemical properties in Metallo-Dithiolene Donor-Acceptor systems

“…showing the capability of the novel derivatives to respond to external stimuli (protons, silver ions, and light-irradiation) to obtain multifunctional linear and nonlinear chromophores will be presented [31][32][33][34][35]. Promising and less promising results in the production of 2 nd NLO-active materials where chromophores are embedded into polymeric PMMA (PolyMethylMethAcrylate) poled films or form crystals belonging to non-centrosymmetric point groups are also here shortly discussed.…”

“…The same A2 Acceptor (R=Bz) has been employed to synthesize Ni-complexes [NiA2-Dn] (n = 3-6), on varying the Donor [33]. Despite, as said, the corresponding platinum-complexes would exhibit larger NLO responses, the use of nickel-metal offers advantages in terms of cost and depletion of precious metals and in terms of higher solubility of related complexes in common organic solvents.…”

“…During the cooling process and after the removal of the electric field, the SHG signal is monitored as a function of time and temperature, to check whether or not reorientation of the chromophores within the polymeric matrix occurs in the explored time and temperature range. This technique has been employed on thin films of [NiA2-Dn] (A2 = Bz2pipdt, n = 3-6) [33] and of Bu4N[PdA1D1]; Bu4N[PdA1D4] and Bu4N[PtA1D4] [35] dispersed in PMMA matrix. The SHG signals, negligible at room temperature, reach a maximum value as the temperature is increased around Tg of the PMMA and the electric field applied.…”

Substituent and redox effects on the second-order NLO response of Ru(ii) complexes with polypyridine ligands: a theoretical study

“…14,15 Both experimental and theoretical investigations showed that organometallic complexes possess low-lying charge-transfer transitions and fine-tuned NLO properties due to their diversity of ligands and the presence of a redox-active metal center. [16][17][18][19][20][21][22] Therefore, organometallic NLO materials must have more extensive applications compared to those pure inorganic or organic NLO materials. [23][24][25][26] Among various organometallic complexes, compounds containing transition metals, Ru(II), Ir(III), Os(II), Pt(II), Pd(II) or Zn(II), have attracted considerable attention due to their unique structural and high environmental stability.…”