Butterfly and Nest‐Shaped Tp*‐W‐Cu‐S Cluster Monomers and Dimers with Hexamethylenetetramine as Ligand: Anion‐Dependent Structures and Nonlinear Optical Properties

Abstract

Main observation and conclusion The assembly of [Et4N][Tp*WS3] (1) with CuX (Tp* = hydridotris(3,5‐dimethylpyrazol‐1‐yl)borate; X = Cl, Br, and I) or [Cu(MeCN)4][PF6] in the presence of tetratopic ligand hexamethylenetetramine (HMT) afforded an array of four cluster‐based compounds, which are either neutral or anionic. These compounds include [Tp*WS3Cu3Cl2(HMT)] (2, monomer, neutral), [Tp*WS3Cu3Br2(HMT)] (3, monomer, neutral), [Tp*WS3Cu3I1.5(HMT)]2I (4, dimer, anionic), and [Tp*WS3Cu2(HMT)]2(PF6)2 (5, dimer, anionic). The size of the halogen is found to dictate the structures (2/3 versus 4), and the presence/absence of halogen also affects the utilization of coordinate site of HMT (4 versus 5) by creating more available Cu(I) site in the case of 5. The structures of 2—5 are also characterized using elemental analysis, Fourier‐transform infrared (FT‐IR) spectra, and ultraviolet‐visible (UV‐Vis) spectroscopy, with the dimeric structure of 5 also selected for the third‐order nonlinear optical (NLO) property investigations. The NLO measurement results suggest that the hyperpolarizability value (γ) of 5, reflecting its NLO properties as a neat material, features 2.12×10−30 esu, and it is comparable to other W/Cu/S cluster‐based molecular entities, rendering 5 a promising NLO‐active material.

Bucket Effect to Improve Third‐Order Nonlinear Optical Response on Metal‐Heteroaromatic Compounds

“…With the development of optical quantum information technology, nonlinear optical (NLO) materials demonstrate broad application perspectives in various emerging fields, such as atomic cooling, [ 1 ] quantum information storage, [ 2 ] photonic flywheel, [ 3 ] optical switching, [ 4 ] and functional THz emitters, [ 5 ] which put forward more requirements for the design and synthesis of novel NLO materials with high response coefficients. [ 6‐7 ] Previous studies have illustrated the profound influence of intermolecular packing of crystal structures, solvent effect, [ 8 ] and the interpenetrated structures [ 9 ] on third‐order NLO effects. Furthermore, the π‐conjugated systems of both organometallic rings [ 10 ] and ligands [ 11‐12 ] also effectively promote the NLO effects, which have been verified in former research.…”

Adipic acid directed self-healable supramolecular metallogels of Co(ii) and Ni(ii): intriguing scaffolds for comparative optical-phenomenon in terms of third-order optical non-linearity

“…46 MOFs belong to a versatile class of materials that exhibit numerous applications in terms of their optical nature. 47,48 Non-linear optically active materials possess imminent futuristic applications in various fields, [49][50][51][52][53] such as optical devices, including signal processors, 54,55 optical limiters, [56][57][58] and optical switches. 59 But, the targeted design and synthesis of self-healable metallogel have yet not been offered through prognostic acuity.…”

Recent Progress in Design of Organic Electro‐optic Materials with Ultrahigh Electro‐optic Activities†

“…The next information technological revolution needs the chip‐ scale integrations between electronic and photonic devices. [ 6,36,39‐44 ] Compared to electronics, EO devices possess too large footprints and drive voltages to be integrated with CMOS in chip scale by monolithic manner. To reduce the footprint and drive voltage needs high‐performance EO materials and novel device design to improve the light‐materials interaction.…”