Rectangle and [2]catenane from cluster modular construction

Abstract

Reaction of [Et4N][Tp*WS3] (1) with [Cu(MeCN)4]PF6, CsCl, isonicotinic acid and CuCN, and treatment of [Et4N][Tp*WS3(CuCl)3] (2)/[Et4N][{Tp*WS3Cu3Cl}2(μ-Cl)2(μ4-Cl)] (3) with AgOTf and bpp (Tp* = hydridotris(3,5-dimethylpyrazol-1-yl)borate; bpp = 1,3-di(4-pyridyl)propane) give rise to [Et4N]2[{Tp*WS3Cu3(CN)0.5}2(μ-Cl)2(μ4-Cl)]2(PF6)2 (4) and [(Tp*WS3Cu3)2(μ3-Cl)2(bpp)3]2(OTf)4 (5), respectively. Compounds 4 and 5 feature cluster-based rectangle and [2]catenane architecture, and both exhibit enhanced third-order nonlinear optical responses relative to those of 1.

Structure Types and Magnetic Behavior of Cobalt Nanoclusters

“…Polynuclear metal macrocyclic complexes have attracted much attention due to their applications in catalysis, photoluminescence, magnetic properties, and host–guest exchange. − At present, the research on macrocyclic polynuclear metal complexes is mainly focused on metal crown ethers. Metal crown ethers can be regarded as a new type of polynuclear metal macrocyclic complex produced by metal ions and nitrogen atoms replacing carbon atoms in crown ether rings. − Its structure is similar to that of metal cluster compounds, and its crown ether ring contains at least three metal atoms. Because of their unique structure, metal crown ethers have strong visible absorption spectra and redox properties.…”

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

“…Transition metal clusters of organo‐thiometallates such as [Cp*MS 3 ] − (Cp* = pentamethylcyclopentadienyl; M = Mo, W), [ 1 ] [TpMoS(S 4 )] − , [Tp*MoS(S 4 )] − , [TpWS 3 ] − and [Tp*WS 3 ] − (Tp = hydridotris(pyrazol‐1‐yl)borate; Tp* = hydridotris(3,5‐dimethylpyrazol‐ 1‐yl)borate) [ 2 ] have been extensively investigated in the last two decades because of their diverse structural characteristics, [ 3‐9 ] their revelation to biological systems, [ 10‐13 ] catalysis, [ 14‐15 ] and optoelectronic materials. [ 3,16‐24 ] In this regard, we and others have developed a keen interest in the development of molecular arrays from preformed Mo(W)‐Cu(Ag)‐S clusters. [ 25‐29 ] Some of these molecular entities are capable of gas adsorption, [ 30 ] sensing, [ 31 ] or exhibit nonlinear optical properties.…”

“…[ 25‐29 ] Some of these molecular entities are capable of gas adsorption, [ 30 ] sensing, [ 31 ] or exhibit nonlinear optical properties. [ 17‐19,21,30,32‐37 ] We have further investigated a diverse array of molecular entities using rigid/flexible ditopic ( e.g ., 4,4’‐bipyridine, bipy), [ 19 ] tritopic ( e.g ., 2,4,6‐tri(4‐ pyridyl)‐1,3,5‐triazine, tpt), [ 7,19,38 ] and tetratopic N ‐based ligands ( e.g ., 5,10,15,20‐tetra(4‐pyridyl)‐21 H ,23 H ‐porphyrin, H 2 tpyp), [ 7 ] wherein these N sites are co‐planar. Further introducing a tetratopic ligand with four N sites spatially arranged in a tetrahedral manner is expected to yield high‐dimensional networks of interest.…”

Third-order nonlinear optical adjusting behavior in azobenzene metal complexes

“…Such metal complexes show the same advantages of organic molecules, while the central metal ions also effectively influences the electronic properties of the organic molecules, improving the response of the third-order NLO compounds [17][18][19]. More importantly, metal complexes usually exhibit diverse spatial structures and conjugated modes and can provide a wealth of electronic flow systems to enhance and extend NLO behaviors [20][21][22][23][24][25][26][27]. Therefore, metal complexes are excellent candidates to develop third-order NLO switches.…”