[PyH][{TpMo(μ3-S)4Cu3}4(μ12-I)]: a unique tetracubane cluster derived from the S–S bond cleavage and the iodide template effects and its enhanced NLO performances

Abstract

Reactions of [Et4N][TpMoS(S4)] with three equiv. of CuI in MeCN or in pyridine gave rise to one dicubane and one tetracubane anionic clusters, [Et4N]2[{TpMo(μ3-S)3Cu3I}2(μ-I){Cu(μ-I)2(μ4-I)2}] and [PyH][{TpMo(μ3-S)4Cu3}4(μ12-I)], and their third-order nonlinear optical (NLO) responses were greatly enhanced relative to that of the precursor.

Heterometallic transition metal clusters and cluster-supported coordination polymers derived from Tp- and Tp*-based Mo(W) sulfido precursors

“…These sulfur atoms, upon release, serve as sticking ligands to bridge Cu centers from the nest-shaped cluster cores, yielding a tetrahedral cage. This in situ released sulfur is likely a template in the generation of the tetrahedral cages of 43 [71] and 44 [77]. The tetrahedral topology is also in line with the C 3 symmetry of the Tp or Tp* ligand.…”

“…The cause of the NLO performance enhancement, though lacking direct experimental evidence due to the difficulty in monitoring the in situ-formed species under laser irradiation, is tentatively proposed by Lang et al to originate from the disconnected molecular entities such as dimers, corroborated by those identified under ESI-MS conditions [77,99].…”

“…We are particularly interested in inspecting the performance changes upon networking the discrete cluster cores into molecular superstructures or coordination polymers. It is obvious that upon constructing clusters using P3 which exhibits almost no NLO response (Entry 2), the double-cubane type cluster 27 (Entry 40) and tetrahedral cage compounds 44 based on nest-shaped cluster (Entry 29) exhibited much better performance [77]. The NLO Fig.…”

“…All Tp*(43) and Tp(44) groups are omitted. The S atoms from the nest-shaped clusters and the face-capping S are differentiated by yellow and orange[71,77].…”

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.…”