Six [Tp*WS3Cu2]-based clusters derived from [Et4N][Tp*WS3], Cu(i) salts and phosphine ligands: syntheses, structures and enhanced third-order NLO properties

Abstract

Treatment of [Et4N][Tp*WS3] (Tp* = hydridotris(3,5-dimethylpyrazol-1-yl)borate) (1) with CuX (X = Br, SCN) and PPh3 or 1,1-bis(diphenylphosphino)methane (dppm) produced two neutral trinuclear clusters [Tp*W(μ3-S)(μ-S)2Cu2Br(PPh3)] (2) and [Tp*W(μ3-S)(μ-S)2Cu2(SCN)(dppm)]2·MeCN·Et2O (3·MeCN·Et2O). Reactions of 1 with [Cu(MeCN)4]PF6, NH4PF6 and 1,3-bis(diphenylphosphino)propane (dppp), N,N-bi(diphenylphosphanylmethyl)-2-aminopyridine (bdppmapy), N,N,N',N'-tetra(diphenylphosphanylmethyl)ethylenediamine (dppeda), or 1,4-N,N,N',N'-tetra(diphenylphosphanylmethyl)benzenediamine (dpppda) afforded four clusters containing butterfly-shaped [Tp*WS3Cu2] cores, [Tp*W(μ3-S)(μ-S)2Cu2(dpppds)](PF6)·1.25MeCN (dpppds = 1,3-bis(diphenylphosphino)propane disulfide) (4·1.25MeCN), [Tp*W(μ3-S)(μ-S)2Cu2(bdppmapy)](PF6)·3MeCN (5·3MeCN) and {[Tp*W(μ3-S)(μ-S)2Cu2]2(L)]}(PF6)2·Sol (6·Et2O: L = dppeda, Sol = Et2O; 7·1.25MeCN: L = dpppda, Sol = 1.25MeCN). Compounds 2-7 were characterized by elemental analysis, IR, UV-Vis, (1)H and (31)P{(1)H} NMR spectra, electrospray ion mass spectra (ESI-MS) and single-crystal X-ray diffraction. Compound 2 or 3 has a butterfly-shaped [Tp*WS3Cu2] core in which one [Tp*WS3] unit binds two Cu(I) centers via one μ3-S and two μ-S atoms. In the cationic structure of 4 or 5, one in situ-formed dpppds or bdppmapy combines with the [Tp*WS3Cu2] core via each of its two S atoms or two P atoms coordinated at each Cu(I) center. In the bicationic structure of 6 or 7, two [Tp*WS3Cu2] cores are linked by one dppeda or dpppda bridge to form a bicyclic structure. The isolation of 2-7 with unstable [Tp*WS3Cu2] cores may be ascribed to the coordination of P- or S-donor ligands at Cu(i) centers of these cores. The third-order nonlinear optical (NLO) properties of 2-7 in DMF were also investigated by using the femtosecond degenerate four-wave mixing (DFWM) technique at 800 nm.

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

“…[ 47 ] It is also higher than those found in known W/Cu/S clusters derived from 1 (Table 1), e.g ., [Tp*WS 3 Cu 2 (bipy) 1.5 ](PF 6 ) (3.2 × 10 −31 esu), [ 42 ] K[Tp*WS 3 Cu 3 (DMF){Cu 2 (CN) 4.5 }] 2 (4.39 × 10 −31 esu) (DMF = N , N ‐dimethylformamide), [ 3 ] [Tp*WS 3 Cu 3 (DMF)(CN) 3 Cu] (4.36 × 10 −31 esu), [ 32 ] and [Tp*WS 3 Cu 2 (bdppmapy)](PF 6 ) (2.43 × 10 −31 esu) (bdppmapy = N , N ‐ bi‐(diphenylphosphanylmethyl)‐2‐aminopyridine). [ 48 ] These values are similar to those of [(Tp*WS 3 Cu 2 Cl) 2 (dppe)] (4.71 × 10 −30 esu; dppe = 1,2‐bis‐(diphenylphosphino)ethane) [ 18 ] and [Tp*WS 3 Cu 2 (CN) 2 Cu](pz) 0.5 (3.69 × 10 −30 esu; pz = pyrazine). [ 16 ] They are slightly lower than those of [(Cp*MoS 3 Cu 3 ) 2 (bpe) 2 Br 4 ] (4.29 × 10 −29 esu; bpe = 1,2‐bis(4‐pyridyl)ethane) [ 8 ] and [Cp*MoS 3 Cu 3 (pyz)(NCS) 2 ] (2.96 × 10 −29 esu; pyz = 1,4‐pyrazine).…”

Bioinorganic modeling chemistry of carbon monoxide dehydrogenases: description of model complexes, current status and possible future scopes

“…[48][49][50][51] Individual W VI (μ 2 -S) 2 Cu I rhombs are, however, relatively uncommon and tend to be bridged with similar units either through metal atom or through sulfido atoms thus forming μ 3 -S structures. [52][53][54][55][56][57][58] The high probability of the rhomb formation was best demonstrated by the formation of 5, even when using a monosulfido species, [(bdt)WO 2 S] 2− as a starting material. Future work should build up on the remedies of these synthetic problems.…”

Diverse Tp*-Capped W–Cu–S Clusters from One-Pot Assembly Involving in Situ Thiolation of Phosphines

“…has experienced a sustainable development since the pioneering studies of Müller − and Sécheresse, − fueled by the identification of the iron–molybdenum cofactor (FeMoco) − and later carbon monoxide dehydrogenase, , respectively featuring [Mo–Fe–S] and [Mo–Cu–S] cluster cores. In the last 3 decades, such a research scope was significantly broadened, merging into the rapid development of supramolecular chemistry and coordination polymers. − New properties accordingly appeared such as nonlinear-optical (NLO) properties, ,− catalysis, ,− and adsorption and sensing. , The advancement of the research paradigm accordingly spurs material design at the molecular level, as witnessed from the evolvement of Mo (W)–S synthons from inorganic [MO x S 4– x ] 2– ( x = 0, 1, and 2) − through organometallic [Cp*MS 3 ] − ,− to [TpMoS­(S 4 )] − /[Tp*MoS­(S 4 )] − /[TpWS 3 ] − /[Tp*WS 3 ] − (M = Mo, W; Cp* = pentamethylcyclopentadiene; Tp = hydridotris­(pyrazol-1-yl)­borate; Tp* = hydridotris­(3,5-dimethylpyrazol-1-yl)­borate), to which we are currently dedicated. ,− Introducing both Cp* and Tp/Tp* imparts solubility into the final molecular ensembles to facilitate their isolation in pure crystalline form and their subsequen...…”