Search

The reactions of the tungsten trisulfido complex of hydridotris(3,5-dimethylpyrazol-1-yl)borate (Tp*) [[Et.sub.4]N][Tp*W[S.sub.3]] with 3 equiv CuCl in CH[Cl.sub.3] has yielded a tetranuclear anionic cluster. The third order nonlinear optical (NLO) properties of these complexes are examined in solution under the femtosecond degenerate four-wave mixing method.

A demonstration that the acid-induced assembly of two interesting W/Cu/S supramolecular compounds, [Et4N]3[(WS4Cu2)2-(mu-CN)3].2MeCN and [PPH4][WS4Cu3(mu-CN)2].MeCN from performed clusters [Et4N or PPh4]2WS4(CuCN)2 is presented. The general strategy of using a weak acid to remove cynaide without causing decomposition of the cluster appears to be suitable only at lower concentrations of acetic acid.

An unprecedented pentanuclear lanthanum thiolate oxide complex is isolated as a result of the adventitious water but is regenerated in an acceptable yield through control of hydrolysis. This synthetic strategy can be used in the preparation of other new oxolanthanide thiolate complexes with better catalytic performances.

The assembly reactions of [P[Ph.sub.4]][[[eta].sup.5]-[C.sub.5][Me.sub.5])Mo[S.sub.3][(CuX).sub.3]] (X = Br, NCS) with 1,2-bis(4-bipyridyl)ethane (bpe) or 1,3-bis(4-pyridyl)propane (bpp) are examined and a family of [[[eta].sup.5]-[C.sub.5][Me.sub.5])Mo[S.sub.3][Cu.sub.3]]-supported compounds with one-dimensional arrays is isolated. The assembly reactions, crystal structures and third-order nonlinear optical properties in aniline are described.

A set of new [W[S.sub.4][Cu.sub.4]]- or [MoO[S.sub.3][Cu.sub.3]-based supramolecular assemblies are prepared from reactions of preformed cluster compounds [[[Et.sub.4]N].sub.4][W[S.sub.4][Cu.sub.4][I.sub.6]] and [[[(n-Bu).sub.4]N].sub.2][MoO[S.sub.3][Cu.sub.3][X.sub.3] (X = I, SCN) with flexible ditopic ligands. The results have provided new routes to the rational design and construction of complicated cluster-based supramolecular arrays.

A route to construction of two tetranuclear metal string compounds [{[[(Tab).sub.2]Ag][Au[(CN).sub.2]]}.sub.2] and [{[[(Tab).sub.2]Ag][Au[(CN).sub.2]]}.sub.2] from reactions of preformed complexes [[Au[(Tab).sub.2]].sub.2][([PF.sub.6]).sub.2] and [Ag[(Tab).sub.2]]([PF.sub.6])with K[Au[(CN).sub.2]] is demonstrated. These did not show luminescence, because these compounds, when dissolved tend to dissociate into nonemissive monomeric species, in which ionic interactions and aurophilic bonding interactions are not present.

Approaches to assembly of [[[eta.sup.5]-[C.sub.5][Me.sub.5]]W[S.sub.3][Cu.sub.3]]-based supramolecular compounds from pre-formed incomplete cubane-like clusters [P[Ph.sub.4]][[eta.sup.5]-[C.sub.5][Me.sub.5]]W[S.sub.3][Cu[X.sub.3]] (X=CN, Br) is investigated. The successful construction of compounds from the geometry-fixed clusters expands the scope of the rational design and construction of cluster-based supramolecular assemblies.

Hg(OAc)2 reacts with TabHPF6 [TabH=4-(trimethylammonio)benzenethiol] in MeCN/MeOH to form a mononuclear linear complex [Hg(tab)2](PF6)2. By using this complex as precursor, a new family of mercury(II) zwitterionic thiolate complexes, are prepared and characterized by elemental analysis, IR spectra, UV-vis spectra, H NMR and single-crystal X-ray crystallography.

The introduction of Li(super +) and Cl(super -) ions into lanthanide amide complexes afforded three unprecedented Ln-thiolate compounds when treated with a low concentration of benzenthiol. It is anticipated that the synthetic methodology might be applied to other Ln-amide compounds to yield previously unknown species with better catalytic activities.

Reactions of (NH4)2[MoOS3] with [Cu(MeCN)4](ClO4) and bis(3,5-dimethylpyrazolyl)methane (dmpzm) (molar ratio = 1:3:3) in MeCN produced a cationic cluster [MoOS3Cu3(dmpzm)3](ClO4) (1). 1consists of a unique 3D hydrogen-bonded network with empty C3-symmetry cavities. A set of C3(cyclohexane) or non-C3-symmetry solvent molecules (aniline, N,N′-dimethylformamide, formamide, and water) could recognize these C3-symmetry cavities and smartly fit themselves into them by converting themselves into C3-symmetry species through intriguing ways of symmetry-oriented molecular disorder and trimerlization. [ABSTRACT FROM AUTHOR]

The construction of a new set of [(η5-C5Me5)MoS3Cu3]-based supramolecular compounds with different one-dimensional (1D) arrays from two preformed clusters [PPh4][(η5-C5Me5)MoS3(CuX)3] (X = Br (1a), NCS (1b)) with 1,2-bis(4-pyridyl)ethane (bpe) and 1,3-bis(4-pyridyl)propane (bpp) is presented. Reactions of 1a with bpe in different molar ratios afforded {[{(η5-C5Me5)MoS3Cu3}2(μ-bpe)3.5Br4] · MeCN}n (2), {[{(η5-C5Me5)MoS3Cu3}2(μ-bpe)3Br4] · Sol)n (3a: Sol = DMSO · 3MeCN; 3b: Sol = 2aniline·3MeCN), {E{(η5-C5Me5)MoS3Cu3}2(μ-bpe)3(bpe)Br4] · 0.35DMF}n (4), and {[{(η5-C5Me5)MoS3Cu3}2(μ-bpe)2(μ-Br)(μ3-Br)Br2] · DMF· MeCN}n (5). On the other hand, treatment of 1a or 1b with bpp produced [(η5-C5Me5)MoS3Cu3(μ-bpp)(μ-Br)Br]n (6) and {[{(η5-C5Me5)MoS3Cu3)2(μ-bpp)3(μ-NCS)2(NCS)](NCS)}n (7). Compounds 2-7 have been characterized by elemental analysis, UV-vis spectroscopy, IR spectroscopy, ¹H NMR, and X-ray analysis. In 2, each [(η5-C5Me5)MoS3Cu3] core serves as an angular two-connecting node to link other equivalent cores by single and double bpe bridges to form a 1D "Great Wall-like chain. In 3a and 3b, the [(η5-C5Me5)MoS3Cu3] cores are linked alternatively by single and double bpe bridges to give a 1D zigzag chain. In 4, six cluster cores (two as a two-connecting node and four as a three-connecting node) are connected by four single bpe and two double bpe bridges to form a cyclohexane-shaped repeating unit, which is further fused with other units to generate a 1D double-stranded chain. Compound 5 has a simple 1D zigzag chain consisting of the cluster cores linked by single bpe bridges. In 6, the cluster cores are linked by single bpp bridges to give a 1D helical chain, which further holds two symmetry-related chains through CH⋯Br hydrogen-bonding interactions, thereby forming a 1D H-bonded triple-stranded chain. Compound 7 has a rare 1D quadruple chain, in which the [(η5-C5Me5)MoS3Cu3] cores work as planar four- and five-connecting nodes to interconnect other equivalent cores through single bpp bridges and single and double thiocyanate bridges. In addition, the third-order nonlinear optical properties of 1a, 2, 3a, and 4-7 in aniline were also investigated by using the Z-scan technique with a 4.5 ns pulse laser at 532 nm. [ABSTRACT FROM AUTHOR]

Reaction of a cluster precursor [Et 4N] 2[MoOS 3(CuCN)] ( 1) with equimolar [Cu(MeCN) 4](PF 6) in MeCN/aniline gave rise to an interesting polymeric cluster {[Et 4N] 2[MoOS 3Cu 2(μ-CN)] 2·2aniline} n( 2), while treatment of 1in MeCN with 2 equiv of CuCN and KCN in H 2O afforded the other polymeric cluster {[Et 4N] 4[MoOS 3Cu 3CN(μ′-CN)] 2(μ-CN) 2} n( 3). Generated by addition of one or two Cu +onto the [MoOS 3Cu] cluster core in 1, the butterfly shaped [MoOS 3Cu 2] fragment in 2or the incomplete cubanelike [MoOS 3Cu 3] fragment in 3was dimerized into a prismatic [MoOS 3Cu 2] 2cage core or a double incomplete cubanelike [MoOS 3Cu 3] 2core. These two expanded cores serve as a unique planar 4-connecting node ( 2) or a rare chairlike 4-connecting node ( 3) to link equivalent nodes via cyanide bridges, forming two kinds of different 2D (4,4) networks. The third-order nonlinear optical (NLO) properties of 1− 3in DMF were also investigated. [ABSTRACT FROM AUTHOR]

The assembly of a new family of [(η5-C5Me5)MoS3Cu3]-supported supramolecular compounds from a preformed cluster [PPh4][(η5-C5Me5)MoS3(CuNCS)3]·DMF (1·DMF) with four multitopic ligands with different symmetries is described. Reactions of 1 with 1,2-bis(4-pyridyl)ethane (bpe) (Cs symmetry) or 1,4-pyrazine (1,4-pyz) (D2h symmetry) in aniline gave rise to two polymeric clusters {[{(η5-C5Me5)MoS3Cu3}2(NCS)3(µ-NCS)(bpe)3]·3aniline}n (2) and [(η5-C5Me5)MoS3Cu3(1,4-pyz)(µ-NCS)2]n (3). On the other hand, solid-state reactions of 1 with 2,4,6-tri(4-pyridyl)-1,3,5-triazine (tpt) (D3h symmetry) or 5,10,15,20-tetra(4-pyridyl)-21H,23H-porphyrin (H2tpyp) (D4h symmetry if 21H and 23H of the H2tpyp are omitted) at 100 °C for 12 h followed by extraction with aniline yielded another two polymeric clusters {[(η5-C5Me5)MoS3Cu3(tpt)(aniline)(NCS)2]·0.75aniline·0.5H2O}n (4) and {[(η5-C5Me5)MoS3-Cu3(NCS)(µ-NCS)(H2tpyp)0.4(Cu-tpyp)0.1]η2anilineη2.5benzene}n (5). These compounds were characterized by elemental analysis, IR spectra, UV-vis spectra, ¹H NMR, and X-ray analysis. Compound 2 consists of a 2D (6,3) network in which [(η5-C5Me5)MoS3Cu3) cores serve both a 1-shaped three-connecting node and an angular two- connecting node to interconnect other equivalent units through single bpe bridges, double bpe bridges, and µ-NCS bridges. Compound 3 has a 3D diamondlike framework in which each [(η5-C5Me5)MoS3Cu3] core, acting as a tetrahedral connecting node, links four other neighboring units by 1,4-pyz bridges and µ-NCS bridges. Compound 4 contains a honeycomb 2D (6,3)core(6,3)tpt network in which each cluster core, serving a trigonal-planar three-connecting node, links three pairs of equivalent cluster cores via three tpt lignads. Compound 5 has a rare scalelike 2D (4,6²)core(4²,6²)Iigand network in which each cluster core acts as a 1-shaped three-connecting node to link with other equivalent ones through µ-NCS bridges and H2tpyp (or Cu-tpyp) ligands. The results showed that the formation of the four different multidimensional topological structures was evidently affected by the symmetry of the ligands used. In addition, the third-order nonlinear optical properties of 1-5 in aniline were also investigated by using Z-scan techniques at 532 nm. [ABSTRACT FROM AUTHOR]

Isocyanurate-containing silsesquioxane-bridged periodic mesoporous organosilicas (ICS−PMOs) were synthesized by self-assembly of the nonionic surfactant P123, EO20PO70EO20, and trimethoxysilyl-functionalized isocyanurate (ICS−Si) under acidic conditions in the presence of inorganic additives. The ICS−PMOs have been modified by an alkyl-bridged organosilane (i.e., Et−Si; Et −CH2CH2−) by substituting ICS−Si with Et−Si in the precursors, at various molar ratios, resulting in bifunctionalized PMOs exhibiting two types of bridged groups (ICS−Et−PMOs). The obtained bifunctionalized ICS−Et−PMOs have been characterized by X-ray diffraction, transmission electron microscopy, nitrogen physical sorption, and solid-state 29Si and 13C magic angle spinning NMR spectroscopy. Experiments show that the ICS−Et−PMOs exhibit hexagonal mesoscopic structures. Increasing the content of the Et−Si functionality in the precursors is found to significantly improve the mesostructural ordering of the product. It is suggested that fluoride anions as additives play an important role in the formation of well-ordered ICS−PMOs and as well the bifunctionalized ICS−Et−PMOs in the presented experiments. The ICS−PMO materials were used to chemically adsorb H2PtCl6, and Pt nanoparticles were subsequently prepared within the mesopores of ICS−PMO by NaBH4reduction in solution, highlighting the simplicity in exploiting the application of such PMOs in nanomaterials fabrication. [ABSTRACT FROM AUTHOR]

The reaction of Aul with 2 equiv of TabHPF6 [TabH = 4-(trimethylammonio)benzenethiol] in the presence of excess Et3N in dimethylformamide (DMF)/MeOH afforded a binuclear gold(l) complex [Au(Tab)2]2I2•2H2O (1). Anion exchange of 1 with NH4PF6 in DMF gave rise to the more soluble complex [Au(Tab)2]2(PF6)2 (2). Treatment of 2 with K[Au-(CN)2] produced a tetranuclear gold(l) complex {[(Tab)2Au]IAu(CN)2]}2 (3). Analogous reactions of two known mononuclear complexes [Ag(Tab)2](PF6) (4) and [Hg(Tab)2](PF6)2 (5) with 1 or 2 equiv of K[Au(CN)2] generated one Ag2Au2 complex {[(Tab)2Ag][Au(CN)2]}2 (6) and one Au/Hg complex {[Hg(Tab)2][Au(CN)2]2} (7), respectively. Compounds 1-3, 6, and 7 were fully characterized by elemental analysis, IR spectra, UV-vis spectra, ¹H NMR, and single-crystal X-ray crystallography. 1 and 2 have a similar [Au(Tab)2]22+ dimeric structure in which the two [Au(Tab)2]+ cations are connected via one Au-Au aurophilic interaction. In the structure of 3 or 6, each of the two pairs of [M(Tab)2]+ cation and [Au(CN)2]- anion is held together via ionic interactions to form a {[(Tab)2M][Au-(CN)2}} species (M = Au, 3; Ag, 6). Two such species are further connected by one Au-Au aurophilic bonding interaction to form an uncommon Au4 or Ag2Au2 linear string structure with three ligand-unsupported metal-metal bonds. For 7, the [Hg(Tab)2]2+ dication and the [Au(CN)2]22- dianion are interconnected by the secondary Hg⋯N(CN) interactions to form a 1D chain structure. The thermal and luminescent properties of 1-3, 6, and 7 in solid state were also investigated. [ABSTRACT FROM AUTHOR]

Reactions of [Et 4N] 2[MoS 4(CuCN) 2]·H 2O with bis-(4-pyridyl)propane (bpp) and [Cu(MeCN) 4][ClO 4] in aniline produced [MoS 4Cu 4(bpp) 2(CN) 2]·1.5(aniline) ( 1a). 1aconsists of a new three-dimensional [MoS 4Cu 4]-supported open coordination polymer which has a relatively large channel with a volume of ca. 618 Å 3per unit cell. 1aunderwent a two-step host–guest process in which the aniline molecules residing in its channels could be partly exchanged with MeCN molecules in 3d and then completely with dimethylformamide molecules in a month, forming {[MoS 4Cu 4(bpp) 2(CN) 2]·(aniline)·(MeCN)} n( 1b) and {[MoS 4Cu 4(bpp) 2(CN) 2]·(DMF)·(MeCN)} n( 1c), respectively. [ABSTRACT FROM AUTHOR]

Approaches to the assembly of (η5-C5Me5)WS3Cu3-based supramolecular compounds from two preformed incomplete cubane-like clusters [PPh4][(η5-C5Me5)WS3(CuX)3] (X = CN, 1a; X = Br, 1b) have been investigated. Treatment of 1a with LiBr/1,4-pyrazine (1,4-pyz), pyridine (py), LiCl/py, or 4,4′-bipyridine (4,4′-bipy) and treatment of 1b with 4,4′-bipy gave rise to a new set of W/Cu/S cluster-based compounds, [Li{((η5-C5Me5)WS3Cu3(μ3-Br))2(μ-CN)3}·C6H6]∞. (2), [(η5-C5Me5)WS3Cu3(μ-CN)2(py)]∞. (3), {[PPh4][(η5-C5Me5)WS3Cu3(μ3-Cl)(μ-CN)(CN)]·py}∞. (4), [PPh4]2-[(η5-C5Me5)WS3Cu3(CN)2]2(μ-CN)2(4,4′-bipy) (5), and {[(η5-C5Me5)WS3Cu3Br(μ-Br)(4,4′-bipy)]·Et2O}∞. (6). The structures of 2-6 have been characterized by elemental analysis, IR spectra, and single-crystal X-ray crystallography. Compound 2 displays a 1D ladder-shaped chain structure built of squarelike {[(η5-C5Me5)WS3Cu3(μ3-Br)(μ-CN)]4}∞ (μ-CN)22- anions via two pairs of Cu-μ-CN-Cu bridges. Compound 3 consists of a single 3D diamondlike network in which each (η5-C5Me5)WS3Cu3 unit, serving as a tetrahedral node, interconnects with four other nearby units through Cu-μ-CN-Cu bridges. Compound 4 contains a 1D zigzag chain array made of cubane-like [(η5-C5Me5)WS3-Cu3(μ3-Cl)(μ-CN)(CN)]- anions linked by a couple of Cu-μ-CN-Cu bridges. Compound 5 contains a dimeric structure in which the two incomplete cubane-like [(η5-C5Me5)WS3(CuCN)2(μ-CN)] anions are strongly held together via a pair of Cu-μ-CN-Cu bridges. Compound 6 contains a 2D brick-wall layer structure in which dimers of [(η5-C5-Me5) WS3Cu3Br(4,4′-bipy)]2 are interconnected via four Cu-μ-Br-Cu bridges. The successful construction of (η5-C5Me5)WS3Cu3-based supramolecular compounds 2-6 from the geometry-fixed clusters la and lb may expand the scope of the rational design and construction of cluster-based supramolecular assemblies. [ABSTRACT FROM AUTHOR]

Reactions of two preformed trinuclear W/Cu/S clusters, [A]2[WS4(CuCN)2] (1: A = Et4N; 2: A = PPh4), with different concentrations of acetic acid in MeCN generate two interesting 2D polymeric clusters [Et4N]3[(WS4Cu2)2(mu;-CN)3]·2MeCN (3), and [PPh4][WS4Cu3(mu;-CN)2]·MeCN (4), respectively. Compound 4 can also be readily obtained in a high yield from the reaction of 2 with equimolar [Cu(MeCN)4]PF6 in MeCN. These compounds have been characterized by elemental analysis, IR spectra, thermal analysis, and single-crystal X-ray diffraction. An X-ray analysis reveals that compound 3 retains the WS4Cu2 cluster core, which serves as a 3-connecting node to link equivalent nodes via single cyanide bridges, forming an anionic 2D (6,3) net. Compound 4 consists of a T-shaped WS4Cu3 core, which also acts as a 3-connecting node, with links to 3 equivalent clusters either through single or double cyanide bridges, affording a different anionic 2D (6,3) network. The acetic acid induced aggregation of 3 and 4 from the two cluster precursors 1 and 2 suggests that this simple synthetic strategy is likely to be applicable to many related systems. [ABSTRACT FROM AUTHOR]

This article presents information on the construction of polymeric and oligomeric lanthanide(IlI) thiolates from preformed complexes. Several synthetic approaches to lanthanide thiolates, including metathesis of a lanthanide halide with an alkali metal thiolate, oxidative addition of organic disulfide RSSR to lanthanide(II) complexes or lanthanide metals under the presence of catalyst, and the reactions of lanthanide thiolates with elemental sulfur, have been developed. However, an additional approach, protonolysis of preformed lanthanide complexes with thiols, has been less explored for synthesizing polymeric or oligomeric lanthanide thiolate complexes.