Polyhedral {Ag12} and {Ag16} Clusters: Synthesis, Structural Characterization and Third-Order Nonlinear Optical Properties.

Two polyhedral silver-thiolate clusters, [S@Ag16(Tab)10(MeCN)8](PF6)14 (Ag16) and [Ag12(Tab)6(DMF)12](PF6)12 (Ag12), were synthesized by using electroneutral Tab species as protective ligands (Tab=4-(trimethylammonio)benzenethiolate, DMF=N,N-dimethylformamide, MeCN=acetonitrile). Ag16 has a decahedral shape composed of eight pentagon {Ag5} units and two square {Ag4} units. The structure of Ag12 is a cuboctahedron, a classical Archimedean structure composed of six triangular faces and eight square faces. The former configuration is discovered in silver-thiolate cluster for the first time, possibly benefited from the more flexible coordination between the Tab ligand and Ag+ facilitated by the electropositive -N(CH3)3 + substituent group. Third-order nonlinear optical studies show that both clusters in DMF exhibit reverse saturate absorption response under the irradiation of 532 nm laser.

Construction of cluster-based supramolecular wire and rectangle.

Reactions of [Et4N][Tp*WS3(CuCl)3] (1) (Tp* = hydridotris(3,5-dimethylpyrazol-1-yl)borate) with 2 equiv. of AgOTf (OTf- = trifluoromethanesulfonate) and 1 equiv. of several bidentate pyridine ligands including 2,5-bis(pyridine-4-yl)thiazolo[5,4-d]thiazole (L1), 2,7-di(pyridin-4-yl)-9H-fluorene (L2), 2,7-di(pyridin-4-yl)-9H-carbazole (L3), and 2,7-di(pyridin-4-yl)-9H-fluoren-9-one (L4) afforded four W/Cu/S cluster-based supramolecular compounds [(Tp*WS3Cu2Cl)2(L1)] (2), {[(Tp*WS3Cu3)2(µ-Cl)2(µ4-Cl)]2(L2)2}(OTf)2 (3), {[(Tp*WS3Cu3)2(µ-Cl)2(µ4-Cl)]2(L3)2}(OTf)2 (4) and {[(Tp*WS3Cu3)2(µ-Cl)2(µ4-Cl)]2(L4)2}(OTf)2 (5). Compounds 2-5 were characterized by elemental analysis, IR, UV-vis, 1H NMR, and single-crystal X-ray diffraction analysis. The neutral cluster 2 behaves as a supramolecular wire constructed by L1 bridging two butterfly-shaped [Tp*WS3Cu2Cl] cores. The cluster cations of 3-5 contain two [(Tp*WS3Cu3)2(µ-Cl)2(µ4-Cl)]+ cores linked by two L2, L3, or L4 ligands, which finally formed a cationic supramolecular rectangle. The third-order nonlinear-optical (NLO) properties of 3-5 in DMF were also investigated by Z-scan techniques and their NLO responses were enhanced compared to those of their precursor 1.

Flexible Vertex Engineers the Controlled Assembly of Distorted Supramolecular Tetrahedral and Octahedral Cages.

Designing and building unique cage assemblies attract increasing interest from supramolecular chemists but remain synthetically challenging. Herein, we propose the use of a flexible vertex with adjustable angles to selectively form highly distorted tetrahedral and octahedral cages, for the first time, in which the flexible vertex forms from the synergistic effect of coordination and covalent interactions. The inherent interligand angle of the vertex can be modulated by guest anions present, which allows for the fine-tuning of different cage geometries. Furthermore, the reversible structural transformation between tetrahedral and octahedral cages was achieved by anion exchange monitored by mass spectrometric technique, the smaller anions favoring tetrahedral cages, while the larger anions supporting octahedral cages. Additionally, the KBr-based cage thin films exhibited prominent enhancement of their third-order NLO responses in two or three orders of magnitude compared to those obtained for their corresponding solutions. This work not only provides a new methodology to build irregular polyhedral structures in a controlled and tunable way but also provides access to new kinds of promising functional optical materials.

The Covalent and Coordination Co-Driven Assembly of Supramolecular Octahedral Cages with Controllable Degree of Distortion.

Discovering and constructing novel and fancy structures is the goal of many supramolecular chemists. In this work, we propose an assembly strategy based on the synergistic effect of coordination and covalent interactions to construct a set of octahedral supramolecular cages and adjust their degree of distortion. Our strategy innovatively utilizes the addition of sulfur atoms of a metal sulfide synthon, [Et4N][Tp*WS3] (A), to an alkynyl group of a pyridine-containing linker, resulting in a novel vertex with low symmetry, and of Cu(I) ions. By adjusting the length of the linker and the position of the reactive alkynyl group, the control of the deformation degree of the octahedral cages can be realized. These supramolecular cages exhibit enhanced third-order nonlinear optical (NLO) responses. The results offer a powerful strategy to construct novel distorted cage structures as well as control the degree of distortion of supramolecular geometries.

Synthesis, self-assembly and nonlinear optical activity of selenium-annulated perylene diimide.

A novel Se-annulated perylene diimide derivative tethered with polyhedral oligosilsesquioxane (POSS) nanoparticles (POSS-2SePDI-POSS) was designed and prepared. The introduction of selenium atoms endows POSS-2SePDI-POSS with significant fluorescence quenching but enhanced excited-state absorption. As a result, POSS-2SePDI-POSS exhibits a distinct reverse saturable absorption characteristic, suggesting its potential application in optical limiting.

Series of Mitochondria/Lysosomes Self-Targetable Near-Infrared Hemicyanine Dyes for Viscosity Detection.

Six mitochondria/lysosomes self-targetable and viscosity-sensitive dyes (1a-1f) were developed via simple structure modification on cyanine-derived dyes. They all showed remarkable OFF-ON fluorescent response to viscosity in the near-infrared region (652-690 nm) and exhibited good linear relationship with solution viscosity. The transient absorption spectra were used to evaluate the excited-state lifetime of dye 1a in different viscosity environments. Furthermore, cellular imaging assays indicated that different derivatives (1a-1f) with the same chromophore core exhibited different organelle-targeting abilities. Among them, dyes 1a-1c could sense lysosomal viscosity fluctuations while dyes 1d-1f could be applied in mitochondrial viscosity detections.

Polyhedral oligosilsesquioxane tethered perylene diimide for application in optical limiting and rapid detection of fluoride ions.

A novel perylene diimide derivative equipped with polyhedral oligosilsesquioxane nanocages (POSS-AMPDI) was designed and synthesized for application in optical limiting. Moreover, due to the dual mechanisms of POSS collapse and intermolecular proton transfer, POSS-AMPDI exhibits high sensitivity and rapid selectivity to fluoride ions, with a detection limit as low as 1.64 × 10-8 M.

Evaluating the component contribution to nonlinear optical performances using stable [Ni4O4] cuboidal clusters as models.

Five stable clusters sharing the cuboidal [Ni4O4] skeleton are subjected to third-order nonlinear optical (NLO) property measurements. Preliminary results suggest that the NLO property is largely defined by the cluster core skeleton and the directly coordinated atoms, with limited contribution from the heavy atoms peripherally attached to the aromatic ligands.

Rectangle and [2]catenane from cluster modular construction.

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.

Controlling Crystallization of All-Inorganic Perovskite Films for Ultralow-Threshold Amplification Spontaneous Emission.

All-inorganic lead halide perovskites have gained considerable interest owing to their potential applications in an array of high-performance optoelectronic devices. However, producing highly luminescent, nearly pinhole-free, all-inorganic perovskite films through a simple solution process remains challenging. Here, we provide a detailed investigation of the crystallization control of inorganic perovskite films fabricated by a one-step spin-coating process. Our results reveal that the coating temperature in the fabrication process is of paramount importance in influencing perovskite crystallization and that lowering the coating temperature and fine stoichiometry modification of the precursors favor the suppression of trap states in CsPbBr3 perovskite films. A broad range of experimental characterizations help us identify that nonsynergistic assembly of solutes, resulting from poor diffusion capability of inorganic salts, is the dominant cause for the inhomogeneous element distribution, low luminescence yield, and poor surface coverage of the resulting films. Importantly, we find that polyethylene glycol can also be used for tailoring the crystallization process, which enables the attainment of high-quality CsPbBr3 films with a maximum luminescence yield of ∼30%. Finally, we demonstrate that amplification spontaneous emission with an ultralow threshold can be readily accomplished by using the developed film as an emissive component. Our findings provide deep insights into the crystallization control of CsPbBr3 perovskite films and establish a systematic route to high-quality all-inorganic perovskite films, paving the way for widespread optoelectronic applications.

Tungsten(VI)-Copper(I)-Sulfur Cluster-Supported Metal-Organic Frameworks Bridged by in Situ Click-Formed Tetrazolate Ligands.

Six analogous two-dimensional (2D) [Tp*WS3Cu3]-based (Tp* = hydridotris(3,5-dimethylpyrazol-1-yl)borate) networks, namely, {[(Tp*WS3Cu3)2L3](µ3-N3)}n (2: L = 5-methyltetrazolate (Mtta); 3a: L = 5-ethyltetrazolate (Etta)) and {[(Tp*WS3Cu3)2L3]BF4}n (3b: L = Etta; 4: L = 5-propyltetrazolate (Ptta); 5: L = 5-butyltetrazolate (Btta); 6: L = 5-pentyltetrazolate (Petta)) were synthesized by reactions of [Et4N][Tp*WS3] (1), [Cu(CH3CN)4]BF4, NaN3, and NH4BF4 in different nitrile solvents (CH3(CH2)nCN, n = 0, 1, 2, 3, and 4) under solvothermal conditions. In the structures of 2-6, each alkyl tetrazolate L as a bridging ligand was generated in situ from the "click" reaction between azide and nitrile. These 2D (6,3) networks support two types of voids wherein the pendant alkyl groups are accommodated. A tetrahedron cage-like cluster [Tp*W(µ3-S)3(µ3-S')Cu3]4 (7) was also formed in some of the above reactions and can be readily separated by solvent extraction. The proportion of 7 increased with the elongation of the alkyl chains and finally became the exclusive product when heptylnitrile was employed. Further use of CuCN as a surrogate for [Cu(CH3CN)4]BF4 with the aim of introducing additional CN bridges into the network led us to isolate a tetrazolate-free compound, {[Et4N]{(Tp*WS3Cu3)[Cu2(CN)4.5]}2·2PhCH2CN}n (8·2PhCH2CN), a unique 2D network that features {(Tp*WS3Cu3)[Cu2(CN)5]}22-, {(Tp*WS3Cu3)3[Cu3(CN)7]2[Cu(CN)3]}4-, and {(Tp*WS3Cu3)[Cu4(CN)9]}26- ring subunits. Compounds 5-8 are soluble in DMF and exhibit a reverse saturable absorption and self-focusing third-order nonlinear optical (NLO) effect at 532 nm with hyperpolarizability γ values in the range of 4.43 × 10-30 to 5.40 × 10-30 esu, which are 400-500 times larger than that of their precursor 1. The results provide an interesting insight into the synergetic synthetic strategy related to the assembly of the [Tp*WS3Cu3]2+ cluster core, the "click" formation of the tetrazolate ligands, and the construction of the [Tp*WS3Cu3]2+ cluster-based 2D networks.

Three-dimensional super-resolution longitudinal magnetization spot arrays.

We demonstrate an all-optical strategy for realizing spherical three-dimensional (3D) super-resolution (∼λ3/22) spot arrays of pure longitudinal magnetization by exploiting a 4π optical microscopic setup with two high numerical aperture (NA) objective lenses, which focus and interfere two modulated vectorial beams. Multiple phase filters (MPFs) are designed via an analytical approach derived from the vectorial Debye diffraction theory to modulate the two circularly polarized beams. The system is tailored to constructively interfere the longitudinal magnetization components, while simultaneously destructively interfering the azimuthal ones. As a result, the magnetization field is not only purely longitudinal but also super-resolved in all three dimensions. Furthermore, the MPFs can be designed analytically to control the number and locations of the super-resolved magnetization spots to produce both uniform and nonuniform arrays in a 3D volume. Thus, an all-optical control of all the properties of light-induced magnetization spot arrays has been demonstrated for the first time. These results open up broad applications in magnetic-optical devices such as confocal and multifocal magnetic resonance microscopy, 3D ultrahigh-density magneto-optic memory, and light-induced magneto-lithography.

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

In the absence/presence of S8, the one-pot assembly of [Et4N][Tp*WS3] [1; Tp* = hydridotris(3,5-dimethylpyrazol-1-yl)borate] with [Cu(MeCN)4]PF6 and bis- or tetraphosphine ligands 1,2-bis(diphenylphosphino)ethane (dppe), 1,3-bis(diphenylphosphino)propane (dppp), 1,4-bis(diphenylphosphino)butane (dppb), and N,N,N',N'-tetrakis(diphenylphosphinomethyl)ethylenediamine (dppeda) produces six W-Cu-S clusters, namely, [(Tp*WS3Cu2Cl)2(dppe)] (2), [Tp*WS3Cu4(dppp)2(µ4-Cl)(µ-Cl)]PF6·MeCN (3·MeCN), [(Tp*WS3Cu3)2(µ4-Cl)(µ-Cl)2(dpppS2)] (4), [(Tp*WS3Cu2Cl)2(dppbS2)]·2MeCN·2H2O (5·2MeCN·2H2O), [(Tp*WS3Cu3Cl2)2(dppbS2)] (6), and [(Tp*WS3Cu3)2(Ph2PS2)3(µ6-Cl)0.5](PF6)0.5·0.75CH2Cl2 (7·0.75CH2Cl2). Compounds 2-7 are characterized by elemental analysis, IR, UV-vis, (1)H and (31)P{(1)H} NMR, electrospray ionization mass spectrometry, and X-ray crystallography. For 2, the dppe ligand bridges a pair of butterfly-shaped [Tp*WS3Cu2] cores to form a double-butterfly-shaped structure. For 4, the dppp ligand is susceptible toward S association and forms an in situ generated dpppS2 ligand, supporting an octanuclear double-half-open-cubane structure and contrasting an analogous system wherein a pentanuclear motorcycle-shaped cationic cluster 3 is formed with the absence of S8. A longer dppb ligand readily converts to S-based ligands in 5 and 6, subsequently serving as bridges between a pair of a butterfly-shaped (5) and nest-shaped (6) clusters. Further use of a tetraphosphine ligand, dppeda, in the cluster formation, with the presence of S8, leads to an unexpected ligand degradation to give the [Ph2PS2](-) anions. Three [Ph2PS2](-) anions juxtapose a pair of nest-shaped cluster cores to yield an octanuclear cluster, 7, featuring a cage to encapsulate µ6-Cl(-). The third-order nonlinear-optical (NLO) properties of 2-7 in N,N-dimethylformamide, investigated using a Z-scan technique at 532 nm, show that 2-6 have a reverse saturable absorption, while 7 has a notable saturable absorption. All of 2-7 exhibit a self-focusing effect with hyperpolarizability γ values in the range of 4.71 × 10(-30)-1.02 × 10(-29) esu, which are 440-1000 times higher than that of 1. The formation of 4-7 from 1 through the in situ thiolation of phosphine ligands presents a new approach to the design and assembly of the W-Cu-S clusters with interesting structural arrays and better NLO properties.

Unexpected optical limiting properties from MoS2 nanosheets modified by a semiconductive polymer.

Direct solvent exfoliation of bulk MoS2 with the assistance of poly(3-hexylthiophene) (P3HT) produces a novel two-dimensional organic/inorganic semiconductor hetero-junction. The obtained P3HT-MoS2 nanohybrid exhibits unexpected optical limiting properties in contrast to the saturated absorption behavior of both P3HT and MoS2, showing potential in future photoelectric applications.

Broadband optical limiting response of a graphene-PbS nanohybrid.

Graphene-based materials have shown promising nonlinear optical properties in the visible range. To extend their nonlinear optical response to the near infrared (NIR) region, we prepared a new nanohybrid consisting of uniform PbS quantum dots (QDs) attached on the reduced graphene oxide, named rGO-PbS, via a facile, low-cost, and phosphine-free method. The rGO-PbS nanohybrid exhibited superior optical limiting properties to either graphene oxide or PbS QDs upon both 532 nm and 1064 nm excitation in the nanosecond laser pulse regime, which is attributed to the synergetic effects stemming from charge transfer between the two components. Meanwhile, the thin films containing the rGO-PbS nanohybrid dispersed in polymethylmethacrylate (PMMA) also showed excellent optical limiting properties with high transparency, implying the potential applications of this hybrid material in broadband nonlinear optical devices.

Formation of dimeric and polymeric W/Cu/S clusters via degradation or expansion of the cluster core in [Et4N]4[WS4Cu4I6].

The reactions of a precursor cluster [Et4N]4[WS4Cu4I6] (1) with two equiv. of 1,1'-(1,4-butanediyl)bis(3,5-dimethyl-pyrazole) (bbd) or 1,3,5-tris(3,5-dimethyl-pyrazolyl-1-ylmethyl)-2,4,6-trimethylbenzene (tdtb) in MeCN/DMF afforded the dimeric clusters [WS4Cu3I(mut-bbd)]2 (2) and [{WS4Cu3(tdtb)}2(mu-I)2].2DMF (3.2DMF), respectively. Solvothermal reactions of 1 with two equiv. of bbd in MeCN/DMF at 90 degrees C for 24 h resulted in the formation of the dimeric cluster [Et4 N]6[{WS4Cu5(mu-I)2I4}2(mu-bbd)] (4) while those of 1 with two equiv. of 1,3,5-tris(imidazol-1-ylmethyl)-2,4,6-trimethylbenzene (titb) in DMF at 120 degrees C afforded the polymeric cluster {[WS4Cu2(titb)].0.5H2O}n (5). Compounds 2-5 were characterized by elemental analysis, IR, UV-vis, 1H NMR and single-crystal X-ray crystallography. Compound 2 has a double nido-shaped structure in which two nido-shaped [WS4Cu3] cores are connected by a pair of bbd ligands while 3 has a double butterfly-shaped structure in which two [WS4Cu3(tdtb)] fragments are linked by two bridging iodides. Compound 4 has a double-double half-open cubane-like structure in which a couple of double half-open cubane-like [WS4Cu5] cores are bridged by one bbd ligand. Compound 5 has a unique two-fold interpenetrated 3D (10(2) x 12)core(10(2) x 12)tib network in which each linear [WS4Cu2] core acts as a T-shaped 3-connecting node and each titb ligand works as a trigonal pyramidal 3-connecting node. The core structures of 2-5 are different from the saddle-shaped [WS4Cu4] core of 1, which may be attributed to the degradation or expansion of the cluster core of 1 during the reactions. In addition, the third-order non-linear optical (NLO) properties of 1-4 in DMF were also investigated by using Z-scan techniques at 532 nm.

From trans-[(eta5-C5Me5)2Mo2S2(mu-S)2] to [(eta5-C5Me5)2Mo2(mu3-S)4(CuMeCN)2]2+ to [(eta5-C5Me5)2Mo2(mu3-S)4Cu2]-based polymeric and dimeric clusters: syntheses, structures and enhanced third-order non-linear optical performances.

Reactions of trans-[(eta5-C5Me5)2Mo2S2(mu-S)2] (1) with 2 equiv. of [Cu(MeCN)4]X (X = PF6-, ClO4-) produced two acetonitrile-coordinated cubane-like cationic clusters [(eta5-C5Me5)2Mo2(mu3-S)4Cu2(MeCN)2]X2 (X = PF6- (2), ClO4- (3)). Treatment of 2 or 3 with 4,4'-bipyridine (4,4'-bipy) or trans-1,2-bis(4-pyridyl)ethylene) (bpee) afforded two polymeric clusters {[(eta5-C5Me5)2Mo2(mu3-S)4Cu2(L)]X2}n (4: L = 4,4'-bipy, X = PF6-; 5: L = bpee, X = ClO4-), while analogous reactions of 2 or 3 with 1,2-bis(4-pyridyl)ethane (bpea), 1,2-bis(diphenylphosphine)ethane (dppe), or 1,4-bis-(diphenylphosphine)butane) (dppb) formed three dimeric clusters [(eta5-C5Me5)2Mo2(mu3-S)4Cu2(L)]2X4 (6: L = bpea; X = PF6-; 7: L = dppe, X = ClO4-; 8: L = dppb, X = ClO4-). Clusters 2-8 consist of a cubane-like [(eta5-C5Me5)2Mo2(mu3-S)4Cu2] core with each Cu being coordinated by one labile MeCN molecule (2, 3) or by bridging dipyridyl or diphosphino ligands (4-8). 4 or 5 has a 1D zigzag chain structure while 6-8 contain cyclic dimeric structures. The third-order non-linear optical (NLO) properties of 2-8 in MeCN were investigated by Z-scan technique at 532 nm. These compounds showed strong third-order NLO absorption effects and self-defocusing properties, and their NLO performances were remarkably enhanced relative to those of 1.

Assembly of [(eta5-C5Me5)MoS3Cu3]-supported one-dimensional chains with single, double, triple, and quadruple strands.

The construction of a new set of [(eta5-C5Me5)MoS3Cu3]-based supramolecular compounds with different one-dimensional (1D) arrays from two preformed clusters [PPh4][(eta5-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 ([((eta5-C5Me5)MoS3Cu3) 2(mu-bpe)3.5Br4].MeCN) n (2), ([((eta5-C5Me5)MoS3Cu3)2(mu-bpe)3Br4].Sol)n (3a: Sol = DMSO.3MeCN; 3b: Sol = 2aniline.3MeCN), ([((eta5-C 5Me5)MoS3Cu3)2(mu-bpe)3(bpe)Br4].0.35DMF)n (4), and ([((eta5-C5Me5)MoS3Cu3)2(mu-bpe)2(mu-Br)(mu3-Br)Br2].DMF.MeCN)n (5). On the other hand, treatment of 1a or 1b with bpp produced [(eta5-C5Me5)MoS3Cu3(mu-bpp)(mu-Br)Br]n (6) and ([((eta5-C5Me5)MoS3Cu3)2(mu-bpp)3(mu-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 [(eta5-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 [(eta5-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 [(eta5-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.

Construction of [(eta5-C5Me5)MoS3Cu3]-based supramolecular assemblies from the [(eta5-C5Me5)MoS3(CuNCS)3]- cluster anion and multitopic ligands with different symmetries.

The assembly of a new family of [(eta5-C5Me5)MoS3Cu3]-supported supramolecular compounds from a preformed cluster [PPh4][(eta5-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 {[{(eta5-C5Me5)MoS3Cu3}2(NCS)3(mu-NCS)(bpe)3].3aniline}n (2) and [(eta5-C5Me5)MoS3Cu3(1,4-pyz)(mu-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 degrees C for 12 h followed by extraction with aniline yielded another two polymeric clusters {[(eta5-C5Me5)MoS3Cu3(tpt)(aniline)(NCS)2].0.75aniline. 0.5H2O}n (4) and {[(eta5-C5Me5)MoS3Cu3(NCS)(mu-NCS)(H2tpyp)0.4(Cu-tpyp)0.1].2aniline.2.5benzene}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 [(eta5-C5Me5)MoS3Cu3] cores serve both a T-shaped three-connecting node and an angular two-connecting node to interconnect other equivalent units through single bpe bridges, double bpe bridges, and mu-NCS bridges. Compound 3 has a 3D diamondlike framework in which each [(eta5-C5Me5)MoS3Cu3] core, acting as a tetrahedral connecting node, links four other neighboring units by 1,4-pyz bridges and mu-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)ligand network in which each cluster core acts as a T-shaped three-connecting node to link with other equivalent ones through mu-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.

Two-dimensional phase-measuring profilometry.

An improved method is proposed to perform contouring of an object based on phase-measuring profilometry with a grid grating. Two phases unwrapped in perpendicular directions are obtained with the help of an adaptive bandpass filter and are used to unwrap the phases and to appoint the edge points of a shaded area and the object area. The height distribution of the object is obtained with the geometric relationship between coordinates and phases. The main axis of the projector and the main axis of the camera are not crossed and are also not in the same plane in order to arrange a measuring system easily and conveniently. The experimental results show that this technique is available for practical applications.