Thiacalix[4]arene-protected alkynyl Agn (n = 9, 18) nanoclusters: syntheses, structural characterizations, photocurrent responses and fluorescence properties.

Two thiacalix[4]arene-protected silver(I) alkynyl nanoclusters, [Na2(H2O)2][Ag9(TC4A)(tBuCC)4(CH3OH)2(SbF6)0.5(OH)2.5]·3.5H2O·CH3OH (1, abbreviated as Ag9) and [Ag9(TC4A)(tBuCC)4(CF3COO)]2·4CH3OH (2, abbreviated as Ag18), were synthesized by the reaction of [tBuCCAg]n, p-tert-butylthiacalix[4]arene (H4TC4A), NaBH4, and AgSbF6 or CF3COOAg in the mixed solvent of methanol-trichloromethane-toluene under solvothermal conditions, respectively. Driven by SbF6- and CF3COO- with different coordination properties, the structural unit [Ag9(TC4A)(tBuCC)4]+ in both the compounds migrated in different modes, accompanied by distinct Ag⋯Ag distances. Ag9 and Ag18 exhibit similar UV-Vis absorption and diffuse reflection spectra along with contrary tendency between photocurrent responses and solid-state fluorescence. The solution stability of Ag9 and Ag18 was demonstrated by 1H NMR and MALDI-TOF mass spectrometry. The fluorescence responses of Ag9 and Ag18 towards different organic molecules were also investigated, which indicated that the polarity of solvent has a certain effect on the emission intensities of Ag9 and Ag18. This study provides a positive guide for the controlled synthesis and further study of the structure-activity relationship of thiacalix[4]arene-protected silver alkynyl nanoclusters.

Post-synthetic atomically precise single-CuII sites in a thiacalix[4]arene-supported octahedral Na@Co24 cluster: the Cu-Co synergistic effect for selective photocatalytic conversion of CO2 to CO.

A thiacalix[4]arene-supported octahedral Na@Co24 cluster has been fabricated by the modular assembly of six Co4-(TC4A) polynuclear secondary building units (PSBUs) and eight 2,4,6-PTC linkers. The post-modification of Na@Co24 by ion exchange of Na+ with Cu2+ on the surface of the octahedron afforded a structurally well-defined Cu@Co24 cluster. The obtained Cu@Co24 cluster achieved improved visible-light absorption and selective photoreduction of CO2 to CO due to the Cu-Co synergistic effect.

Carboxylate Ligand-supported Agn (n=21 and 24) Alkynyl Clusters Induced by Single/Double Carbonate Ions.

Structural transformation is important for the study of silver cluster compounds, in which controlled synthesis of their shapes and sizes via anion template-driven is one key scientific question. In this work, the CO3 2- anion templates were captured by the [t BuC≡CAg]n system under the stimulation induced by carboxylate ligand CF3 COO- /PhCOO- , and two silver alkynyl clusters [(CO3 2- )@Ag21 (t BuC≡C)16 (CF3 COO)3 (H2 O)]⋅DMF⋅2CH2 Cl2 (1) and [(CO3 2- )2 @Ag24 (t BuC≡C)16 (PhCOO)4 ]⋅CH3 OH⋅4DMF (2) have been successfully isolated and charactered. With the increase of the number of CO3 2- templates from single to double, the outer silver atoms from twenty-one to twenty-four, accompanied by the growth of the cluster skeleton from 9.8 Š×6.9 Šof the (CO3 2- )@Ag21 unit to 10.5 Š×7.3 Šof the (CO3 2- )2 @Ag24 unit. In addition, the syntheses, structures, photocurrent responses, cyclic voltammetry characteristics, luminescence, and photodegradation of compounds 1 and 2 have been studied.

Trapping a [W10 O32 ]6- Decatungstate Anion in an Ag44 Nanowheel.

Compound [Ag44 (W10 O32 )(St Bu)24 (CF3 COO)8 ](CF3 COO)6 ⋅ 6H2 O (1) was synthesized through a one-pot method. This is the first case of isolating a new silver thiolate cluster containing a [W10 O32 ]6- template which transforms from WO4 2- polyoxoanion through a self-assembly process. The anionic nature of the reduced [W10 O32 ]6- template and the effective silver-oxygen interaction contribute to the formation of the Ag44 nanowheel in 1. The luminescence, photocatalytic activity and electrochemistry properties of 1 were studied.

Imidazole-Functionalized Polyoxometalate Catalysts for the Oxidation of 5-Hydroxymethylfurfural to 2,5-Diformylfuran Using Atmospheric O2.

Biomass as a sustainable and abundant carbon source has attracted considerable attention as a potential alternative to petroleum resources. The selective oxidation of 5-hydroxymethylfurfural (HMF), a versatile platform molecule, to value-added 2,5-diformylfuran (DFF) provides an efficient pathway for biomass valorization. Herein, three discrete imidazole-functionalized polyoxometalates (POMs), HPMo8VVI4O40(VVO)2[(VIVO)(IM)4]2·nH2O·(IM)m (IM = 1-methylimidazole, n = 4, m = 8 for 1; IM = 1-ethylimidazole, n = 4, m = 9 for 2; IM = 1-propylimidazole, n = 0, m = 4 for 3), have been successfully synthesized by a facile solvothermal method and thoroughly characterized by routine techniques. Compounds 1-3 contain a bi-capped pseudo-Keggin {HPMo8V4O40(VO)2} and two imidazole-functionalized {(VO)(IM)4} groups, which, to our knowledge, represent the first examples of organic-functionalized Mo-V clusters. Compounds 1-3 as heterogeneous catalysts can effectively promote the transformation of HMF to DFF using atmospheric O2 as oxidant. Under minimally optimized conditions, 95% of HMF was converted by 1 with 95% selectivity for DFF and its catalytic activity was basically maintained after five cycles. Moreover, the important roles of the bi-capped pseudo-Keggin cluster and the functionalized V groups in the selective oxidation of HMF have been explored. According to experimental and spectroscopic results, a three-step oxidation mechanism of HMF to DFF has been proposed.

Various Cd(ii) coordination polymers induced by carboxylates: multi-functional detection of Fe3+, anions, aspartic acids and bovine serum albumin.

By adjusting carboxylates, six Cd(ii) coordination polymers based on a naphthalene-methylene mixed-bridged-amide ligand, [Cd(L)(DNBA)2] (1), [Cd2(L)2(BDC)2(H2O)2]·2H2O (2), [Cd(L)(1,4-CHDA)] (3), [Cd(L)(HIPA)(H2O)]·H2O (4), [Cd(L)(MIP)]·H2O (5), and [Cd(L)(PMA)0.5(H2O)]·H2O (6) [L = N,N'-bis(4-methylenepyridin-4-yl)-1,4-naphthalene dicarboxamide, HDNBA = 3,5-dinitrobenzoic acid, H2BDC = 1,4-benzenedicarboxylic acid, 1,4-H2CHDA = 1,4-cyclohexanedicarboxylic acid, H2HIPA = 5-hydroxyisophthalic acid, H2MIP = 5-methylisophthalic acid and H4PMA = pyromellitic acid] have been synthesized under hydrothermal conditions. 1 shows a 4-c sql coplanar structure. 2 exhibits a 2-fold vertical interpenetrating structure based on wave-like 4-c sql layers. 3 shows a (3,5)-c pnh network containing a unique µ3-L. 4 features a 4-c sql wave-like network. 5 and 6 exhibit 3D structures with 6-c pcu and 4-c mog topologies. The number of carboxyl groups and functional group positions of the carboxylates have an important influence on the structures of the title complexes. The fluorescent responses of 1-6 towards Fe3+, anions, aspartic acid and bovine serum albumin were investigated. Among them, 4 shows sensitivity and selectivity (KSV = 1.16 × 104 L mol-1 for Fe3+, 1.03 × 104 L mol-1 for CrO42-, 1.08 × 104 L mol-1 for Cr2O72-, 1.17 × 104 L mol-1 for MnO4- and 1.05 × 104 L mol-1 for aspartic acid).

Thiacalixarene-Supported Irregular Co26 and Ni28 High-Nuclearity Clusters with Pyridyl-Diphosphonates: Strategies to Create Active Metal Sites and Fabricate Multicomponent Materials.

Two new irregularity high-nuclearity clusters [Co26(TC4A)6(HL)4Cl4(HCOO)4(CH3O)2(OH)2(DMF)10(H2O)5] (+ solvent) (Co26) and [Ni28(TC4A)6(HL)6(PO4)2(µ3-O)2Cl2(CH3OH)14(H2O)2(DMF)8][(CH3NH2CH3)4] (+ solvent) (Ni28) have been solvothermally synthesized by p- tert-butylthiacalix[4]arene (H4TC4A), transition metals (CoCl2·6H2O/NiCl2·6H2O), and 1-hydroxy-2-(3-pyridinyl)ethylidene-1,1-diphosphonic acid (H5L). The clusters were structurally characterized by single crystal X-ray diffraction, PXRD, TGA, and FT-IR spectrum and Raman spectrum. Co26 features a rodlike Co26 core constructed by six Co4-TC4A secondary building units (SBUs) and four HL4- with two extra cobalt ions. Ni28 cluster represents a flowerlike Ni28 core built from six Ni4-TC4A SBUs, six HL4-, and four additional nickel ions. The multidentate risedronic acid displaying various new coordination mode bonds with SBUs to assemble two nanoclusters that enable high density possible coordinatively unsaturated metal sites (PCUMSs). Co26 and Ni28 clusters can be directly dispersed on carbon paper (CP) and showed extraordinary oxygen evolution reaction (OER) activity due to the larger exposed liable coordination active metal sites. The thermodecomposition of both nanoclusters at different temperatures afforded serial multicomponent complexes.

A Highly Symmetric Ionic Crystal Constructed by Polyoxoniobates and Cobalt Complexes for Preferential Water Uptake over Alcohols.

An ionic crystal assembled by PNb12O40(VO)6 and tris(1,2-diaminopropane)cobalt complexes was hydrothermally isolated and structurally characterized by routine methods. The compound exhibits three-dimensional channels with a pore size of 3.68 Å × 2.30 Å and composed of hydrophilic oxygen atoms of polyanions and hydrophobic -CH3 groups of 1,2-diaminopropane ligands. With increasing vapor pressure, the compound shows preferable adsorption toward water over alcohols, and a gate-opening behavior was deduced from the water adsorption isotherm.

Chiral Dodecanuclear Palladium(II) Thio Cluster: Synthesis, Structure, and Formation Mechanism Explored by ESI-MS and DFT Calculations.

The chiral dodecanuclear palladium(II) thio cluster LaPd12(C3H5NO2S)3(C3H6NO2S)21 (1) was prepared by reacting l-cysteine (l-Cys) with PdCl2 and La2O3 in aqueous solution under carefully controlled conditions. Compound 1 was structurally characterized by single-crystal XRD, TGA, IR, UV-vis, (13)C NMR, and CD spectroscopy. Insight into the dimerization process of 1 was obtained by ESI-MS and DFT calculations.

Three new imidazole-functionalized hexanuclear oxidovanadium clusters with exceptional catalytic oxidation properties for alcohols.

Cluster cat: Three new imidazole-functionalized neutral hexanuclear vanadium clusters have been prepared, one of which shows exceptional catalytic activity in the selective aerobic oxidation of alcohols (see scheme). Furthermore, these new polyoxovanadium clusters can be readily recycled and reused with unchanged catalytic activity. A plausible catalytic cycle is also proposed.

Controlled solvothermal synthesis of novel organic functionalized polyoxovanadates.

Four novel organic functionalized polyoxovanadates are solvothermally synthesized by altering the reaction temperature and using different organoarsonic acids. These POVs are fully characterized and the phase transitions between different POVs structures are confirmed by X-ray diffraction analyses. Such a transition is temperature-dependent and thus controlled synthesis of new POVs can be achieved.

Cation-induced synthesis of new polyoxopalladates.

Seven polyoxopalladate compounds, [Pd(15)(SeO(3))(10)(µ(3)-O)(10)](10-), with Na(+) (1) and K(+) (2) as counterions, and Na(6)[M(II){Pd(12)(SeO(3))(8)(µ(4)-O)(8)}]·nH(2)O (M = Co (3), Zn (4), Ni (5), Cu (6), Mn (7); n = 7-9), have been prepared and characterized by SXRD, FT-IR, UV-vis, EA, TGA, and ESI-MS. These compounds comprise two distinct cluster configurations, {Pd(15)} and {M(II)Pd(12)}, which reveals the possibility of obtaining desired noble metal clusters with a certain nuclearity by using different cations as potential structural directing or template agents in synthesis. All compounds showed apparent absorptions in the visible light region, while 3 and 7 were found to show paramagnetic behavior typical of mononuclear Co(II) and Mn(II) complexes with zero-field splitting.

Self-assembly of organic-inorganic hybrid materials constructed from eight-connected coordination polymer hosts with nanotube channels and polyoxometalate guests as templates.

Two polyoxometalate-templated organic-inorganic hybrid porous frameworks, namely, [Cu2(H2O)2(bpp)2Cl][PM12O40].approximately 20H2O (for 1, M = W; for 2, M = Mo; bpp = 1,3-bis(4-pyridyl)propane), were self-assembly obtained and structurally determined by elemental analyses, inductively coupled plasma analyses, infrared spectroscopy, and single-crystal X-ray diffraction analyses. Single-crystal X-ray analysis of these crystals revealed that both of the structures are constructed from eight-connected three-dimensional coordination polymer hosts [Cu2(H2O)2(bpp)2Cl]n(3n+) and ball-shaped Keggin-type guests [PM12O40]n(3n-) as templates. The polymer hosts resulted from a bcc-type framework with nanotubes, and the nanotubes can be regarded as a tetra-stranded helix structure. Furthermore, compounds 1 and 2 exhibit photoluminescent properties at ambient temperature, and the compound 2 bulk-modified carbon paste electrode ( 2-CPE) displays good electrocatalytic activity toward the reduction of nitrite.