Synthesis and characterization of a nanocluster-based silver(i) tert-butylethynide compound with a large second-harmonic generation response.

A new nanocluster-based silver(i) tert-butylethynide compound, namely, (tBuC[triple bond, length as m-dash]CAg)2(Ag4SiW12O40)(DMSO)6 (HT-1), has been synthesized and structurally characterized by X-ray crystallography. The two kinds of nanocluster synthons (a silver aggregate named [(tBuC[triple bond, length as m-dash]C)2Ag6(DMSO)6] and a SiW12 polyoxoanion) are assembled into a three-dimensional coordination network, which has a non-centrosymmetric crystal lattice. Powder second-harmonic generation (SHG) measurements reveal that HT-1 belongs to the phase-matchable class with a moderately strong SHG response of about 3 times that of the KH2PO4 (KDP) sample. HT-1 represents the first example of a Ag(i) alkynyl cluster compound with a SHG response. The present study not only extends the application fields of Ag(i) alkynyl clusters but also demonstrates a new paradigm for understanding the Ag(i) alkynyl structural chemistry.

[1]  T. Pradeep,et al.  Formation of an NIR-emitting Ag34S3SBB20(CF3COO)62+ cluster from a hydride-protected silver cluster. , 2019, Dalton transactions.

[2]  Mao‐Lin Hu,et al.  Trivalent Tetrahedral Anion Template: A 26-Nucleus Silver Alkynyl Cluster Encapsulating Vanadate. , 2019, Inorganic chemistry.

[3]  M. Shao,et al.  Various Silver Phosphinate Inorganic Architectures in Three-Dimensional Frameworks with Argentophilic Interactions , 2019, Crystal Growth & Design.

[4]  Guo‐Yu Yang,et al.  Zr4-Substituted polyoxometalate dimers decorated by d-tartaric acid/glycolic acid: syntheses, structures and optical/electrochemical properties , 2019, CrystEngComm.

[5]  Xing Lu,et al.  High-Nuclearity Heterometallic tert-Butylethynide Clusters Assembled with tert-Butylphosphonate. , 2018, Chemistry.

[6]  C. Tung,et al.  A giant 90-nucleus silver cluster templated by hetero-anions. , 2018, Chemical communications.

[7]  C. Tung,et al.  Elimination-Fusion Self-Assembly of a Nanometer-Scale 72-Nucleus Silver Cluster Caging a Pair of [EuW10 O36 ]9- Polyoxometalates. , 2018, Chemistry.

[8]  Xing Lu,et al.  Structure-Directing Role of Phosphonate in the Synthesis of High-Nuclearity Silver(I) Sulfide-Ethynide-Thiolate Clusters. , 2017, Inorganic chemistry.

[9]  Canzhong Lu,et al.  Synthesis and characterization of polyoxometalate-based silver(I) phenylethynide compounds with antibacterial and antifungal activities , 2017 .

[10]  Rui Cao,et al.  Two- and three-dimensional silver acetylide frameworks with high-nuclearity silver cluster building blocks assembled using a bifunctional (4-ethynylphenyl)diphenyl phosphine ligand , 2017 .

[11]  Quan‐Ming Wang,et al.  [Mn(III)Mn(IV)2Mo14O56](17-): A Mixed-Valence Meso-Polyoxometalate Anion Encapsulated by a 64-Nuclearity Silver Cluster. , 2016, Inorganic chemistry.

[12]  Samahe Sadjadi and Majid M. Heravi.  Recent Advances in Applications of POMs and Their Hybrids in Catalysis , 2016 .

[13]  Jin Yang,et al.  Silver(I) Cage and Infinite Chain Stabilized by Bowl-Shaped Resorcin[4]arene Tetraethynide Ligands , 2016 .

[14]  Bao Li,et al.  A Luminescent 3D Organometallic Network Based on Silver Clusters and Star-like Tris(4-ethynylphenyl)amine , 2015 .

[15]  Guanggang Gao,et al.  Self-assembly of an unprecedented polyoxomolybdate anion [Mo20O66]12- in a giant peanut-like 62-core silver-thiolate nanocluster. , 2015, Nanoscale.

[16]  Guanggang Gao,et al.  A silver-alkynyl cluster encapsulating a fluorescent polyoxometalate core: enhanced emission and fluorescence modulation. , 2015, Dalton transactions.

[17]  Z. Su,et al.  Rational synthesis, structural characterization and theoretical exploration on third-order nonlinear optical properties of isolated Agn (n = 5, 8, 12) alkynyl clusters , 2015 .

[18]  F. Arisaka,et al.  Asymmetrically fused polyoxometalate-silver alkynide composite cluster. , 2015, Inorganic chemistry.

[19]  Z. Su,et al.  An ultrastable {Ag55Mo6} nanocluster with a Ag-centered multishell structure. , 2014, Chemical communications.

[20]  Quan‐Ming Wang,et al.  [Ag(70)(PW(9)O(34))(2)((t)BuC[triple bond, length as m-dash]C)(44)(H(2)O)(2)](8+): ionothermal synthesis of a silver cluster encapsulating lacunary polyoxometalate ions. , 2014, Chemical communications.

[21]  T. Mak,et al.  Silver(I) multiple salts assembled with phosphonate, perfluorocarboxylate, and the multinuclear silver-ethynediide supramolecular synthon. , 2013, Inorganic chemistry.

[22]  F. Gao,et al.  A giant metallo-supramolecular cage encapsulating a single-molecule magnet. , 2013, Chemical communications.

[23]  Liang Zhao,et al.  Assembly of Silver-Organic Frameworks and Discrete Molecules Containing Embedded 1,3-Butadiyne-1,4-diide with Ancillary Heteroaromatic N-Donor Ligands , 2012 .

[24]  Eugenio Coronado,et al.  Magnetic polyoxometalates: from molecular magnetism to molecular spintronics and quantum computing. , 2012, Chemical Society reviews.

[25]  Ji-qing Xu,et al.  Two supramolecular structures constructed from Keggin-type polyoxometalates and 4,4′-bipyridine , 2012 .

[26]  T. Mak,et al.  High-nuclearity silver ethynide clusters assembled with phosphonate and metavanadate precursors. , 2012, Angewandte Chemie.

[27]  T. Mak,et al.  Silver-Ethynide Clusters with Oxovanadate Components , 2012, Journal of Cluster Science.

[28]  Liang Zhao,et al.  Supramolecular Assembly of Silver(I) Complexes with Argentophilic and Silver…Carbon Interactions , 2012 .

[29]  T. Mak,et al.  Enlargement of globular silver alkynide cluster via core transformation. , 2012, Journal of the American Chemical Society.

[30]  T. Mak,et al.  A pyrovanadate-templated silver(I)-ethynide cluster circumscribed by macrocyclic polyoxovanadate(V). , 2012, Chemical communications.

[31]  M. Jansen,et al.  Supramolecular Intercluster Compounds Consisting of 1D Arrays of Silver Alkynyl Clusters and Wells–Dawson Anions, Displaying Ligand‐Free Interfaces , 2011 .

[32]  Shuangquan Zang,et al.  Silver(I)-organic networks constructed with flexible silver-ethynide supramolecular synthon o-, m-, , 2011 .

[33]  Liang Zhao,et al.  Designed synthesis of metal cluster-centered pseudo-rotaxane supramolecular architectures. , 2011, Journal of the American Chemical Society.

[34]  T. Mak,et al.  Silver(I)-ethynide clusters constructed with phosphonate-functionized polyoxovanadates. , 2011, Journal of the American Chemical Society.

[35]  M. Jansen,et al.  Packing requirements and short-range interactions as structure-directing forces in the intercluster compounds based on silver clusters , 2010 .

[36]  Fei Wang,et al.  A new IR non-linear optical material with 2D 3-fold interpenetrated topology† , 2010 .

[37]  Hongbing Song,et al.  Rational assembly and luminescence properties of 2 and 3D organometallic networks using silver(I) 4-pyridylethynide and 5-pyrimidylethynide complexes as building units , 2010 .

[38]  M. Jansen,et al.  {[Ag42(CO3)(C[triple bond]CtBu)27(CH3CN)2][CoW12O40]2}[BF4]: an intercluster sandwich compound. , 2010, Angewandte Chemie.

[39]  Franziska Gruber and,et al.  {[Ag42(CO3)(CCtBu)27(CH3CN)2][CoW12O40]2}[BF4]: An Intercluster Sandwich Compound , 2010 .

[40]  Annamalai Senthil Kumar,et al.  Ru(DMSO)4Cl2 nano-aggregated Nafion membrane modified electrode for simultaneous electrochemical detection of hypoxanthine, xanthine and uric acid , 2010 .

[41]  J. Qiao,et al.  A giant silver alkynyl cage with sixty silver(I) ions clustered around polyoxometalate templates. , 2010, Angewandte Chemie.

[42]  M. Jansen,et al.  Structure-directing forces in intercluster compounds of cationic [Ag(14)(C[triple bond]CtBu)(12)Cl](+) building blocks and polyoxometalates: long-range versus short-range bonding interactions. , 2010, Chemistry.

[43]  Guanggang Gao,et al.  Acid-induced surface functionalization of polyoxometalate by enclosure in a polyhedral silver-alkynyl cage. , 2009, Journal of the American Chemical Society.

[44]  M. Dressel,et al.  Polyoxometalates: Fascinating structures, unique magnetic properties , 2009 .

[45]  G. Guo,et al.  Synthesis and structural characterization of silver(I) double and multiple salts containing the acetylenediide dianion , 2007 .

[46]  S. Ma,et al.  RhI‐Catalyzed Bimolecular Cyclization between Two Different 1,5‐Bisallenes: A Combinatorial One‐Step Approach to Heterosteroids and Mechanistic Implications , 2007 .

[47]  Y. B. Xie,et al.  Photoelectrochemical Reactivity of a Hybrid Electrode Composed of Polyoxophosphotungstate Encapsulated in Titania Nanotubes , 2006 .

[48]  W. Wong,et al.  Novel mu5-coordination modes of aryl and alkyl ethynides and classification of metal-ligand interactions in silver(I) complexes. , 2006, Chemistry.

[49]  Liang Zhao,et al.  Silver(I) 1,3-butadiynediide and two related silver(I) double salts containing the C4(2-) dianion. , 2004, Journal of the American Chemical Society.

[50]  Keigo Kamata,et al.  Efficient Epoxidation of Olefins with ≥99% Selectivity and Use of Hydrogen Peroxide , 2003, Science.

[51]  Matt Probert,et al.  First-principles simulation: ideas, illustrations and the CASTEP code , 2002 .

[52]  Yuji Suzuki,et al.  Nanocluster crystals of lacunary polyoxometalates as structure-design-flexible, inorganic nonlinear materials , 2001 .

[53]  Andrew J. P. White,et al.  Anion-Templated Syntheses of Rhombohedral Silver-Alkynyl Cage Compounds. , 2001, Angewandte Chemie.

[54]  M. Payne,et al.  Electronic structure, properties, and phase stability of inorganic crystals: A pseudopotential plane‐wave study , 2000 .

[55]  R. Schinazi,et al.  Polyoxometalates in Medicine. , 1998, Chemical reviews.

[56]  X. You,et al.  Second-order non-linear optical response of a novel type ofcharge-transfer complex,[4-DMSP]4[NH2Me2]2HSiFeMo11O40·3H2O , 1997 .

[57]  X. You,et al.  Preparation, characterization and X-ray crystal structure of a charge transfer salt (DMNP)4[SiW12O40] · 2DMF , 1997 .

[58]  Achim Müller,et al.  Polyoxometalate Chemistry: An Old Field with New Dimensions in Several Disciplines , 1991 .

[59]  M. Jansen.  Homoatomic d10–d10 Interactions: Their Effects on Structure and Chemical and Physical Properties , 1987 .

[60]  R. Thouvenot,et al.  Vibrational investigations of polyoxometalates. 2. Evidence for anion-anion interactions in molybdenum(VI) and tungsten(VI) compounds related to the Keggin structure , 1983 .

[61]  S. K. Kurtz,et al.  A powder technique for the evaluation of nonlinear optical materials , 1968 .

[62]  F. Cotton,et al.  SULFOXIDES AS LIGANDS. II. THE INFRARED SPECTRA OF SOME DIMETHYL SULFOXIDE COMPLEXES , 1960 .