Activation and amplification of the third-order NLO and luminescent responses of a precursor cluster by a supramolecular approach.

Solvothermal reactions of [Et(4)N][Tp*WS(3)(CuCl)(3)] (1) (Tp* = hydridotris(3,5-dimethylpyrazol-1-yl)borate) with CuCN and KCu(CN)(2) afforded two [Tp*WS(3)Cu(3)]-based coordination polymers [Tp*WS(3)Cu(3)(μ(3)-DMF){Cu(CN)(3)}](2) (2) and K[Tp*WS(3)Cu(3)(μ(3)-DMF){Cu(2)(CN)(4.5)}](2) (3). The third-order NLO and PL responses of 1 were activated and greatly amplified through its assembly via the [Cu(CN)(3)](2-) and [Cu(4)(CN)(9)](5-) species in 2 and 3.

[1]  Yinglin Song,et al.  Modulation of Third‐Order Nonlinear Optical Properties by Backbone Modification of Polymeric Pillared‐Layer Heterometallic Clusters , 2008 .

[2]  Yinglin Song,et al.  Ultrafast Response and Superior Optical Limiting Effects of Planar “Open” Heterothiometallic Clusters , 2002 .

[3]  Michael O'Keeffe,et al.  Secondary building units, nets and bonding in the chemistry of metal-organic frameworks. , 2009, Chemical Society reviews.

[4]  J. Lang,et al.  Cracking the framework of bulk CuCN with flexible bipyrazolyl-based ligands to assemble [CuCN]n-based coordination polymers. , 2010, Dalton transactions.

[5]  K. Summer,et al.  Tetrathiomolybdate causes formation of hepatic copper-molybdenum clusters in an animal model of Wilson's disease. , 2003, Journal of the American Chemical Society.

[6]  Leroy Cronin,et al.  Modular assembly of a functional polyoxometalate-based open framework constructed from unsupported AgI--AgI interactions. , 2007, Angewandte Chemie.

[7]  J. Lang,et al.  Single-crystal-to-single-crystal transformations of two three-dimensional coordination polymers through regioselective [2+2] photodimerization reactions. , 2010, Angewandte Chemie.

[8]  Wenhao Zhang,et al.  Syntheses, crystal structures, and third-order nonlinear optical properties of two novel Mo/Cu/S clusters: [MoS4Cu4(α-MePy)5Br2] · 2(α-MePy)0.5 and {[MoS4Cu4(α-MePy)3Br](μ-Br) · (α-MePy)}n (α-MePy = α-methylpyridine) , 2005 .

[9]  J. Lang,et al.  Assembly of a supramolecular cube, [(Cp*WS3Cu3)8 Cl8(CN)12Li4] from a preformed incomplete cubane-like compound [PPh4][Cp*WS3(CuCN)3]. , 2003, Journal of the American Chemical Society.

[10]  Xiao‐Ping Zhou,et al.  pH-Induced formation of metalloligand: increasing structure dimensionality by tuning number of ligand functional sites. , 2007, Chemical communications.

[11]  Mark E. Davis.  Ordered porous materials for emerging applications , 2002, Nature.

[12]  Yinglin Song,et al.  Self-assembly of interpenetrating coordination nets formed from interpenetrating cationic and anionic three-dimensional diamondoid cluster coordination polymers. , 2004, Angewandte Chemie.

[13]  N. Gadegaard,et al.  Supramolecular silver polyoxometalate architectures direct the growth of composite semiconducting nanostructures. , 2009, Angewandte Chemie.

[14]  F. Cotton,et al.  A Calix[4]arene Carceplex with Four Rh24+ Fasteners , 2004 .

[15]  Qing-feng Xu,et al.  Structural aspects of copper(I) and silver(I) sulfide clusters of pentamethylcyclopentadienyl trisulfido tungsten(VI) and molybdenum(VI) , 2003 .

[16]  Jingui Duan,et al.  Enhanced CO2 binding affinity of a high-uptake rht-type metal-organic framework decorated with acylamide groups. , 2011, Journal of the American Chemical Society.

[17]  Quan‐Ming Wang,et al.  Construction of heterometallic cages with tripodal metalloligands. , 2009, Angewandte Chemie.

[18]  E. Wang,et al.  Bottom-up synthesis of porous coordination frameworks: apical substitution of a pentanuclear tetrahedral precursor. , 2009, Angewandte Chemie.

[19]  T. Rauchfuss,et al.  {K⊂[Mo6(μ‐CN)9(CO)18]}8−: A Trigonal‐Prismatic Cyanometalate Cage , 2000 .

[20]  Jun He,et al.  Novel thermochromism relating to supramolecular cuprophilic interaction: design, synthesis, and luminescence of copper(I) pyrazolate trimer and polymer. , 2008, Inorganic chemistry.

[21]  G. Blasse,et al.  Host lattice dependence of the Bi3+ luminescence in orthoborates LnBO3 (with Ln = Sc, Y, La, Gd, or Lu) , 1985 .

[22]  Paras N. Prasad,et al.  Probing two-photon excitation dynamics using ultrafast laser pulses , 1998 .

[23]  R. Neumann,et al.  New heterogeneous polyoxometalate based mesoporous catalysts for hydrogen peroxide mediated oxidation reactions. , 2004, Journal of the American Chemical Society.

[24]  Keigo Kamata,et al.  Epoxidation of olefins with hydrogen peroxide catalyzed by polyoxometalates , 2005 .

[25]  Q. Guo,et al.  Synthesis and luminescent properties of CaMoO4:Tb3+, R+ (Li+, Na+, K+) , 2009 .

[26]  Mian Li,et al.  Supramolecular helix-to-helix induction: a 3D anionic framework containing double-helical strands templated by cationic triple-stranded cluster helicates. , 2008, Angewandte Chemie.

[27]  M. Shao,et al.  Hydrothermal synthesis and crystal structure of a novel cyanide-bridged double helical copper(I) coordination polymer [Cu3(CN)3(phen)]n , 2006 .

[28]  Jin Yang,et al.  An unusual ten-connected self-penetrating metal-organic framework based on tetranuclear cobalt clusters. , 2010, Chemical communications.

[29]  U. Schubert.  Cluster-based inorganic-organic hybrid materials. , 2011, Chemical Society reviews.

[30]  Paras N. Prasad,et al.  New Class of Two-Photon-Absorbing Chromophores Based on Dithienothiophene , 2000 .

[31]  Guodong Qian,et al.  A luminescent microporous metal-organic framework for the recognition and sensing of anions. , 2008, Journal of the American Chemical Society.

[32]  J. Lang,et al.  {[WS4Cu4(4,4′‐bpy)4][WS4Cu4I4(4,4′‐bpy)2]}∞—An Unusual 3D Porous Coordination Polymer Formed from the Preformed Cluster [Et4N]4[WS4Cu4I6] , 2004 .

[33]  M. Shao,et al.  Syntheses, structures and luminescent properties of four copper(I) cyanide coordination polymers based on 2-(n-pyridyl)benzimidazole ligands (n = 2,3,4) , 2007 .

[34]  Y. Ohki,et al.  Sulfido-bridged dinuclear molybdenum-copper complexes related to the active site of CO dehydrogenase: [(dithiolate)Mo(O)S2Cu(SAr)]2- (dithiolate = 1,2-S2C6H4, 1,2-S2C6H2-3,6-Cl2, 1,2-S2C2H4). , 2005, Inorganic chemistry.

[35]  J. Lang,et al.  Stepwise addition of CuNCS onto [Et(4)N][Tp*WS(3)]: design, syntheses, structures and third-order nonlinear optical properties. , 2009, Dalton transactions.

[36]  Yinglin Song,et al.  Correlations between molecular structures and third-order non-linear optical functions of heterothiometallic clusters: A comparative study , 2007 .

[37]  Leroy Cronin,et al.  Polyoxometalate clusters, nanostructures and materials: from self assembly to designer materials and devices. , 2007, Chemical Society reviews.

[38]  Jianjun Zhang,et al.  Directed assembly of cluster-based supramolecules into one-dimensional coordination polymers. , 2007, Angewandte Chemie.

[39]  Jianjun Zhang,et al.  A 3D canted antiferromagnetic porous metal-organic framework with anatase topology through assembly of an analogue of polyoxometalate. , 2005, Journal of the American Chemical Society.

[40]  Mircea Dincă,et al.  Hydrogen storage in metal-organic frameworks. , 2009, Chemical Society reviews.

[41]  Yuhua Wang,et al.  Influence of alkali metal ions doping content on photoluminescence of (Y, Gd) BO3:Eu red phosphors under VUV excitation , 2010 .

[42]  Zhiping Zheng,et al.  Ligand-bridged oligomeric and supramolecular arrays of the hexanuclear rhenium selenide clusters--exploratory synthesis, structural characterization, and property investigation. , 2003, Accounts of chemical research.

[43]  Zhenda Lu,et al.  Solvatochromic behavior of a nanotubular metal-organic framework for sensing small molecules. , 2011, Journal of the American Chemical Society.