Cu4I4 clusters supported by P^N-type ligands: new structures with tunable emission colors.

A series of Cu(4)I(4) clusters (1-5) supported by two P^N-type ligands 2-[(diRphosphino)methyl]pyridine (1, R = phenyl; 2, R = cyclohexyl; 3, R = tert-butyl; 4, R = iso-propyl; 5, R = ethyl) have been synthesized. Single crystal X-ray analyses show that all five clusters adopt a rare "octahedral" geometry. The central core of the cluster consists of the copper atoms arranged in a parallelogram with μ(4)-iodides above and below the copper plane. The copper atoms on the two short edges of the parallelogram (Cu-Cu = 2.525(2)-2.630(1) Å) are bridged with μ(2)-iodides, whereas the long edges (Cu-Cu = 2.839(3)-3.035(2) Å) are bridged in an antiparallel fashion by the P^N ligands. This Cu(4)I(4) geometry differs significantly from the "cubane" and "stairstep" geometries reported for other Cu(4)I(4)L(4) clusters. Luminescence spectra of clusters 3 and 4 display a single emission around 460 nm at room temperature that is assigned to emission from a triplet halide-to-ligand charge-transfer ((3)XLCT) excited state, whereas clusters 1, 2, and 5 also have a second band around 570 nm that is assigned to a Cu(4)I(4) cluster-centered ((3)CC) excited state. The structural and photophysical properties of a dinuclear Cu(2)I(2)(P^N)(2) complex obtained during the sublimation of cluster 3 is also provided.

[1]  J. Boilot,et al.  Thermochromic luminescence of copper iodide clusters: the case of phosphine ligands. , 2011, Inorganic chemistry.

[2]  Zhiwei Liu,et al.  A codeposition route to CuI-pyridine coordination complexes for organic light-emitting diodes. , 2011, Journal of the American Chemical Society.

[3]  Y. Ozawa,et al.  Flexibility of cubane-like Cu4I4 framework: temperature dependence of molecular structure and luminescence thermochromism of [Cu4I4(PPh3)4] in two polymorphic crystalline states. , 2010, Chemical communications.

[4]  Thierry Gacoin,et al.  Mechanochromic and thermochromic luminescence of a copper iodide cluster. , 2010, Journal of the American Chemical Society.

[5]  Alexander J. M. Miller,et al.  E-type delayed fluorescence of a phosphine-supported Cu2(mu-NAr2)2 diamond core: harvesting singlet and triplet excitons in OLEDs. , 2010, Journal of the American Chemical Society.

[6]  Richard Eisenberg,et al.  Tetranuclear copper(I) iodide complexes of chelating bis(1-benzyl-1H-1,2,3-triazole) ligands: structural characterization and solid state photoluminescence. , 2010, Inorganic chemistry.

[7]  N. Gerasimchuk,et al.  Reversible Cu(4) <--> Cu(6) core interconversion and temperature induced single-crystal-to-single-crystal phase transition for copper(I) carboxylate. , 2010, Inorganic chemistry.

[8]  X. You,et al.  A photoluminescent interpenetrating diamondoid metal–organic framework based on Cu4I4clusters with high thermal stability , 2009 .

[9]  Gregory D. Phelan,et al.  Complexes of Osmium with the 2-[(Diphenylphosphanyl)-methyl]-pyridine Ligand† , 2008 .

[10]  A. F. Richards,et al.  Copper halide clusters and polymers supported by bipodal heteroelemental ligands , 2008 .

[11]  Fernando Hung-Low,et al.  Silver coordination complexes of 2-(diphenylphosphinomethyl)pyridine and their bipyridine derivatives , 2008 .

[12]  Noboru Kitamura,et al.  Synthesis, Structure, and Emissive Properties of Copper(I) Complexes [CuI2(μ-X)2(μ-1,8-naphthyridine)(PPh3)2] (X = I, Br) with a Butterfly-Shaped Dinuclear Core Having a Short Cu-Cu Distance , 2007 .

[13]  D. Datta,et al.  Estimation of the van der Waals radii of the d-block elements using the concept of bond valence , 2007 .

[14]  Akira Tsuboyama,et al.  Photophysical properties of highly luminescent copper(I) halide complexes chelated with 1,2-bis(diphenylphosphino)benzene. , 2007, Inorganic chemistry.

[15]  F. De Angelis,et al.  Electronic transitions involved in the absorption spectrum and dual luminescence of tetranuclear cubane [Cu4I4(pyridine)4] cluster: a density functional theory/time-dependent density functional theory investigation. , 2006, Inorganic chemistry.

[16]  J. Díez,et al.  Tetra-, di-, and mononuclear copper(I) complexes containing (S,S)-iPr-pybox and (R,R)-Ph-pybox ligands. , 2006, Inorganic chemistry.

[17]  J. Dinda,et al.  Polynuclear and tetranuclear cuprous iodide complexes derived from N -(2-thienylmethylidene)-2-pyridylamine derivatives , 2006 .

[18]  S. Ng,,et al.  Increasing structure dimensionality of copper(I) complexes by varying the flexible thioether ligand geometry and counteranions. , 2006, Inorganic chemistry.

[19]  Yabo Xie,et al.  A novel tetranuclear CuI complex with a flexible monothioether ligand , 2006 .

[20]  T. Mochida,et al.  Metal complexes from 1,1'-di(pyrazinyl)ferrocene: coordination polymers and bridged diferrocenes. , 2006, Dalton transactions.

[21]  Zichuan Ma,et al.  Synthesis and crystal structure of the copper(I) complex with 2-[(o-pyridyl)-sulfanylmethyl]-pyrimidine ligand , 2006 .

[22]  Noboru Kitamura,et al.  Luminescence ranging from red to blue: a series of copper(I)-halide complexes having rhombic {Cu2(mu-X)2} (X = Br and I) units with N-heteroaromatic ligands. , 2005, Inorganic chemistry.

[23]  M. Omary,et al.  Photophysics of supramolecular binary stacks consisting of electron-rich trinuclear Au(I) complexes and organic electrophiles , 2005 .

[24]  S. Galli,et al.  New structural motifs, unusual quenching of the emission, and second harmonic generation of copper(I) iodide polymeric or oligomeric adducts with para-substituted pyridines or trans-stilbazoles. , 2005, Inorganic chemistry.

[25]  Oussama Elbjeirami,et al.  Brightly phosphorescent trinuclear copper(I) complexes of pyrazolates: substituent effects on the supramolecular structure and photophysics. , 2005, Journal of the American Chemical Society.

[26]  X. Bu,et al.  Syntheses and crystal structures of the copper(I) complexes with quinoline-based monothioether ligands , 2005 .

[27]  B. le Guennic,et al.  Synthesis, photophysics, electrochemistry, theoretical, and transient absorption studies of luminescent copper(I) and silver(I) diynyl complexes. X-ray crystal structures of [Cu3(micro-dppm)3(micro3-eta1-C triple bond CC triple bond CPh)2]PF6 and [Cu3(micro-dppm)3(micro3-eta1-C triple bond CC triple , 2004, Journal of the American Chemical Society.

[28]  A. Vega,et al.  Bonding in tetrahedral Cu4(mu3-X)4L4 copper(I) clusters: a DFT investigation. , 2004, Inorganic chemistry.

[29]  C. Che,et al.  Cuprophilic interactions in luminescent copper(I) clusters with bridging bis(dicyclohexylphosphino)methane and iodide ligands: spectroscopic and structural investigations. , 2004, Chemistry.

[30]  C. Jacob,et al.  Rhodium complexes containing the hybrid P,O ligand PPh2NHC(O)Me or its anion, [PPh2NC(O)Me]− , 2003 .

[31]  M. Sawamoto,et al.  Metal-catalyzed living radical polymerization. , 2001, Chemical reviews.

[32]  S. Batsanov,et al.  Van der Waals Radii of Elements , 2001 .

[33]  M. Lemaire,et al.  Nitrogen-containing ligands for asymmetric homogeneous and heterogeneous catalysis. , 2000, Chemical reviews.

[34]  Peter C. Ford,et al.  Photoluminescence Properties of Multinuclear Copper(I) Compounds. , 1999, Chemical reviews.

[35]  D. McMillin,et al.  Photoprocesses of Copper Complexes That Bind to DNA. , 1998, Chemical reviews.

[36]  C. Su,et al.  Synthesis and Crystal Structure of the Tetranuclear Copper(I) Complex [Cu4I4(MPTQ)2] with a N,S,N′-Tridentate Ligand(MPTQ = 8-((2-Pyridylmethyl)thio)quinoline) , 1997 .

[37]  Tasuku Ito,et al.  Intermolecular Ferromagnetic and Antiferromagnetic Interactions in Halogen-Bridged Copper(I) Imino Nitroxides: Crystal Structures and Magnetic Properties of [Cu(I)(&mgr;-X)(imino nitroxide)](2) (X = I or Br). , 1996, Inorganic chemistry.

[38]  Peter C. Ford,et al.  Photochemical and photophysical studies of tetranuclear copper(I) halide clusters: an overview , 1994 .

[39]  Chong Kul Ryu,et al.  Ab initio studies of the copper(I) tetramers Cu4X4L4 (X = I, Br, Cl). Effects of cluster structure and of halide on photophysical properties , 1994 .

[40]  T. Mak,et al.  Synthesis and characterization of copper(I) halide/pseudohalide adducts of 2-benzoylpyridine and x-ray crystal structure of [di-μ-iodo-bis(N,O-2-benzoylpyridine)dicopper(I)] , 1993 .

[41]  P. C. Ford,et al.  Photochemical and photophysical properties of tetranuclear and hexanuclear clusters of metals with d10 and s2 electronic configurations , 1993 .

[42]  M. Vitale,et al.  Origins of the double emission of the tetranuclear copper(I) cluster Cu4I4(pyridine)4: an ab initio study , 1992 .

[43]  P. C. Ford,et al.  Photophysical studies in solution of the tetranuclear copper(I) clusters Cu4I4L4 (L = pyridine or substituted pyridine) , 1991 .

[44]  A. Tóth,et al.  Copper(I)−benzimidazole adducts: from mononuclear to polymeric complexes , 1987 .

[45]  J. C. Dyason,et al.  LEWIS BASE ADDUCTS OF GROUP 11 METAL COMPOUNDS. 15. STRUCTURAL STUDIES OF MONONUCLEAR ADDUCTS OF COPPER(I) HALIDES WITH PYRIDINE BASES OF STOICHIOMETRY XCUL2,3 , 1985 .

[46]  J. Strähle,et al.  Strukturisomere von Kupfer(I)iodid · Pyridin und ihre Lumineszenzeigenschaften. Darstellung und Kristallstruktur einer neuen Modifikation von Cul · NC5H5 / Structural Isomers of Copper(I) Iodide Pyridine and their Luminescence Properties Synthesis and Crystal Structure of a New Modification of Cul · , 1980 .

[47]  A. Bondi.  van der Waals Volumes and Radii , 1964 .

[48]  A. Listorti,et al.  Photochemistry and Photophysics of Coordination Compounds: Copper , 2007 .

[49]  P. Delhaès,et al.  Synthesis and characterization of an extended tetrathiafulvalenederivative coordinated to copper iodide and its charge-transfer andradical ion salts , 1997 .

[50]  M. Vitale,et al.  Photoluminescence properties of the structurally analogous tetranuclear copper(I) clusters Cu4X4(dpmp)4 (X = I, Br, Cl; dpmp = 2-(diphenylmethyl)pyridine) , 1993 .

[51]  J. Kildea,et al.  Lewis-Base Adducts of Group 11 Metal(I) Compounds. XLII : [Cu4X4L4] 'cubane' clusters, L = hindered N-base ligand: synthesis and structures of the L = 2-(diphenymethyl)pyridine complexes (X = Cl, Br, I) , 1989 .

[52]  J. Kildea,et al.  Lewis-Base Adducts of Group 11 Metal(I) Compounds. XLIII : Synthesis and structural systematics of 1:1 copper(I) halide/nitrogen base adducts as [(N-base)1(CuX)1]∞ 'split-stair' polymers (X = Cl, Br, I; N-base = acridine, quinaldine and 2,6-dimethyl- a , 1989 .

[53]  P. Healy,et al.  Lewis-Base Adducts of Group 11 Metal(I) Compounds. XXXVII. A Novel Isomerism in the Heterobimetallic 1:1 Adducts of Copper(I) Halides With Tris(dithiocarbamato)cobalt(III) , 1988 .

[54]  E. M. Holt,et al.  Fluorescent copper(I) complexes: an X-ray diffraction study of complexes of copper(I) iodide and pyridine derivatives of rhombic, [Cu2I2(3Me-py)4], and polymeric structure, [{Cul(2me-py)}∞] and [{Cul(2,4Me2-py)}∞] , 1986 .

[55]  P. Healy,et al.  Lewis-base adducts of Group 1B metal(I) compounds. Part 18. Stereo-chemistries and structures of the 1 : 1 neutral complexes of CuIX with 1,10-phenanthroline (X = I) or 2,9-dimethyl-1,10-phenanthroline (X = I, Br, or Cl) , 1985 .

[56]  G. Soloveichik,et al.  Crystal and molecular structure of complex compound (C5H5)2Re(H)CuRe(H)(C5H5)2: A first direct proof of the formation of the Cu(I)Cu(I) bond , 1984 .

[57]  C. Raston,et al.  Lewis-base adducts of Group 1B metal(I) compounds. Part 1. Synthesis and structure of CuILn complexes (L = nitrogen base, n⩽ 1.5) , 1983 .

[58]  C. Raston,et al.  Crystal structure of the copper(I) iodide–pyridine (1/1 ) tetramer , 1976 .