Red and blue luminescent metallo-supramolecular coordination polymers assembled through π–π interactions

The use of π-stacking interactions to control the aggregation of photo-active metal centres is explored through the design of bis(2,2′;6′,2′′-terpyridyl) metal complexes functionalised with biphenyl ‘tails’. Aryl–aryl interactions control the aggregation of the metal complexes into polymetallic arrays in the solid state. Cobalt(II), ruthenium(II), nickel(II), copper(II), zinc(II) and cadmium(II) bis-ligand complexes and a mixed ligand ruthenium(II) complex have been structurally characterised. The solid-state structures are dependent on which units dominate the π-stacking. For cobalt, ruthenium, nickel and copper, biphenylene–biphenylene interactions lead to linear rod-like arrays, while for the group 12 d10 ions zinc and cadmium, biphenylene–pyridyl interactions lead to two-dimensional sheets. The addition of the biphenylene tail has favourable effects on the photophysical-properties of the complexes which exhibit room temperature red (ruthenium) or blue (zinc and cadmium) luminescence, both in solution and the solid state.

[1]  Z. Pikramenou,et al.  An efficient synthesis of versatile terpyridine analogues for cyclometallated luminescent cyclodextrins , 1999 .

[2]  M. Rehahn,et al.  Synthesis and properties in solution of rodlike 2,2':6',2''-terpyridine-based ruthenium(II) coordination polymers , 1999 .

[3]  F. Barigelletti,et al.  Synthesis and Photophysical Properties of Iridium(III) Bisterpyridine and Its Homologues: a Family of Complexes with a Long-Lived Excited State , 1999 .

[4]  H. Goodwin,et al.  Crystal supramolecular motifs: two-dimensional grids of terpy embraces in [ML2]z complexes (L=terpy or aromatic N3-tridentate ligand) , 1999 .

[5]  M. Linford,et al.  Metallosupramolecular Thin Polyelectrolyte Films. , 1998, Angewandte Chemie.

[6]  A. V. Zelewsky,et al.  On the Way towards New Materials: Metal Complexes as Building Blocks , 1998, CHIMIA.

[7]  V. Balzani,et al.  Photoinduced processes in 4′-(9-anthryl)-2,2′:6′,2″-terpyridine, its protonated forms and Zn(II), Ru(II) and Os(II) complexes , 1998 .

[8]  A. Harriman,et al.  Fine-Tuning the Electronic Properties of Binuclear Bis(terpyridyl)ruthenium(II) Complexes. , 1998, Angewandte Chemie.

[9]  A. Harriman,et al.  Building photoactive molecular-scale wires , 1998 .

[10]  M. Ward,et al.  Assemblies of luminescent ruthenium(II)— and osmium(II)—polypyridyl complexes based on hydrogen bonding , 1998 .

[11]  Y. Tor,et al.  Metal-Containing Oligonucleotides: Solid-Phase Synthesis and Luminescence Properties , 1998 .

[12]  V. Balzani,et al.  Designing Dendrimers Based on Transition-Metal Complexes. Light-Harvesting Properties and Predetermined Redox Patterns , 1998 .

[13]  M. Ward,et al.  Crystal structures of a series of CoII, CuII and ZnII complexes of 4′-(3,4-dihydroxyphenyl)-2,2′ : 6′,2″-terpyridine and 4′-(3,4-dimethoxyphenyl)-2,2′:6′,2″-terpyridine , 1998 .

[14]  R. Blessing.  Outlier Treatment in Data Merging , 1997 .

[15]  E. Constable,et al.  The coordination chemistry of 4′-(4-tert-butylphenyl)-2,2′ : 6′,2″-terpyridine—a solubilising oligopyridine , 1997 .

[16]  Z. Otwinowski,et al.  [20] Processing of X-ray diffraction data collected in oscillation mode. , 1997, Methods in enzymology.

[17]  J. Sessler,et al.  A rigid cytidine-RuII(bpy)3 conjugate. A potential precursor for non-covalent electron transfer modeling , 1996 .

[18]  David A. Fletcher,et al.  The United Kingdom Chemical Database Service , 1996, J. Chem. Inf. Comput. Sci..

[19]  Vincenzo Balzani,et al.  Luminescent and Redox-Active Polynuclear Transition Metal Complexes. , 1996, Chemical reviews.

[20]  V. Balzani,et al.  Complexes of the Ruthenium(II)-2,2':6',2''-terpyridine Family. Effect of Electron-Accepting and -Donating Substituents on the Photophysical and Electrochemical Properties , 1995 .

[21]  A. F. Williams,et al.  SUCCESSIVE USE OF METAL ION COORDINATION AND HYDROGEN BONDING TO GENERATE INTERPENETRATING INFINITE RHOMBOHEDRAL NETWORKS , 1995 .

[22]  R. Blessing,et al.  An empirical correction for absorption anisotropy. , 1995, Acta crystallographica. Section A, Foundations of crystallography.

[23]  V. Balzani,et al.  Ruthenium(II) and Osmium(II) Bis(terpyridine) Complexes in Covalently-Linked Multicomponent Systems: Synthesis, Electrochemical Behavior, Absorption Spectra, and Photochemical and Photophysical Properties , 1994 .

[24]  Giovanni Luca Cascarano,et al.  Completion and refinement of crystal structures with SIR92 , 1993 .

[25]  E. Constable,et al.  SYNTHESIS, CHARACTERIZATION AND SPECTROSCOPIC PROPERTIES OF RUTHENIUM(II)-2,2'-6',2''-TERPYRIDINE COORDINATION TRIADES X-RAY STRUCTURES OF 4'-(N,N-DIMETHYLAMINO)-2,2'-6',2''-TERPYRIDINE AND BIS(4'-(N,N-DIMETHYLAMINO)-2,2'-6',2''-TERPYRIDINE)RUTHENIUM(II) HEXAFLUOROPHOSPHATE ACETONITRILE SOLVATE , 1992 .

[26]  J. Sauvage,et al.  3,3',5,5'-Tetrapyridylbiphenyl, a bis-cyclometalating bridging ligand with a high coupling ability in ruthenium(III), ruthenium(II) mixed valence systems , 1991 .

[27]  Paul R. Raithby,et al.  The coordination chemistry of 4′-phenyl-2,2′:6′, 2″-terpyridine; the synthesis, crystal and molecular structures of 4′-phenyl-2,2′:6′,2″-terpyridine and bis(4′-phenyl-2,2′:6′,2″-terpyridine)nickel(II) chloride decahydrate , 1990 .

[28]  G. Sheldrick.  Phase annealing in SHELX-90: direct methods for larger structures , 1990 .

[29]  Vincenzo Balzani,et al.  Ru(II) polypyridine complexes: photophysics, photochemistry, eletrochemistry, and chemiluminescence , 1988 .

[30]  P. Yohannes,et al.  [Co(terpy)2] [NO3]2ṡ2H2O: Tetragonal Compression with Elongated Equatorial Bonds , 1986 .

[31]  A. M. Glazer,et al.  A nitrogen‐gas‐stream cryostat for general X‐ray diffraction studies , 1986 .

[32]  B. Figgis,et al.  Crystal structure of bis(2,2':6',2''-terpyridyl) cobalt-(II) perchlorate c-1,3 hydrate , 1983 .

[33]  B. Figgis,et al.  Crystal structure of bis(2,2':6',2''-terpyridyl) cobalt (II) iodide dihydrate at 295 K and at 120 K , 1983 .

[34]  M. C. Hughes,et al.  Dual role of para-phenyl substituents in aromatic imine ligand complexes of cobalt and iron , 1980 .

[35]  J. Demas,et al.  Measurement of photoluminescence quantum yields. Review , 1971 .