Copper(I) oligomers and polymers with dicyanobenzene and cyanopyridine ligands
Autor: | Daniel May, Mark K. Broderick, Robert D. Pike, Aaron D. Nicholas, Howard H. Patterson, Congqi Yang |
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Rok vydání: | 2016 |
Předmět: |
Ligand
Dimer chemistry.chemical_element Trimer 02 engineering and technology Crystal structure 010402 general chemistry 021001 nanoscience & nanotechnology Photochemistry 01 natural sciences Toluene Copper 0104 chemical sciences law.invention Inorganic Chemistry Solvent chemistry.chemical_compound Crystallography chemistry law Materials Chemistry Physical and Theoretical Chemistry Crystallization 0210 nano-technology |
Zdroj: | Polyhedron. 114:333-343 |
ISSN: | 0277-5387 |
Popis: | The reaction of [Cu(MeCN)4]BF4 with o-, m-, or p-dicyanobenzene (DCB) or o-, m-, or p-cyanopyridine (CPy) in the presence of two equivalents of PPh3 produces DCB- or CPy-bridged copper(I) complexes. Cyclic dimers are formed for the ortho ligands, and zigzag polymers are formed using the para ligands. m-DCB produces a polymer, however m-CPy results in a cyclic trimer. Multiple lattice-bound solvates are formed upon crystallization of the o-DCB dimer from various solvents. A total of 11 X-ray crystal structures are reported for [Cun(PPh3)2n(bridge)n](BF4)n·(solvent): bridge = o-DCB, n = 2, solvent (per dimer) = none, ½ CH2Cl2, CH2Cl2, 2 CHCl3/H2O, or 2 THF; bridge = m-DCB, n = ∞, solvent = none; bridge = p-DCB, n = ∞, solvent = CH2Cl2 (two polymorphs), bridge = o-CPy, n = 2, solvent (per dimer) = 2 toluene; bridge = m-CPy, n = 3, solvent = none; bridge = p-CPy, n = ∞, solvent = ½ acetone. All complexes are photoluminescent with excitation in the range 340–400 nm. The meta complexes emit in the blue region, while the other complexes emit in the green. Dimer complexes of o-DCB exhibit structural flexibility in the central macrocyclic ring. Complexes of m-DCB and p-CPy show orientational disorder in the ligand. Polymeric complexes show helicity. Smaller Stokes shifts are noted for DCB than for CPy complexes, suggesting less excited state distortion for cyanoaromatic ligand complexes of Cu(I). |
Databáze: | OpenAIRE |
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