Synthesis and Characterization of Three New Emissive Mononuclear CuI Heteroleptic Complexes with Functionalized 6-Cyano-2,2′-bipyridine Chelating Ligands

2020 ◽  
Vol 73 (7) ◽  
pp. 640
Author(s):  
Wan-Man Wang ◽  
Peng Ju ◽  
Man-Hong Jing ◽  
Ping Yu ◽  
Qin Huang

A new series of luminescent mononuclear CuI complexes with functionalized 6-cyano-2,2′-bipyridine chelating ligands, [Cu(xantphos)(cbpy)]ClO4 (1), [Cu(xantphos)(4,4’-Me2cbpy)]ClO4·CH2Cl2·H2O (2), and [Cu(POP)(cbpy)]ClO4·CH2Cl2 (3) (xantphos=4,5-bis(diphenylphosphino)-9,9-dimethylxanthene; POP=bis(2-diphenylphosphinophenyl)ether; 4,4’-Me2cbpy=4,4’-dimethyl-6-cyano-2,2′-bipyridine; cbpy=6-cyano-2,2′-bipyridine) have been successfully prepared, and their structures and photophysical properties are investigated. Single crystal structures of the three complexes reveal a distorted tetrahedral coordination geometry around the CuI centres with the P atoms of diphosphane ligands and N donors of 2,2′-bipyridine ring. Luminescence measurements indicate that these CuI complexes display good emission properties both in the solution and solid states at room temperature, which can be well modulated through modifying the structure of 6-cyano-2,2′-bipyridine. It is shown that the introduction of two electron-donating methyl groups at the 4,4’-positions of the 6-cyano-2,2′-bipyridine is favourable to enhance the luminescence properties of the CuI complexes.

2007 ◽  
Vol 63 (3) ◽  
pp. m800-m802 ◽  
Author(s):  
William T. Eckenhoff ◽  
Tomislav Pintauer

In the title compound, [Cu(C14H12N2)2]C24H20B·CH2Cl2, CuI is chelated by two 2,9-dimethyl-1,10-phenanthroline (2,9-Me2phen) ligands, in a distorted tetrahedral coordination geometry. The average Cu—N bond length is 2.032 Å, and the interligand dihedral angle is 77.60 (6)°. The complexes form π–π stacking interactions between 2,9-Me2phen ligands, with a perpendicular interplanar separation of 3.652 (5) Å.


2014 ◽  
Vol 70 (5) ◽  
pp. m184-m184
Author(s):  
Xiao-Juan Wang ◽  
Yun-Long Feng

The title hydrated complex, [Zn2Cl4(C9H12N4)2]·2H2O, is a discrete dinuclear zinc complex with 1,3-bis(1H-imidazol-1-yl)propane as the bridging ligand. The complex molecule lies about a crystallographic inversion centre. The ZnIIatom exhibits a distorted tetrahedral coordination geometry defined by two imidazole N atoms and two Cl atoms. O—H...Cl hydrogen bonding between the lattice water molecules and the terminal Cl atoms of the molecule lead to a two-dimensional structure extending parallel to (100).


2013 ◽  
Vol 69 (9) ◽  
pp. 1017-1021
Author(s):  
Liu-cheng Gui ◽  
Guang-ming Liang ◽  
Hua-hong Zou ◽  
Zhong Hou

The title complexes, poly[[bis[μ2-2-ethyl-1-(pyridin-3-ylmethyl)-1H-benzimidazole-κ2N1:N3]copper(I)] tetrafluoroborate acetonitrile monosolvate], {[Cu(C15H15N3)2]BF4·CH3CN}n, (I), and poly[[bis[μ2-2-ethyl-1-(pyridin-3-ylmethyl)-1H-benzimidazole-κ2N1:N3]silver(I)] perchlorate methanol monosolvate], {[Ag(C15H15N3)2]ClO4·CH3OH}n, (II), are isostructural and exhibit one-dimensional ladder-like structures in which each asymmetric unit contains one metal ion (Cu+or Ag+), two 2-ethyl-1-(pyridin-3-ylmethyl)-1H-benzimidazole (bep) ligands, one counter-anion (tetrafluoroborate or perchlorate) and one interstitial molecule (acetonitrile or methanol). Each metal ion exhibits a distorted tetrahedral coordination geometry consisting of two pyridyl and two benzimidazole N atoms from four distinct ligands. Two metal ions are linked by two bep ligands to form a centrosymmetric 18-memberedM2(bep)2metallacycle, while adjacentM2(bep)2metallacycles are further interlinked by another two bep ligands resulting in a ladder-like array. In the extended structure, four adjacent ladder-like arrays are connected together through C—H...F, O—H...O and C—H...O hydrogen bonds between bep ligands, solvent molecules and counter-anions into a three-dimensional supramolecular structure.


1979 ◽  
Vol 57 (14) ◽  
pp. 1823-1825 ◽  
Author(s):  
Steven J. Rettig ◽  
Alan Storr ◽  
James Trotter

Crystals of bis[methyltris(1-pyrazolyl)gallato]nickel(II) are rhombohedral, a = 9.6670(5), c = 23.893(1) Å, Z = 3, space group [Formula: see text]. The structure was solved by direct methods and was refined by full-matrix least-squares procedures to a final R of 0.030 and Rw = 0.035 for 925 reflections with I ≥ 3σ (I). The crystal structure consists of well separated molecules of [MeGa-(N2C3H3)3]2Ni having exact [Formula: see text] (S6) symmetry and approximate D3d symmetry. The coordination geometry about the nickel atom is octahedral with Ni—N = 2.109(2) Å, N—Ni—N = 90.65(6) and 89.35(6)°. The gallium atom has distorted tetrahedral coordination geometry with Ga—N = 1.939(2), Ga—C = 1.940(4) Å, N—Ga—N = 99.55(6), and N—Ga—C = 118.16(5)°.


2000 ◽  
Vol 57 (1) ◽  
pp. m25-m27 ◽  
Author(s):  
Miao Du ◽  
Xian-He Bu ◽  
Lin-Hong Weng ◽  
Xue-Bing Leng ◽  
Ya-Mei Guo

In the crystal structure of the title complex, [Cu(C10H9N3)2](ClO4)2, the CuIIcenter is four-coordinated by the nitrogen donors of the pyridine rings of the ligand, bis(2-pyridyl)amine. The crystal structure reveals that the CuN4coordination sphere has a distorted tetrahedral coordination geometry with a crystallographicC2axis through the CuIIcenter. The perchlorate anions link the complex cations to form a chain structure through C—H...O close contacts and N—H...O hydrogen bonds.


2007 ◽  
Vol 63 (11) ◽  
pp. m2707-m2707 ◽  
Author(s):  
Hai-Yan Liu ◽  
Ji-Cheng Ma ◽  
Jin Yang

In the title compound, [Ag(C6H6NO3S)(C8H8N2)], the AgI cation is four-coordinated by three N atoms from two different 2,3-diethylpyrazine ligands and one –NH2 group of a 4-aminobenzenesulfonate ligand, and one sulfonate O atom in a distorted tetrahedral coordination geometry. The AgI centers are doubly bridged by both types of ligands, forming a one-dimensional chain. N—H...O hydrogen bonds complete the structure.


2015 ◽  
Vol 71 (6) ◽  
pp. m133-m134 ◽  
Author(s):  
Arunpatcha Nimthong-Roldán ◽  
Janejira Ratthiwal ◽  
Yupa Wattanakanjana

In the dinuclear title complex, [Ag2Cl2(C7H8N2S)(C25H22P2)2]·0.5CH3CN, each AgIion displays a distorted tetrahedral coordination geometry with two P atoms from two bis(diphenylphosphanyl)methane (dppm) ligands, one bridging chloride ion, one terminal chloride ion and one terminal S atom from theN,N′-phenylthiourea (ptu) ligand. The dppm ligands and the bridging chloride ion force the two Ag atoms into close proximity, with a short Ag...Ag separation of 3.2064 (2) Å. In the crystal, complex molecules are linked by N—H...Cl hydrogen bonds forming a dimer. The dimers are linkedviaweak C— H...Cl hydrogen bonds forming a two-dimensional supramolecular architecture in theyzplane. In addition, an intramolecular N—H...Cl hydrogen bond is observed.


1979 ◽  
Vol 57 (23) ◽  
pp. 3099-3106 ◽  
Author(s):  
Kenneth S. Chong ◽  
Steven J. Rettig ◽  
Alan Storr ◽  
James Trotter

A series of anionic pyrazolyl-bridged nickel nitrosyl complexes, M+[(ON)Ni(μ-L2)(μ-X)Ni(NO)]− (where L = pyrazolyl, N2C3H3, or 3,5-dimethylpyrazolyl, N2C5H7; X = Cl, Br, I, or N2C5H7; and M = Na, (CH3)4N, or (C2H5)4N) is described. Crystallographic analyses have been carried out on two of these complexes. Crystals of [(C2H5)4N]+[(ON)Ni(μ-I)(μ- N2C5H7)2Ni(NO)]− are orthorhombic, a = 19.910(1), b = 14.0330(7), c = 9.3195(9) Å, Z = 4, space group Pn21a and crystals of [(C4H8O)2Na][(ON)Ni(μ-N2C5 H7)3Ni(NO)] are orthorhombic, a = 19.897(2), b = 19.529(3), c = 15.894(2) Å, Z = 8, space group Pbca. Both structures were solved by Patterson and Fourier syntheses and were refined by full-matrix least-squares procedures to R = 0.027 and 0.057 for 2572 and 2168 reflections with I ≥ 3σ(I) respectively. The structure of [(C2H5)4N]+[(ON)Ni(μ-I)(μ-N2C5H7)2Ni(NO)]− consists of discrete cations and binuclear anions which have approximate C2v symmetry. The nickel atoms have distorted tetrahedral coordination geometry. Important mean molecular dimensions (distances corrected for libration) are: Ni—I—Ni, 73.67(2)°, Ni—I, 2.765(3), Ni—NO, 1.649(5), Ni—N(pyrazolyl), 1.980(14) Å, and Ni—N—O, 172.5(18)°. The structure of [(C4H8O)2Na][(ON)Ni(μ-N2C5 H7)3Ni(NO)] consists of discrete ion-pair units in which the two NiNO moieties are bridged by three N2C5H7 ligands, two of which are coordinated to the sodium ion via a novel η2(N,N) π-interaction (mean Na—N = 2.61(3) Å). The sodium is also coordinated to two tetrahydrofuran oxygen atoms to give a distorted tetrahedral coordination geometry about the sodium (Na—O = 2.301(6) and 2.266(5) Å). Except for disordered tetrahydrofuran carbon atoms, the molecular unit has approximate C2v symmetry. The nickel atoms have distorted tetrahedral coordination geometry, the mean distances being Ni—NO, 1.591(6), Ni—N(pyrazolyl), 1.985(2) for the unique pyrazolyl group and 2.016(5) Å for the pyrazolyl nitrogen atoms coordinated to Na. The mean Ni—N—O angle is 176.9(11)°.


2008 ◽  
Vol 6 (4) ◽  
pp. 613-616 ◽  
Author(s):  
Zu-Fu Yao ◽  
Xin Gan ◽  
Wen-Fu Fu

AbstractA novel triply bridged dinuclear copper(I) complex: Cu2(μ-paa)(μ-dcpm)2(BF4)2·2CH2Cl2 [ paa = pyridine-2-carbaldehyde azine (C12H10N4) and dcpm = bis(dicyclohexylphosphino)methane(C25H46P2) ] has been synthesized and structurally characterized. Crystallographic studies of the complex showed that two copper(I) ions were bridged by one paa ligand and two dcpm ligands. The paa ligand adopted the Z configuration at the partially double N-N bond and the two copper ions have distorted tetrahedral coordination geometry. Because of the steric effect of dcpm, the pyridine rings of the paa ligand are obviously not on the same plane (the dihedral angle is 43.610). The interaction between neighboring ligands results in a N-N bond length (1.374(7) Å) contraction. The UV-vis spectra of the complex exhibited intense high-energy absorptions at λmax


Author(s):  
Peter W. R. Corfield ◽  
Uwe Seeler

In the title compound, [Cu(C4H12P2S2)2]BF4, both diphosphine disulfide molecules bind to the CuIatom, as chelating ligandsviathe S atoms, forming a monovalent cation with a slightly distorted tetrahedral coordination around the CuIatom. The average Cu—S distance is 2.350 (15) Å, with small but possibly significant differences within each chelate ring. Ligand P=S distances average 1.964 (3) Å, and the P—P distances are 2.2262 (13) and 2.2166 (14) Å. The ligand chelate rings are twisted in opposite directions, with one in the λ and one in the δ configuration. Although the anisotropic displacement parameters of the F atoms of the anion are quite large compared to that of the B atom, difference Fourier syntheses indicate only one set of sites for the F atoms. In the crystal, possible C—H...F hydrogen bonds may stabilize the orientation. The B—F distances, uncorrected for libration, average 1.359 (6) Å.


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