C–C bond cleavage in acetonitrile by copper(ii)–bipyridine complexes and in situ formation of cyano-bridged mixed-valent copper complexes

Tao, Tao; Zhang, Kun; Wang, Xiaoxu; Huang, Wei; You, Xiao‐Zeng

doi:10.1039/c2dt32281a

Cited by 39 publications

(16 citation statements)

References 62 publications

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“…The flexibility of the [Cu(phen) 2 ] + complexes has been observed in the crystalline state, depending on the substitution and the crystal packing. Dihedral angles between the ligands are 87° in [Cu I (2,9-dibutylphen) 2 ](ClO 4 ), but flattens to 46° [Cu I (phen) 2 ](PF 6 ), 17 presumably due to intermolecular π-stacking interactions.…”

Section: Introductionmentioning

confidence: 99%

Design of Bis(1,10-phenanthroline) Copper(I)-Based Mechanochromic Indicators

et al. 2022

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In the growing field of single-molecule mechanochromism, the potential of transition metal complexes is yet to be examined. In this work, we have synthesized a series of [Cu(phen) 2 ] + complexes: bis-Cu(I)-phenanthroline, bis-Cu(I)-phenanthroline-2-amine, and bis-Cu(I)-phenanthroline-2-acetamide. After that, we characterized the complexes by UV–vis spectroscopy and employed density functional theory (DFT) calculations to investigate the changes in UV–vis upon mechanical pulling via force calculations. The results of our examination of time-dependent (TD)-DFT-calculated UV–vis suggests that the bis-Cu(I)-phenanthroline-2-acetamide complex is predicted to have an observable shift of the metal-to-ligand charge transfer band upon pulling from 0 to 0.6 nN in the visible region. We have demonstrated the ability to synthesize and characterize bis-Cu(I)-phenanthroline-2-acetamide. In addition, the TD-DFT calculations predict an observable shift in the visible region of the UV–vis spectrum. This indicates that transition metal complexes are feasible candidates as mechanophores and are worthy of further exploration as to their potential role in a new subclass of mechanochromic indicators.

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Section: Introductionmentioning

confidence: 99%

Design of Bis(1,10-phenanthroline) Copper(I)-Based Mechanochromic Indicators

et al. 2022

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“…23 The Cu-N bond distances are 1.9999 18and 2.0189(18) Å and are similar to the corresponding distances found in previously reported dinuclear copper-bipyridine complexes. 24 Cu-O distances of the complex are quite asymmetrical. The Cu-O bond distances in the equatorial plane are 1.9441(16) and 1.9800(15) Å which are typical of the Cu-O equatorial distances of the previously reported dimeric 25 and polymeric 26,27 complexes.…”

Section: Structural Description Of the Complexmentioning

confidence: 90%

Dinuclear Ternary Copper(II) Complex: Synthesis, Characterization, Structure and DNA-Binding Studies

Iqbal

Mushtaq

Ali

et al. 2018

ACSi

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A dinuclear centrosymmetric copper(II) complex has been prepared and characterized via FT-IR, UV-Visible and electron spin resonance spectroscopy, electrochemical method, and powder and single crystal XRD techniques. The two copper(II) ions are connected by two μ-1,1-O atoms belonging to para-fluorophenyl acetate ligands. Each copper(II) ion is coordinated by two other carboxylate ligands in monodentate and a 2,2ʹ-bipyridine molecule in bidentate manner. Thus the geometry around each penta-coordinated copper(II) ion is square pyramidal with distortion factor τ = 0.04. Purity and uniform crystalline nature of the complex was assessed from powder XRD spectrum. ESR signal consisted of partially resolved hyperfine splitting pattern while electrochemical studies revealed diffusion controlled electron transfer processes with diffusion coefficient of 1.628 × 10-7 cm 2 s-1. The results of all spectroscopic experiments support each other. The complex afforded mixed binding mode with DNA yielding DNA-binding constant values of 3.667 × 10 4 and 1.438 × 10 4 M-1 using cyclic voltammetry and absorption spectroscopy, respectively. The preliminary studies heralded good structural and biological importance of the synthesized complex.

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“…These flexible ligands can meet the coordination requirements of metal centers by their torsionally flexible -(CH 2 ) n -backbones and facilitation of supramolecular interactions. The suitable choice of N-containing ligands could lead to help active copper(II) coordination centers with enhanced reducing capacity, which could promote the cleavage of the C-CN bond of acetonitrile to give cyanide anions [14,15]. Furthermore, when searching the Cambridge Structural Database (version 5.37, May 2015) [16] for Cu(I) MOCPs constructed from bis(triazole) and bis(benzimidazole) ligands, very few related crystal structures were found.…”

Section: Introductionmentioning

confidence: 97%

In situ construction of four copper(I) cyanide coordination polymers: crystal structures, fluorescence and catalytic properties

Zhang

Dong

et al. 2015

Transition Met Chem

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Four Cu(I) cyanide coordination polymers, namely [Cu(L1)(CN)] n (1), [Cu 2 (L2)(CN) 2 ] n (2), [Cu 2 (L3)-(CN) 2 ] n (3) and [Cu 2 (L4)(CN) 2 ] n (4) (L1 = 4,4 0 -bis(1,2,4-triazolyl-1-yl)-biphenyl, L2 = 1,4-bis(5,6-dimethylbenzimidazole)butane, L3 = 1,3-bis(2-methylbenzimidazole)propane, L4 = 1,5-bis(5,6-dimethylbenzimidazole)pentane), were synthesized and structurally characterized by X-ray singlecrystal diffraction. The cyanide anions in these complexes were generated in situ by cleavage of the C-C bond of acetonitrile under hydrothermal conditions. Complex 1 possesses a 1D infinite ladder-like chain structure, while complexes 2, 3 and 4 exhibit similar 2D (6,3) networks. Both 3 and 4 are further extended into 3D supramolecular frameworks by C-HÁÁÁp stacking interactions. The fluorescence properties of the complexes and their catalytic activities for the degradation of Congo red azo dye in a Fentonlike process were investigated.

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C–C bond cleavage in acetonitrile by copper(ii)–bipyridine complexes and in situ formation of cyano-bridged mixed-valent copper complexes

Cited by 39 publications

References 62 publications

Design of Bis(1,10-phenanthroline) Copper(I)-Based Mechanochromic Indicators

Design of Bis(1,10-phenanthroline) Copper(I)-Based Mechanochromic Indicators

Dinuclear Ternary Copper(II) Complex: Synthesis, Characterization, Structure and DNA-Binding Studies

In situ construction of four copper(I) cyanide coordination polymers: crystal structures, fluorescence and catalytic properties

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