A new semiconducting 1D Cu(<scp>i</scp>)–Cu(<scp>ii</scp>) mixed-valence coordination polymer with Cu(<scp>ii</scp>) dimethylpiperidine–dithiocarbamate and a tetranuclear Cu(<scp>i</scp>)–Br cluster unit

Himoto, Kento; Suzuki, Shimpei; Okubo, Takashi; Maekawa, Masahiko; Kuroda–Sowa, Takayoshi

doi:10.1039/c7nj04763k

Cited by 13 publications

(7 citation statements)

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“…There Following this initial report, over the past 15 years, Okubo and co-workers have prepared a range of Cu(I)-Cu(II) coordination polymers [134][135][136][137][138][139][140][141][142][143]. Their synthetic strategy is to react [Cu(S 2 CNR 2 ) 2 ] with [CuBr(SMe 2 )] in mixed organic solvents, with crystals forming upon concentration of the filtrate.…”

Section: Mixed-valence Copper Dithiocarbamate Complexesmentioning

confidence: 99%

“…They were first reported in the 1970s upon oxidation of Cu(II) bis(dithiocarbamate) complexes with halides or metal salts [145][146][147] Mixed-valence Cu(I)-Cu(II) dithiocarbamate coordination polymers have interesting physical properties, primarily stemming from their relatively small band gap, which results from the HOMOs of their various components. For example, while the band gap in [Cu(S 2 CN-2,6-Me 2 C 5 H 8 ) 2 ] is 1.30 eV, the coordination polymer generated upon the addition of [CuBr(SMe 2 )] has a band gap of only 1.04 eV [143] and exhibits semi-conducting behaviour. The estimated bulk conductivity at 300 K of 1.4 × 10 −8 S cm −1 is similar to those with other dithiocarbamate ligands, which can be as high as 5.2 × 10 −7 S cm −1 [134].…”

Section: Mixed-valence Copper Dithiocarbamate Complexesmentioning

confidence: 99%

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Copper Dithiocarbamates: Coordination Chemistry and Applications in Materials Science, Biosciences and Beyond

Hogarth

Onwudiwe

2021

Inorganics

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Copper dithiocarbamate complexes have been known for ca. 120 years and find relevance in biology and medicine, especially as anticancer agents and applications in materials science as a single-source precursor (SSPs) to nanoscale copper sulfides. Dithiocarbamates support Cu(I), Cu(II) and Cu(III) and show a rich and diverse coordination chemistry. Homoleptic [Cu(S2CNR2)2] are most common, being known for hundreds of substituents. All contain a Cu(II) centre, being either monomeric (distorted square planar) or dimeric (distorted trigonal bipyramidal) in the solid state, the latter being held together by intermolecular C···S interactions. Their d9 electronic configuration renders them paramagnetic and thus readily detected by electron paramagnetic resonance (EPR) spectroscopy. Reaction with a range of oxidants affords d8 Cu(III) complexes, [Cu(S2CNR2)2][X], in which copper remains in a square-planar geometry, but Cu–S bonds shorten by ca. 0.1 Å. These show a wide range of different structural motifs in the solid-state, varying with changes in anion and dithiocarbamate substituents. Cu(I) complexes, [Cu(S2CNR2)2]−, are (briefly) accessible in an electrochemical cell, and the only stable example is recently reported [Cu(S2CNH2)2][NH4]·H2O. Others readily lose a dithiocarbamate and the d10 centres can either be trapped with other coordinating ligands, especially phosphines, or form clusters with tetrahedral [Cu(μ3-S2CNR2)]4 being most common. Over the past decade, a wide range of Cu(I) dithiocarbamate clusters have been prepared and structurally characterised with nuclearities of 3–28, especially exciting being those with interstitial hydride and/or acetylide co-ligands. A range of mixed-valence Cu(I)–Cu(II) and Cu(II)–Cu(III) complexes are known, many of which show novel physical properties, and one Cu(I)–Cu(II)–Cu(III) species has been reported. Copper dithiocarbamates have been widely used as SSPs to nanoscale copper sulfides, allowing control over the phase, particle size and morphology of nanomaterials, and thus giving access to materials with tuneable physical properties. The identification of copper in a range of neurological diseases and the use of disulfiram as a drug for over 50 years makes understanding of the biological formation and action of [Cu(S2CNEt2)2] especially important. Furthermore, the finding that it and related Cu(II) dithiocarbamates are active anticancer agents has pushed them to the fore in studies of metal-based biomedicines.

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Section: Mixed-valence Copper Dithiocarbamate Complexesmentioning

confidence: 99%

Section: Mixed-valence Copper Dithiocarbamate Complexesmentioning

confidence: 99%

Copper Dithiocarbamates: Coordination Chemistry and Applications in Materials Science, Biosciences and Beyond

Hogarth

Onwudiwe

2021

Inorganics

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“…This type of mixed-valence complex is more interesting than those of Fe or Co because the copper (I) and copper (II) metal centers prefer different geometries and the two oxidation states are very labile and stereo chemically flexible [39,40]. On the other hand, the chemistry of mixed-valence Cu II /Cu I coordination complexes are gaining popularity due to its great applications in various fields like as biological activity [41,42], electronic properties [43,44] and electrical conductivity [45,46]. Although, a first attempt in this context, only a monometallic complex of formula [CuL2(SCN)2] was isolated [30], we present here the synthesis and characterization of the first mixed-valence coordination polymer, [Cu I 3Cu II L2(SCN)5]n, based on L as ligand and thiocyanate as coligand, after a small modification of the preparation method.…”

Section: Introductionmentioning

confidence: 99%

Unusual mixed-valence CuII/CuI coordination polymer based on 2,5-bis(pyridine-2-yl)-1,3,4-thiadiazole and thiocyanate: Synthesis, structural characterization and antimicrobial in vitro activity assessment

et al. 2021

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“…Hiroshi Kitagawa group has synthesized a porous coordination polymer by introducing electron donors and acceptors as building units, which showed high electrical conductivity (6 × 10 –4 S cm –1 ) . Himoto et al have synthesized several semiconducting CP using mixed valance metal ions and dithiocarbamate ligands . Banerjee and coworkers have reported first proton conducting CP based on polyoxometalate and achieved a conductivity of 2.2 × 10 –5 S cm –1 …”

Section: Introductionmentioning

confidence: 99%

Increased Photocatalytic Activity of Post Synthetically Modified Coordination Polymer Derived from Bis‐pyridyldiamide

2020

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A one‐dimensional looped chain coordination polymer (CP1) is synthesized by the reaction of CoII with N1,N3‐di(pyridine‐4‐yl)isophthalamide. Transmetalation reaction of CP1 with CuII showed single‐crystal‐to‐single‐crystal (SC‐SC) transformation to form CP2, which is also a 1D looped chain. Both CP1 and CP2 showed the presence of DMF as guest molecules near the loops of the 1D chains. CP1 and CP2 were found to have bandgap of 2.41 eV and 1.30 eV, respectively, which were calculated by Tauc plot. The difference observed in the optical bandgap of CP1 and CP2 is reflected in photocatalytic dye degradation studies. It was observed that CP2 showed much greater efficiency in degrading the dyes (Methylene blue, Methyl orange and Rhodamine B) as compared to that of CP1. The polar nature of the loops of the chains in CP1 and CP2 due to the presence of DMF was exploited to study the adsorption and desorption of I2. Adsorption of I2 in CP1 and CP2 was found to follow first order kinetics with a rate constant of 8.32 × 10–5 s–1 for CP1 and 9.71 × 10–5 s–1 for CP2. Guest inclusion reaction was performed to incorporate benzotriazole in the CP1. Impedance measurements showed a higher conductivity in the benzotriazole incorporated CP1.

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A new semiconducting 1D Cu(i)–Cu(ii) mixed-valence coordination polymer with Cu(ii) dimethylpiperidine–dithiocarbamate and a tetranuclear Cu(i)–Br cluster unit

Abstract: A new 1D semiconducting mixed-valence Cu(i)–Cu(ii) coordination polymer was synthesized and characterized using impedance measurements.

Cited by 13 publications

References 53 publications

Copper Dithiocarbamates: Coordination Chemistry and Applications in Materials Science, Biosciences and Beyond

Copper Dithiocarbamates: Coordination Chemistry and Applications in Materials Science, Biosciences and Beyond

Unusual mixed-valence CuII/CuI coordination polymer based on 2,5-bis(pyridine-2-yl)-1,3,4-thiadiazole and thiocyanate: Synthesis, structural characterization and antimicrobial in vitro activity assessment

Increased Photocatalytic Activity of Post Synthetically Modified Coordination Polymer Derived from Bis‐pyridyldiamide

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