Synthesis, Crystal Structure, and Electroconducting Properties of a 1D Mixed-Valence Cu(I)–Cu(II) Coordination Polymer with a Dicyclohexyl Dithiocarbamate Ligand

Nakatani, Kazuki; Himoto, Kento; Kono, Yoshio; Nakahashi, Yuuki; Anma, Haruho; Okubo, Takashi; Maekawa, Masahiko; Kuroda–Sowa, Takayoshi

doi:10.3390/cryst5020215

Cited by 8 publications

(4 citation statements)

References 44 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…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%

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

Hogarth

Onwudiwe

2021

Inorganics

View full text Add to dashboard Cite

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.

show abstract

Section: Mixed-valence Copper Dithiocarbamate Complexesmentioning

confidence: 99%

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

Hogarth

Onwudiwe

2021

Inorganics

View full text Add to dashboard Cite

show abstract

“…The higher annealing temperature resulted in a larger size for the red-shift of the absorption edge of the TC composite samples; this was associated with the fact that the CuO formed at the higher annealing temperature had a narrower band-gap energy than that of Cu 2 O [ 40 , 41 ]. Figure 8 b shows the Kubelka–Munk function (F(R)) vs. energy plots for various nanorod samples [ 42 ]. Notably, the TiO 2 and copper oxides used herein were expected to exhibit a direct transition in the band-gap measurements.…”

Section: Resultsmentioning

confidence: 99%

Sputtering-Assisted Synthesis of Copper Oxide–Titanium Oxide Nanorods and Their Photoactive Performances

Liang

2022

Nanomaterials

View full text Add to dashboard Cite

A TiO2 nanorod template was successfully decorated with a copper oxide layer with various crystallographic phases using sputtering and postannealing procedures. The crystallographic phase of the layer attached to the TiO2 was adjusted from a single Cu2O phase or dual Cu2O–CuO phase to a single CuO phase by changing the postannealing temperature from 200 °C to 400 °C. The decoration of the TiO2 (TC) with a copper oxide layer improved the light absorption and photoinduced charge separation abilities. These factors resulted in the composite nanorods demonstrating enhanced photoactivity compared to that of the pristine TiO2. The ternary phase composition of TC350 allowed it to achieve superior photoactive performance compared to the other composite nanorods. The possible Z-scheme carrier movement mechanism and the larger granular size of the attached layer of TC350 under irradiation accounted for the superior photocatalytic activity in the degradation of RhB dyes.

show abstract

“…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

View full text Add to dashboard Cite

Synthesis, Crystal Structure, and Electroconducting Properties of a 1D Mixed-Valence Cu(I)–Cu(II) Coordination Polymer with a Dicyclohexyl Dithiocarbamate Ligand

Cited by 8 publications

References 44 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

Sputtering-Assisted Synthesis of Copper Oxide–Titanium Oxide Nanorods and Their Photoactive Performances

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

Contact Info

Product

Resources

About