Copper(II) Halide Complexes with 1‐tert‐Butyl‐1H‐1,2,4‐triazole and 1‐tert‐Butyl‐1H‐tetrazole

1‐tert‐Butyl‐1H‐1,2,4‐triazole (tbtr) was found to react with copper(II) chloride or bromide to give the complexes [Cu(tbtr)₂X₂]_n and [Cu(tbtr)₄X₂] (X = Cl, Br). 1‐tert‐Butyl‐1H‐tetrazole (tbtt) reacts with copper(II) bromide resulting in the formation of the complex [Cu₃(tbtt)₆Br₆]. The obtained crystalline complexes as well as free ligand tbtr were characterized by elemental analysis, IR spectroscopy, thermal and X‐ray analyses. For free ligand tbtr, ¹H NMR and ¹³C NMR spectra were also recorded. In all the complexes, tbtr and tbtt act as monodentate ligands coordinated by Cu^II cations via the heteroring N⁴ atoms. The triazole complexes [Cu(tbtr)₂Cl₂]_n and [Cu(tbtr)₂Br₂]_n are isotypic, being 1D coordination polymers, formed at the expense of single halide bridges between neighboring copper(II) cations. The isotypic complexes [Cu(tbtr)₄Cl₂] and [Cu(tbtr)₄Br₂] reveal mononuclear centrosymmetric structure, with octahedral coordination of Cu^II cations. The tetrazole compound [Cu₃(tbtt)₆Br₆] is a linear trinuclear complex, in which neighboring copper(II) cations are linked by single bromide bridges.     

Synthesen und Kristallstrukturen neuer chalkogenido‐verbrückter Niob‐Kupfer‐Cluster

Syntheses and Crystal Structures of Novel Chalcogenido‐bridged Niobium Copper Clusters In the presence of tertiary phosphines, the reaction of NbCl₅ and Copper(I) salts with Se(SiMe₃)₂ (E = S, Se) affords the new chalcogenido‐bridged niobium‐copper cluster compounds ( 1 ) and [NbCu₄Se₄Cl (PPh₃)₄] ( 2 ). Using E(R)SiMe₃ (E = S, Se, R = Ph, ⁿPr) instead of the bisilylated selenium species leads to the compounds [NbCu₂(SPh)₆(PMe₃)₂] ( 3 ), [NbCu₂(SPh)₆(PⁿPr₃)₂] ( 4 ), [NbCu₂(SePh)₆(PMe₃)₂] ( 5 ), [NbCu₂(SePh)₆(PⁿPr₃)₂] ( 6 ), [NbCu₂(SePh)₆(PⁱPr₃)₂] ( 7 ), [NbCu₂(SePh)₆(P^tBu₃)₂] ( 8 ), [NbCu₂(SePh)₆(PⁱPr₂Me)₂] ( 9 ), [NbCu₂(SePh)₆(PPhEt₂)₂] ( 10 ), [Nb₂Cu₂(SⁿPr)₈(PⁿPr₃)₂Cl₂] ( 11 ) and [Nb₂Cu₆(SⁿPr)₁₂(PⁱPr₃)₂Cl₄]·2 CH₃CN ( 12 ·2 CH₃CN). By reacting Cu^I salts and NbCl₅ with the monosilylated selenides Se(^tBu)SiMe₃ and Se(ⁱPr)SiMe₃ which have a weak Se–C bond the products [Nb₂Cu₆Se₆(PⁱPr₃)₆Cl₄] ( 13 ), [Nb₂Cu₄Se₂(SeⁱPr)₆(PⁿPr₃)₄Cl₂] ( 14 ) and [Nb₂Cu₆Se₂(SeⁱPr)₁₀(PEt₂Me)₂Cl₂]·DME ( 15 ) are formed which contain selenide as well as alkylselenolate ligands. The molecular structures of all of these new compounds were determined by single crystal X‐ray diffraction measurements.     

Zur Reaktion der Alkin‐Kupfer(I)‐Komplexe [CuCl(S‐Alkin)] und [Cu2Br2(S‐Alkin)(dms)] (S‐Alkin = 3,3,6,6‐Tetramethyl‐1‐thia‐4‐cycloheptin,dms = Dimethylsulfid) mit den Lithiumorganylen Phenyllithium und Fluorenyllithium

Organometallic Compounds of Copper. XX On the Reaction of the Alkyne Copper(I) Complexes [CuCl(S‐Alkyne)] and [Cu₂Br₂(S‐Alkyne)(dms)] (S‐Alkyne = 3,3,6,6‐Tetramethyl‐1‐thiacyclohept‐4‐yne; dms = Dimethylsulfide) with the Lithiumorganyls Phenyllithium und Fluorenyllithium The alkyne copper(I) bromide complex [Cu₂Br₂(S‐Alkyne)(dms)] ( 3 b ) (S‐Alkyne = 3,3,6,6‐tetramethyl‐1‐thiacyclohept‐4‐yne; dms = dimethylsulfide) reacts with phenyllithium to form a tetranuclear copper(I) complex of the composition [Cu₄(C₆H₅)₂(S‐Alkenyl)₂] ( 7 ) in low yield (4%). The reaction of the alkyne copper(I) chloride complex [CuCl(S‐Alkyne)] ( 2 a ) with fluorenyllithium in tetrahydrofuran (thf) affords a lithium cuprate of the composition [Li(thf)₄]⁺ [Cu₂(fluorenyl)₃(S‐Alkyne)₂]^– ( 8 ) (yield 32%). The structures of both new complexes 7 and 8 were determined by X–ray diffraction.     

Synthesen und Kristallstrukturen neuer heterobimetallischer Tantal‐Münzmetall‐Chalkogenido‐Cluster

Syntheses and Crystal Structures of Novel Heterobimetallic Tantalum Coin Metal Chalcogenido Clusters In the presence of phosphine the thiotantalats (Et₄N)₄[Ta₆S₁₇] · 3MeCN reacts with copper to give a number of new heterobimetallic tantalum copper chalcogenide clusters. These clusters show metal chalcogenide units some of which here already known from the chemistry of vanadium and niobium. New Ta—M‐chalcogenide clusters could also be synthesised by reaction of TaCl₅ and silylated chalcogen reagents with copper or silver salts in presence of phosphine. Such examples are: [Ta₂Cu₂S₄Cl₂(PMe₃)₆] · DMF ( 1 ), (Et₄N)[Ta₃Cu₅S₈Cl₅(PMe₃)₆] · 2MeCN ( 2 ), (Et₄N)[Ta₉Cu₁₀S₂₄Cl₈(PMe₃)₁₄] · 2MeCN ( 3 ), [Ta₄Cu₁₂Cl₈S₁₂(PMe₃)₁₂] ( 4 ), (Et₄N)[Ta₂Cu₆S₆Cl₅(PPh₃)₆] · 5MeCN ( 5 ), (Et₄N)[Ta₂Cu₆S₆Cl₅(PPh₂Me)₆] · 2MeCN ( 6 ), (Et₄N)[Ta₂Cu₆S₆Cl₅(P^tBu₂Cl)₆] · MeCN ( 7 ) [Ta₂Cu₂S₄Br₄(PPh₃)₂(MeCN)₂] · MeCN ( 8 ), [Cu(PMe₃)₄]₂[Ta₂Cu₆S₆(SCN)₆(PMe₃)₆] · 4MeCN ( 9 ), [TaCu₅S₄Cl₂(dppm)₄] · DMF ( 10 ), [Ta₂Cu₂Se₄(SCN)₂(PMe₃)₆] ( 11 ), [Cu(PMe₃)₄]₂[Ta₂Cu₆Se₆(SCN)₆(PMe₃)₆] · 4MeCN ( 12 ), [TaCu₄Se₄(PⁿPr₃)₆][TaCl₆] ( 13 ), [Ta₂Ag₂Se₄Cl₂(PMe₃)₆] · MeCN ( 14 ), _∞[TaAg₃Se₄(PMe₃)₃] ( 15 ). The structures of these compounds were obtained by X‐ray single crystal structure analysis.     

Piperazinium,Ethylenediammonium or 4,4′‐Bipyridinium Halocuprates(I) by CuII/Cu0 Comproportionation

1‐Dimensional halocuprate(I) chains [(Cu₂X₄)^2–]_n (= [(CuX₂)^–]_n, X = Cl, Br, I) have been synthesized under hydrothermal conditions through in‐situ reduction of Cu^IIX₂ with Fe^IIX₂ or as phase pure materials through comproportionation of Cu^IIX₂ or Cu^IIO with Cu⁰ metal in the presence of the respective aqueous hydrogen halide HX and a templating amine. Chains of trans edge‐sharing tetrahedra are obtained with piperazinium or ethylenediammonium dications, while the 4,4′‐bipyridinium dication gave chains of cis edge‐sharing tetrahedra. Two monoprotonated piperazinium groups act as cationic ligands (Hpipz⁺) towards copper atoms in a molecular [Cu₄(μ‐Br₆)(Hpipz)₂] cluster. Electrical crystal conductivities of the halocuprate [(Cu₂X₄)^2–]_n (= [(CuX₂)^–]_n) chains (X = Cl, Br, I) are around 10^–8 S · cm^–1 at room temperature.     

Synthesis,Spectroscopy, and Structures of Mono‐ and Dinuclear Copper(I) Halide Complexes with 1,3‐Imidazolidine‐2‐thiones

Copper(I) halides with triphenyl phosphine and imidaozlidine‐2‐thiones (L ‐NMe, L ‐NEt, and L ‐NPh) in acetonitrile/methanol (or dichloromethane) yielded copper(I) mixed‐ligand complexes: mononuclear, namely, [CuCl(κ¹‐S‐L ‐NMe)(PPh₃)₂] ( 1 ), [CuBr(κ¹‐S‐L ‐NMe)(PPh₃)₂] ( 2 ), [CuBr(κ¹‐S‐L ‐NEt)(PPh₃)₂] ( 5 ), [CuI(κ¹‐S‐L ‐NEt)(PPh₃)₂] ( 6 ), [CuCl(κ¹‐S‐L ‐NPh)(PPh₃)₂] ( 7 ), and [CuBr(κ¹‐S‐L ‐NPh)(PPh₃)₂] ( 8 ), and dinuclear, [Cu₂(κ¹‐I)₂(μ‐S‐L ‐NMe)₂(PPh₃)₂] ( 3 ) and [Cu₂(μ‐Cl)₂(κ¹‐S‐L ‐NEt)₂(PPh₃)₂] ( 4 ). All complexes were characterized with analytical data, IR and NMR spectroscopy, and X‐ray crystallography. Complexes 2 – 4 , 7 , and 8 each formed crystals in the triclinic system with P$\bar{1}$ space group, whereas complexes 1 , 5 , and 6 crystallized in the monoclinic crystal system with space groups P2₁/c, C2/c, and P2₁/n, respectively. Complex 2 has shown two independent molecules, [(CuBr(κ¹‐S‐L ‐NMe)(PPh₃)₂] and [CuBr(PPh₃)₂] in the unit cell. For X = Cl, the thio‐ligand bonded to metal as terminal in complex 4 , whereas for X = I it is sulfur‐bridged in complex 3 .     

Kupferchalkogenid‐Clusterverbindungen mit Brom‐funktionalisierter Ligandenhülle

Five new copper chalcogenide cluster molecules, [Cu₄(S–C₆H₄–Br)₄(PPh₃)₄] ( 1 ), [Cu₂₂Se₆(S–C₆H₄–Br)₁₀(PPh₃)₈] ( 2 ), [Cu₂₈Se₆(S–C₆H₄–Br)₁₆(PPh₃)₈] ( 3 ), [Cu₄₇Se₁₀(S–C₆H₄–Br)₂₁(OAc)₆(PPh₃)₈] ( 4 ) and [Cu₈(S–C₆H₄–Br)₆(S₂C–NMe₂)₂(PPh₃)₄] ( 5 ) have been synthesized and characterized by single‐crystal X‐ray structure analysis. Compounds 1 – 4 were prepared from the reaction of CuOAc, p‐Br–C₆H₄–SSiMe₃ and Se(SiMe₃)₂ in the presence of PPh₃. In a further reaction of 1 with ⁱPrMgCl and (Me₂N–CS₂)₂ cluster 5 was crystallized.     

Chalkogenoniobate als Ausgangsverbindungen zur Darstellung neuer heterobimetallischer Niobium‐Münzmetall‐Chalkogenido‐Cluster

Chalcogenoniobates as Reagents for the Synthesis of New Heterobimetallic Niobium Coinage Metal Chalcogenide Clusters In the presence of phosphine chalcogenoniobates such as Li₃[NbS₄] · 4 CH₃CN ( I ), (NEt₄)₄[Nb₆S₁₇] · 3 CH₃CN ( II ) and (NEt₄)₂[NbE′₃(E^tBu)] ( III a : E′ = E = S; III b : E = Se, E′ = S; III c : E = E′ = Se) respectively react with copper and gold salts to give a number of new heterobimetallic niobium copper(gold) chalcogenide clusters. These clusters show metal chalcogenide units already known from the complex chemistry of the tetrachalcogenometalates [ME₄]^n– (M = V, n = 3, E = S; M = Mo, W, n = 2, E = S, Se). The compounds 1 – 8 owe a central tetrahedral [NbE₄] structural unit, which coordinates η² from two to five coinage metal atoms, employing the chalcogenide atoms of the [NbE₄] edges. The compounds 9 – 11 have a [M′₂Nb₂E₄] (M′ = Cu, Au) heterocubane unit in common, involving a metal metal bond between the niobium atoms, while the compounds 12 and 13 show a complete and 14 an incomplete [M′₃NbE₃X] heterocubane structure (X = Cl, Br). 15 consists of a Cu₆Nb₂ cube with the six planes capped by μ₄ bridging selenide ligands forming an octahedra. The compounds 1 – 15 are listed below: (NEt₄) [Cu₂NbSe₂S₂(dppe)₂] · 2 DMF ( 1 ), [Cu₃NbS₄(PPh₃)₄] ( 2 ), [Au₃NbSe₄(PPh₃)₄] · Et₂O ( 3 ), [Cu₄NbS₄Cl(PCy₃)₄] ( 4 ), [Cu₄NbS₄Cl(P^tBu₃)₄] · 0,5 DMF ( 5 ), [Cu₄NbSe₄(NCS)(P^tBu₃)₄] · DMF ( 6 ), [Cu₄NbS₄(NCS)(dppm)₄] · Et₂O ( 7 ), [Cu₅NbSe₄Cl₂‐ (dppm)₄] · 3 DMF ( 8 ), [Cu₂Nb₂S₄Cl₂(PMe₃)₆] · DMF ( 9 ), [Au₂Nb₂Se₄Cl₂(PMe₃)₆] · DMF ( 10 ), (NEt₄)₂[Cu₃Nb₂S₄(NCS)₅(dppm)₂(dmf)] · 4 DMF ( 11 ), [Cu₃NbS₃Br(PPh₃)₃(dmf)₃]Br · [CuBr(PPh₃)₃] · PPh₃ · OPPh₃ · 3 DMF ( 12 ), [Cu₃NbS₃Cl₂(PPh₃)₃(dmf)₂] · 1.5 DMF ( 13 ), (NEt₄)[Cu₃NbSe₃Cl₃(dmf)₃] ( 14 ), [Cu₆Nb₂Se₆O₂(PMe₃)₆] ( 15 ). The structures of these compounds were obtained by X‐ray single crystal structure analysis.     

Syntheses and crystal structures of two heterometallic iodoplumbates containing mixed‐valence copper(I/II)

Mixed‐valence copper(I/II) atoms have been introduced successfully into a Pb/I skeleton to obtain two heterometallic iodoplumbates, namely poly[bis(tetra‐n‐butylammonium) [bis(μ₃‐dimethyldithiocarbamato)dodeca‐μ₃‐iodido‐hexa‐μ₂‐iodido‐tetracopper(I)copper(II)hexalead(II)]], {(C₁₆H₃₆N)₂[Cu₄^ICu^IIPb₆(C₃H₆NS₂)₂I₁₈]}_n , (I), and poly[[μ₃‐iodido‐tri‐μ₂‐iodido‐iodido[bis(1,10‐phenanthroline)copper(I)]copper(I)copper(II)lead(II)] hemiiodine], {[Cu^ICu^IIPbI₅(C₁₂H₈N₂)₂]·0.5I₂}_n , (II), under solution and solvothermal conditions, respectively. Compound (I) contains two‐dimensional anionic layers, which are built upon the linkages of Cu^II(S₂CNMe₂)₂ units and one‐dimensional anionic Pb/I/Cu^I chains. Tetra‐n‐butylammonium cations are located between the anionic layers and connected to them via C—H…I hydrogen‐bonding interactions. Compound (II) exhibits a one‐dimensional neutral structure, which is composed of [PbI₅] square pyramids, [Cu^II₄] tetrahedra and [Cu^IIN₄I] trigonal bipyramids. Face‐to‐face aromatic π–π stacking interactions between adjacent 1,10‐phenanthroline ligands stabilize the structure and assemble compound (II) into a three‐dimensional supramolecular structure. I₂ molecules lie in the voids of the structure.     

Neue Kupfertellurid‐Cluster – Synthesen,Kristallstrukturen und optische Spektren

New Coppertelluride Clusters – Syntheses, Crystal Structures, and Optical Spectra Reactions of copper(I) acetate with Te(SiMe₃)₂ lead in the presence of tertiary phophines PR₃ (R = organic group) to the formation of new coppertelluride clusters: [Cu₈Te₄(PPh₃)₇] ( 1 ), [Cu₁₆Te₉(PPh₃)₈] ( 2 ), [Cu₂₃Te₁₃(PPh₃)₁₀] ( 3 ), [Cu₄₄Te₂₃(PPh₃)₁₅] ( 4 ), [Cu₁₂Te₆(PPh₃)₈] ( 5 ), [Cu₂₆Te₁₂(PEt₂Ph)₁₂] ( 6 ), [Cu₁₆Te₈(PⁿPr₂Ph)₁₀] ( 7 ), [Cu₄₄Te₂₃(PⁿPr₂Ph)₁₅] ( 8 ), [Cu₂₄Te₁₂(PⁱPr₃)₁₂] ( 9 ). Simple electron counting on the basis of Cu¹⁺ and Te^2– suggests that the smaller and medium size clusters 1 , 5 , 7 , and 9 are electron precise compounds and that on the other hand some of the medium size and larger ones 2 , 3 , 4 , and 8 must contain mixtures of Cu¹⁺/Cu²⁺ ions or 6 Cu¹⁺ ions and Cu⁰ atoms. UV‐VIS spectra in the solid state strongly confirms this suggestion by showing broad intervalence bands in the region of higher wavelengths for the cluster compounds formally being not electron precise. Apparently there is also an interesting dependence of these intervalence bands on the size of the cluster molecules.     

Diamond‐ and Graphite‐Like Octacyanometalate‐Based Polymers Induced by Metal Ions

By using cyclohexane‐1,2‐diamine (chxn), Ni(ClO₄)₂ ? 6H₂O and Na₃[Mo(CN)₈] ? 4H₂O, a 3D diamond‐like polymer {[Ni^II(chxn)₂]₂[Mo^IV(CN)₈] ? 8H₂O}_n ( 1 ) was synthesised, whereas the reaction of chxn and Cu(ClO₄)₂ ? 6H₂O with Na₃[M^V(CN)₈] ? 4H₂O (M=Mo, W) afforded two isomorphous graphite‐like complexes {[Cu^II(chxn)₂]₃[Mo^V(CN)₈]₂ ? 2H₂O}_n ( 2 ) and {[Cu^II(chxn)₂]₃[W^V(CN)₈]₂ ? 2H₂O}_n ( 3 ). When the same synthetic procedure was employed, but replacing Na₃[Mo(CN)₈] ? 4H₂O by (Bu₃NH)₃[Mo(CN)₈] ? 4H₂O (Bu₃N=tributylamine), {[Cu^II(chxn)₂Mo^IV(CN)₈][Cu^II(chxn)₂] ? 2H₂O}_n ( 4 ) was obtained. Single‐crystal X‐ray diffraction analyses showed that the framework of 4 is similar to 2 and 3 , except that a discrete [Cu(chxn)₂]²⁺ moiety in 4 possesses large channels of parallel adjacent layers. The experimental results showed that in this system, the diamond‐ or graphite‐like framework was strongly influenced by the inducement of metal ions. The magnetic properties illustrate that the diamagnetic [Mo^IV(CN)₈] bridges mediate very weak antiferromagnetic coupling between the Ni^II ions in 1 , but lead to the paramagnetic behaviour in 4 because [Mo^IV(CN)₈] weakly coordinates to the Cu^II ions. The magnetic investigations of 2 and 3 indicate the presence of ferromagnetic coupling between the Cu^II and W^V/Mo^V ions, and the more diffuse 5d orbitals lead to a stronger magnetic coupling interaction between the W^V and Cu^II ions than between the Mo^V and Cu^II ions.     

Dinukleare Kupfer(II)‐Komplexe mit chiralen makrocyclischen Liganden vom Schiff‐Basen‐Typ: Synthesen und Strukturen

Complexes with Macrocyclic Ligands. V Dinuclear Copper(II) Complexes with Chiral Macrocyclic Ligands of Schiff‐Base Type: Syntheses and Structures The synthesis and properties of four chiral, dinuclear, macrocyclic, cationic copper(II) complexes, [Cu₂(L^m,n)]²⁺ ( 1 – 4 ), are described. The two symmetrical compounds [Cu₂(L^2,2)][ClO₄]₂ ( 1 and 2 ) were synthesized in a one‐step reaction from 2,6‐diformyl‐4‐tert.‐butylphenol, copper(II)‐perchlorate and the chiral diamine (1S,2S)‐1,2‐diphenylethylenediamine (synthesis of 1 ) and (1R,2R)‐1,2‐diaminocyclohexane (synthesis of 2 ), respectively. For the synthesis of the two unsymmetrical compounds [Cu₂(L^Ph,n)][ClO₄]₂ ( 3 and 4 ) the mononuclear, neutral copper(II) complex [CuL^Ph] ( 5 ) [synthesized from 2,6‐diformyl‐4‐tert.‐butylphenol, copper(II)‐acetate and 1,2‐phenylenediamine] was reacted with (1R,2R)‐1,2‐diaminocyclohexane (synthesis of 3 ) and (S)‐1,1′‐binaphthyl‐2,2′‐diamine (synthesis of 4 ), respectively. The structures of the two unsymmetrical copper(II) compounds ( 3 and 4 ) were determined by X‐ray diffraction.     

Luminescent Metal–Organic Frameworks (MOFs) as a Chemopalette: Tuning the Thermochromic Behavior of Dual‐Emissive Phosphorescence by Adjusting the Supramolecular Microenvironments

Two classical copper(I)‐cluster‐based luminophores, namely, Cu₄I₄ and [Cu₃Pz₃]₂ (Pz=pyrazolate), are immobilized in a supramolecular system through the formation of metal–organic framework (MOF) materials. This series of luminescent MOF materials, namely, [Cu₄I₄(NH₃)Cu₃( L1 )₃]_n, [Cu₄I₄(NH₂CH₃)Cu₃( L1 )₃]_n, and [Cu₄I₄Cu₃( L2 )₃]_n ( L1 =3‐(4‐pyridyl)‐5‐(p‐tolyl)pyrazolate; L2 =3‐(4‐pyridyl)‐5‐(2,4‐dimethylphenyl)pyrazolate), exhibit diverse thermochromism attributed to the relative functioning efficacy of the two coordination luminophores. Such an intriguing chemopalette effect is regulated by the different supramolecular microenvironments between the two‐dimensional layers of these MOFs, and in particular, by the fine‐tuned Cu–Cu distances in the excimeric [Cu₃Pz₃]₂ luminophore. The structure–property elucidation of the thermochromic behavior allows one to understand these optical materials with unusual dual‐emissive properties.     

Copper(II) and cadmium(II) isothiocyanate coordination polymers with 4,4′‐bi‐1,2,4‐triazole

The coordination polymers catena‐poly[[[(4,4′‐bi‐1,2,4‐triazole‐κN¹)bis(thiocyanato‐κN)copper(II)]‐μ‐4,4′‐bi‐1,2,4‐triazole‐κ²N¹:N^1′] dihydrate], {[Cu(NCS)₂(C₄H₄N₆)₂]·2H₂O}_n, (I), and poly[tetrakis(μ‐4,4′‐bi‐1,2,4‐triazole‐κ²N¹:N^1′)bis(μ‐thiocyanato‐κ²N:S)tetrakis(thiocyanato‐κN)tricadmium(II)], [Cd₃(NCS)₆(C₄H₄N₆)₄]_n, (II), exhibit chain and two‐dimensional layer structures, respectively. The differentiation of the Lewis acidic nature of Cu^II and Cd^II has an influence on the coordination modes of the triazole and thiocyanate ligands, leading to topologically different polymeric motifs. In (I), copper ions are linked by bitriazole N:N′‐bridges into zigzag chains and the tetragonal–pyramidal CuN₅ environment is composed of two thiocyanate N atoms and three triazole N atoms [basal Cu—N = 1.9530 (18)–2.0390 (14) Å and apical Cu—N = 2.2637 (15) Å]. The structure of (II) contains two types of crystallographically unique Cd^II atoms. One type lies on an inversion center in a distorted CdN₆ octahedral environment, with bitriazole ligands in the equatorial plane and terminal isothiocyanate N atoms in the axial positions. The other type lies on a general position and forms centrosymmetric binuclear [Cd₂(μ‐NCS‐κ²N:S)₂(NCS)₂] units (tetragonal–pyramidal CdN₄S coordination). N:N′‐Bridging bitriazole ligands link the Cd centers into a flat (4,4)‐network.     

Three oxo complexes with a tetra­nuclear [Cu4(μ2‐Cl)6(μ4‐O)] unit

The three title compounds, namely 4‐phenyl‐1H‐imidazolium hexa‐μ₂‐chloro‐chloro‐μ₄‐oxo‐tris­(4‐phenyl‐1H‐imidazole‐κN¹)­tetra­copper(II) monohydrate, (C₉H₉N₂)[Cu₄Cl₇O(C₉H₈N₂)₃]·H₂O, hexa‐μ₂‐chloro‐μ₄‐oxo‐tetra­kis­(pyridine N‐oxide‐κO)tetra­copper(II), [Cu₄Cl₆O(C₅H₅NO)₄], and hexa‐μ₂‐chloro‐tetra­kis(2‐methyl‐1H‐imidazole‐κN¹)‐μ₄‐oxo‐tetra­copper(II) methanol trisolvate, [Cu₄Cl₆O(C₄H₆N₂)₄]·3CH₄O, exhibit the same Cu₄OCl₆ framework, where the O atom at the centre of an almost regular tetra­hedron bridges four copper cations at the corners. This group is in turn surrounded by a Cl₆ octa­hedron, leading to a rather globular species. This special arrangement of the Cu^II cations results in a diversity of magnetic behaviours.     

A three‐dimensional mixed‐valence CuII/CuI coordination polymer constructed from biphenyl‐3,4′,5‐tricarboxylate and 1,4‐bis(1H‐imidazol‐1‐yl)benzene ligands

Coordination polymers (CPs) built by coordination bonds between metal ions/clusters and multidentate organic ligands exhibit fascinating structural topologies and potential applications as functional solid materials. The title coordination polymer, poly[diaquabis(μ₄‐biphenyl‐3,4′,5‐tricarboxylato‐κ⁴O³:O^3′:O^4′:O⁵)tris[μ₂‐1,4‐bis(1H‐imidazol‐1‐yl)benzene‐κ²N³:N^3′]dicopper(II)dicopper(I)], [Cu^II₂Cu^I₂(C₁₅H₇O₆)₂(C₁₂H₁₀N₄)₃(H₂O)₂]_n, was crystallized from a mixture of biphenyl‐3,4′,5‐tricarboxylic acid (H₃bpt), 1,4‐bis(1H‐imidazol‐1‐yl)benzene (1,4‐bib) and copper(II) chloride in a water–CH₃CN mixture under solvothermal reaction conditions. The asymmetric unit consists of two crystallographically independent Cu atoms, one of which is Cu^II, while the other has been reduced to the Cu^I ion. The Cu^II centre is pentacoordinated by three O atoms from three bpt³⁻ ligands, one N atom from a 1,4‐bib ligand and one O atom from a coordinated water molecule, and the coordination geometry can be described as distorted trigonal bipyramidal. The Cu^I atom exhibits a T‐shaped geometry (CuN₂O) coordinated by one O atom from a bpt³⁻ ligand and two N atoms from two 1,4‐bib ligands. The Cu^II atoms are extended by bpt³⁻ and 1,4‐bib linkers to generate a two‐dimensional network, while the Cu^I atoms are linked by 1,4‐bib ligands, forming one‐dimensional chains along the [20] direction. In addition, the completely deprotonated μ₄‐η¹:η¹:η¹:η¹ bpt³⁻ ligands bridge one Cu^I and three Cu^II cations along the a (or [100]) direction to form a three‐dimensional framework with a (10³)₂(10)₂(4².6.10².12)₂(4².6.8².10)₂(8) topology via a 2,2,3,4,4‐connected net. An investigation of the magnetic properties indicated a very weak ferromagnetic behaviour.     

Syntheses,Crystal Structures,and Photocatalytic Activities of Three Copper Coordination Polymers Based on Bis(1H‐imidazol‐4‐yl)benzene/3‐(2‐Pyridyl)pyrazole

Three copper(II) coordination polymers (CuCPs), namely, [Cu_0.5(1,4‐bib)(SO₄)_0.5]_n ( 1 ), {[Cu(1,3‐bib)₂(H₂O)] · SO₄ · H₂O}_n ( 2 ), and [Cu(bpz)(SO₄)_0.5]_n ( 3 ), were assembled from the reaction of three N‐donors [1,4‐bib = 1,4‐bis(1H‐imidazol‐4‐yl)benzene, 1,3‐bib = 1,3‐bis(1H‐imidazol‐4‐yl)benzene, and Hbpz = 3‐(2‐pyridyl)pyrazole] with copper sulfate under hydrothermal conditions. Their structures were determined by single‐crystal X‐ray diffraction analyses and further characterized by elemental analyses (EA), IR spectroscopy, powder X‐ray diffraction (PXRD), and thermogravimetric analyses (TGA). Structure analyses reveal that complex 1 is a 3D 6‐connected {4¹² · 6³}‐ pcu net, complex 2 is a fourfold 3D 4‐connected 6⁶‐ dia net, whereas complex 3 is a 1D snake‐like chain, which further expanded into 3D supramolecular architectures with the help of C–H ··· O hydrogen bonds. Moreover, the photocatalytic tests demonstrate that the obtained CuCPs are photocatalysts in the degradation of MB with the efficiency is 86.4 % for 1 , 75.3 % for 2 , and 91.3 % for 3 after 2 h, respectively.     

Synthesis and Structural Characterization of Six Pentanuclear and Tetranuclear Mo/W‐Cu‐S Clusters with Bis(diphenylphosphanyl) Methane

Six heterothiometalic clusters, namely, [WS₄Cu₄(dppm)₄](ClO₄)₂ · 2DMF · MeCN ( 1 ), [MoS₄Cu₄(dppm)₄](NO₃)₂ · MeCN ( 2 ) [MoS₄Cu₃(dppm)₃](ClO₄) · 4H₂O ( 3 ), [WS₄Cu₃(dppm)₃](NO₃) · 4H₂O ( 4 ), [WS₄Cu₃(dppm)₃]SCN · CH₂Cl₂ ( 5 ), and [WS₄Cu₃(dppm)₃]I · CH₂Cl₂ ( 6 ) [dppm = bis (diphenylphosphanyl)methane] were synthesized. Compounds 1 – 4 were obtained by the reactions of (NH₄)₂MS₄ (M = Mo, W) with [Cu₂(μ₂‐dppm)₂(MeCN)₂(ClO₄)₂] {or [Cu(dppm)(NO₃)]₂} in the presence of 1,10‐phen in mixed solvent (CH₃CN/CH₂Cl₂/DMF for 1 and 2 , CH₂Cl₂/CH₃OH/DMF for 3 and 4 . Compounds 5 and 6 were obtained by one‐pot reactions of (NH₄)₂WS₄ with dppm and CuSCN (or CuI) in CH₂Cl₂/CH₃OH. These clusters were characterized by single‐crystal X‐ray diffraction as well as IR, ¹H NMR, and ³¹P NMR spectroscopy. Structure analysis showed that compounds 1 and 2 are “saddle‐shaped” pentanuclear cationic clusters, whereas compounds 3 – 6 are “flywheel‐shaped” tetranuclear cationic clusters. In 1 and 2 , the MS₄^2– unit (M = W, Mo) is coordinated by four copper atoms, which are further bridged by four dppm molecules. In compounds 3 – 6 , the MS₄^2– unit is coordinated by three copper atoms and each copper atom is bridged by three dppm ligands.     

Synthesen und Kristallstrukturen von Cu‐ und Ag‐Komplexen mit Dithiophosphinat‐ und Trithiophosphonat‐Liganden

Syntheses and Crystal Structures of Copper and Silver Complexes containing Dithiophosphinato and Trithiophosphonato Ligands The reactions of Cu^I and Ag^I salts with diphenyldithiophosphinic acid trimethylsilylester in the presence of tertiary phosphines yield the complexes [Cu(μ‐S)SPPh₂(PR₃)]₂ (R = Me 1a , ⁱPr 1b ), [Ag(μ‐S)SPPh₂(PⁿPr₃)]₂ ( 2 ), [Ag(S₂PPh₂)(PEt₃)]₂ ( 3 ), and [Cu₈(μ₈‐S)(S₂PPh₂)₆] ( 4 ). The cage complex [(PhPS₃)₂Cu₄(PMe₃)₅] ( 5 ) is obtained by the reaction of phenyltrithiophosphonic acid trimethylester. All compounds were structurally characterised by X‐ray crystallography.     

Synthese und thermische Eigenschaften von molekularen Clusterverbindungen zusammengesetzt aus Elementen der Gruppen 11‐13‐16

Syntheses and Thermal Properties of Cluster Molecules, formed from Groups 11‐13‐16 Elements In the presence of PPh₃, CuX (X = Cl, CH₃COO) or AgOC(O)C₆H₅ and GaCl₃ react in THF with S(SiMe₃)₂ or Se(SiMe₃)₂ to yield [Cu₆Ga₈Cl₄S₁₃(PPh₃)₆] ( 1 ), [Cu₆Ga₈Cl₄Se₁₃(PPh₃)₆] ( 2 ), [Ag₆Ga₈Cl₄S₁₃(PPh₃)₆] ( 4 ) and [Ag₆Ga₈Cl₄Se₁₃(PPh₃)₆] ( 5 ). The use of PⁿPr₂Ph instead of PPh₃ and subsequent layering with n‐hexane leads to the formation of the cluster [Cu₆Ga₈Cl₄Se₁₃(PⁿPr₂Ph)₁₂] ( 3a , 3b ). Reaction of CuCl, GaCl₃ and PⁿPr₃ with Se(SiMe₃)₂ in THF results in the crystallisation of the ionic cluster (HPⁿPr₃)₂[Cu₂Ga₄Cl₄Se₆(PⁿPr₃)₄] ( 6 ). The structures of 1 — 6 were determined by X‐ray single crystal structure analysis. Thermogravimetric measurements of the cluster molecules and powder diffraction patterns of the remaining powders reveal the potential use of them as single source precursor compounds for the synthesis of the related ternary solid state materials.