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Reactivity of new tetrahedral rhenium cluster complexes with pnictogenide inner ligands μ

A series of heterometallic tetrahedral cluster complexes with the general formula [{MxRe4−xSe4}(CN)12]n− (M = Mo, W; x = 2, 3) were obtained using the reaction of ReI3 and MO3 with selenium and KCN at elevated temperatures. Compounds [ReW3Se4(CN)12]6− and [Re2W2Se4(CN)12]6− are the first rhenium–tungsten heterometallic clusters. Crystal structures, electrochemical properties in aqueous solutions and magnetic properties of crystalline samples have been studied in detail. It has been shown that new cluster anions demonstrate a regular change in geometric characteristics and redox potentials depending on the composition of the cluster core.

The first vanadium selenoiodide V4O(Se2)4I6·I2 was synthesized at a moderate temperature of 220 °C from V, Se, I2, and water. Its crystal structure (tetragonal space group P42/nbc, a = 11.838(1) A, c = 18.689(1) A) contains O-centered vanadium(IV) tetranuclear fragment [V4(μ4-O)(μ2-Se2)4(μ2-I)2I4], where the edges of the distorted tetrahedron V4 are bridged by four diselenide (Se2)2- and two iodide ligands; four terminal iodides coordinate V atoms additionally. This type of complex is known for Ti, Nb, and Ta but is new for vanadium. Magnetic susceptibility measurements of V4O(Se2)4I6·I2 showed four unpaired electrons on vanadium atoms at room temperature and drop of the effective magnetic moment at cool down, presumably due to partial electron pairing. Probability of this transition to the diamagnetic state is in accord with the calculated electronic structure.

The interaction of rhenium(III) halides Re3Br9 and Re3I9 with aqueous solution of sodium cyanide resulted in the formation of the first trinuclear halide-cyanide rhenium cluster complexes [{Re3X3}(CN)9]5-/[{Re3X3}(CN)9]4- (X = Br or I) crystallized as salts of the compositions Cs4Na[{Re3Br3}(CN)9]·5.25H2O (1), Cs4Na[{Re3I3}(CN)9]·6H2O (2), Cs4[{Re3Br3}(CN)9]·2H2O·0.5CsCl (3), and Cs4[{Re3I3}(CN)9]·(4). All of the compounds are stable in air in the solid state and in aqueous solution. The substitution of apical halide ligands in the parent compounds Re3X9 by cyanides led to reduction of the original metallocluster Re39+ (12 cluster valence electrons (CVEs)) to Re37+ (14 CVEs), forming the compounds 1 and 2. The apical CN- ligands affect the electronic structure of the Re3 metallocluster stabilizing reduced form. Complexes 1 and 2 represent the first examples of triangular rhenium clusters with the Re37+ metallocluster. The reaction of 1 and 2 with H2O2 resulted in formation of compounds 3 and 4 with the formal charge of the Re3 metallocluster equal to 8+, and no further oxidation to Re39+ occurred. The compounds were characterized by the X-ray diffraction analysis, NMR and UV-vis spectroscopies, mass spectrometry, cyclic voltammetry, and magnetic susceptibility measurements.

A reaction between ReI3 and KCN at elevated temperature led to the formation of the new cyanometalate cluster anion [{Re4(μ3-CCN)4}(CN)12]8– (1). The anion contains μ3-CCN3– ligands, which are stab...

The reaction of [Re6Se8(CN)6]4− cluster anions with Ln3+ cations in the presence of thiophene-2,5-dicarboxylate anions in an aqueous solution was studied. Two new framework compounds were synthesized and structurally characterized: [{Yb(H2O)3}2(tdc)-Re6Se8(CN)6]•10H2O (1) and CsK0,5[{Yb4(OH)4(H2O)7,5(NO3)0,5(tdc)2}{Re6Se8(CN)6}]NO3 • 16.5H2O (2) (tdc is the thiophene-2,5-dicarboxylate anion). Compound 1 crystallizes in a wide pH range (3.0–6.5) and has a porous structure with large open voids accessible to guest molecules. Compound 2 crystallizes at pH 6.0–6.5, contains polynuclear cationic complexes [Yb4(OH)4]8+, and also has a framework structure.

The family of chalcogenide molybdenum clusters is well presented in the literature by a series of compounds of nuclearity ranging from binuclear to multinuclear articulating octahedral fragments. Clusters actively studied in the last decades were shown to be promising as components of superconducting, magnetic, and catalytic systems. Here, we report the synthesis and detailed characterization of new and unusual representatives of chalcogenide clusters: square pyramidal complexes [{Mo5(μ3-Se)i4(μ4-Se)i(μ-pz)i4}(pzH)t5]1+/2+ (pzH = pyrazole, i = inner, t = terminal). Individually obtained oxidized (2+) and reduced (1+) forms have very close geometry (proven by single-crystal X-ray diffraction analysis) and are able to reversibly transform into each other, which was confirmed by cyclic voltammetry. Comprehensive characterization of the complexes, both in solid and in solution, confirms the different charge state of molybdenum in clusters (XPS), magnetic properties (EPR), and so on. DFT calculations complement the diverse study of new complexes, expanding the chemistry of molybdenum chalcogenide clusters.

The selective preparation, structural and spectroscopic study of two new rhenium cluster complexes trans-[Re6S8(bpy)4(CN)2] and trans-[Re6S8(bpy)2(CN)4]2− (bpy = 4,4′-bipyridine) obtained by reactions of corresponding hexarhenium cyanohalides with molten bpy are reported. The complexes were crystallized as solvates, displaying supramolecular structures based on cluster units linked by numerous weak interactions with bpy molecules. The molecular compound trans-[Re6S8(bpy)4(CN)2] (1) is insoluble in water and common organic solvents, while the ionic compound trans-Cs1.7K0.3[Re6S8(bpy)2(CN)4] (2) is somewhat soluble in DMSO, DMF and N-methylpyrrolidone. The presence of the redox-active ligand bpy leads to the occurrence of multi-electron reduction transitions in a solution of 2 at moderate potential values. The ambidentate CN− ligand is the secondary functional group, which has potential for the synthesis of coordination polymers based on the new cluster complexes. In addition, both new compounds show a weak red luminescence, which is characteristic of complexes with a {Re6S8}2+ cluster core.

A series of 12 new metal–organic frameworks based on lanthanide cations (Ln = Nd, Sm–Dy), octahedral cluster anions [Re6S8(CN)6]4− or [Re6Se8(CN)6]4− and adipamide (adp) were synthesized under mild conditions in aqueous ethanol solutions. Compounds of the general composition Cs[Ln(adp)2{Re6Q8(CN)6}]·3H2O (Ln = Nd, Sm–Dy; Q = S or Se) crystallize in the hexagonal space group P6422. Despite the presence of solvate H2O molecules in structure cavities, the crystal structures revealed that the coordination environment of lanthanide cations in these 3D polymers did not contain H2O ligands. This rare feature is attributed to the combination of a bulk cluster anion and flexible adp molecules, which occupy the lanthanide coordination sphere to yield a stable lanthanide-based building block. This assumption was confirmed by synthesis of a second crystalline modification of the compound Cs[Nd(adp)2{Re6S8(CN)6}]·3H2O (orthorhombic space group Cccm). Luminescence studies evidence the presence of the typical red luminescence of hexarhenium cluster complexes and the absence of observable luminescence of lanthanide cations for all the compounds except the Nd derivatives. Magnetic data indicate very weak antiferromagnetic exchange interactions between paramagnetic Ln3+ centers.

Influence of the metal core composition and geometry on the structure, spectroscopic properties and redox potentials was investigated for the first time for heterometallic (Re/Mo)6 octahedral clusters. The discrete anionic clusters [Re6-x Mox Se8 (CN)6 ]n- (x=2, 3; n=4, 5) were obtained as individual salts. Their isomeric composition and bond-length distribution were inspected using a combination of single-crystal X-ray structure analysis, NMR, EXAFS, and DFT calculations.

International audience; A number of transition metal cluster compounds can be obtained only in the melt of inorganic cyanides and, therefore, contain terminal cyanide ligands. Substitution of these ligands, which is often necessary to change the physicochemical properties of the clusters, is an urgent problem because of their low reactivity in substitution reactions. In this work, a synthetic approach has been developed for the substitution of CN-ligands in the heterometallic cluster anions [Re(3)Mo(3)Q(8)(CN)(6)](n-) (Q = S, n = 6; Q = Se, n = 5) by the 4-tert-butylpyridine (TBP) molecules. Two new compounds, namely [Re3Mo3S8(TBP)(6)] (1) and [Re3Mo3Se8(TBP)(6)] (2), were obtained with high yields and crystallized under solvothermal conditions. It has been shown that compounds 1 and 2 are based on the paramagnetic cluster cores {Re(3)Mo(3)Q(8)}(0) containing 23 cluster valence electrons (CVE). The geometry of the new compounds has been investigated using X-ray structural analysis. The electronic structure has been analyzed using the DFT calculations showing large distortion of M-6 cluster core.

A high-temperature reactions of equimolar amounts of ReI3, As and S or Se with KCN following by recrystallization of the soluble products from water led to the formation of new cyanometallate cluster complexes K7[{Re4As3S}(CN)12]·10H2O (1) and K7[{Re4As3Se}(CN)12]·9.5H2O (2), respectively. Involvement of As2S3 instead of the mixture of As and S resulted in the formation of a cluster complex K6[{Re4As2S2}(CN)12]·3.5H2O (3). Crystal structures of the obtained compounds were investigated by the X-ray diffraction analysis. It was found that compounds 1–3 contain a new cubane cluster cores composed of the rhenium tetrahedron surrounded by the µ3-As and µ3-Q (Q = S, Se) ligands.

The cubane chalcocyanide cluster anion [Re4Te4(CN)12]4− was used as a pre-made building block for construction of a series of seven new coordination polymers (CPs) based on cationic complexes of Ln3+ ions and 1,10-phenantroline (phen). Together with three previously known compounds of this type, 1D CPs based on [Re4Te4(CN)12]4− anion formed a representative series which includes ten compounds (Ln = La, Pr, Nd, Sm–Ho, Yb). The main structural motif in the new compounds is the 1D chains composed of alternating cluster anions and [Ln(H2O)n(phen)m]3+ cationic fragments. Topology of the chains was found to be independent from the ionic radius and coordination number of the lanthanide ion. However, different number and orientation of coordinated phen and H2O molecules in the coordination environment of the lanthanide ions led to formation of several types of the supramolecular structures formed by non-covalent interactions between H2O, phen and CN− ligands. Influence of coordination environment of the lanthanide ions and conditions of the synthesis to the supramolecular structures is discussed in this work as well as structural relations with 1D coordination polymers based on mononuclear cyanometallate building blocks.

The interaction of rhenium(III) halides Re

Compounds based on new cyanide cluster anions [{Mo6I8}(CN)6]2&ndash, trans-[{Mo6I8}(CN)4(MeO)2]2&ndash, and trans-[{W6I8}(CN)2(MeO)4]2&minus, were synthesized using mechanochemical or solvothermal synthesis. The crystal and electronic structures as well as spectroscopic properties of the anions were investigated. It was found that the new compounds exhibit red luminescence upon excitation by UV light in the solid state and solutions, as other cluster complexes based on {Mo6I8}4+ and {W6I8}4+ cores do. The compounds can be recrystallized from aqueous methanol solutions, besides this, it was shown using NMR and UV-Vis spectroscopy that anions did not undergo hydrolysis in the solutions for a long time. These facts indicate that hydrolytic stabilization of {Mo6I8} and {W6I8} cluster cores can be achieved by coordination of cyanide ligands.

A reaction between ReI

Substitution of terminal halide ligands of octahedral rhenium cluster complexes [Re6Q8X6]4– in a melt of 4,4′-bipyridine (bpy) led to us obtaining four new compounds with the general formula trans-...

Here we explore the effect of the nature of organic ligands in rhenium cluster complexes [Re6 Q8 L6 ]4- (where Q=S or Se, and L=benzotriazole, 1,2,3-triazole or 1,2,4-triazole) on the biological properties of the complexes, in particular on the cellular toxicity, cellular internalization and localization. Specifically, the study describes the synthesis and detailed characterization of the structure, luminescence and electrochemical properties of the four new Re6 clusters with 1,2,3- and 1,2,4-triazoles. Biological assays of these complexes are also discussed in addition to those with benzotriazole using cervical cancer (HeLa) and immortalized human fibroblasts (CRL-4025) as model cell lines. Our study demonstrates that the presence of hydrophobic and π-bonding rich units such as the benzene ring in benzotriazole significantly enhances cellular internalization of rhenium clusters. These ligands facilitate binding of the clusters to DNA, which results in increased cytotoxicity of the complexes.

A first method for obtaining of electron-rich bioctahedral rhenium clusters has been developed. Two cluster salts, namely (Et3NH)4(Me2NH2)4[Re12CS14(µ-S)3Cl6] (1) and (Et4N)4(Me2NH2)4[Re12CS14(µ-S)3Br6] (2), have been synthesized and isolated in the solid state. Single-crystal X-ray diffraction showed that salts 1 and 2 are based on the new cluster anions [Re12CS14(µ-S)3Cl6]8− and [Re12CS14(µ-S)3Br6]8− containing 48 cluster valence electrons (CVE). The correlations between geometry and CVE number of the bioctahedral chalcohalide anions have been examined using the DFT calculations. The dissolution of the salts 1 and 2 is accompanied by the oxidation yielding the [Re12CS14(µ-S)3Cl6]6− and [Re12CS14(µ-S)3Br6]6− anions. Properties of the new clusters in the DMSO solutions have been investigated by UV–Vis spectroscopy and cyclic voltammetry. The latter revealed the presence of multiple reversible one-electron redox waves in a narrow potential window.

In this work, we demonstrate influence of the source of organic ligand on the formation of supramolecular structures based on the octahedral metal clusters. Two series of coordination polymers based on the rhenium clusters [Re6Se8(CN)6]4– and Ln3+ complexes (Ln = Sm, Eu, Tb, Dy) with dimethylformamide (DMF) were obtained. The first series was obtained by direct addition of DMF in the reaction mixture. The series consist of the compounds crystallizing in trigonal crystal system, R3c space group, and possessing a framework porous structures composed of cluster anions and [Ln(dmf)3(H2O)2]3+ complexes. Compounds of the second series were obtained as a result of in situ generation of DMF by hydrolysis of N,N-dimethylformamide dimethyl acetal (DMF DMA). These compounds were crystallized in orthorhombic crystal system, Pnma space group, and possessed a layered structure consisting of cluster anions and [Ln(dmf)2(H2O)2]3+ complexes. It was found that the difference in the structures formed depends on the source of DMF rather than other reaction conditions.

Cluster compounds based on a new {Re3Mo3Se8}n core were obtained and studied. The polymeric solid K6[Re3Mo3Se8(CN)4(CN)2/2] (1) containing 24 cluster valence electrons (CVE) was isolated as a result of high-temperature reaction. Water-soluble salts K5[Re3Mo3Se8(CN)6]·11H2O (2) and Cs5[Re3Mo3Se8(CN)6]·H2O (3) were prepared from compound 1. Crystal structures of the diamagnetic compounds 2 and 3 contain a cluster anion [Re3Mo3Se8(CN)6]5- with a 22-electronic core {Re3Mo3Se8}+. Metathesis reaction followed by recrystallization from CH3CN yielded paramagnetic salt (Ph4P)4[Re3Mo3Se8(CN)6]·2CH3CN (4) containing the {Re3Mo3Se8}2+ core with 21 CVE. Cyclic voltammetry of the solution of 4 displayed three quasi-reversible waves with E1/2 = -0.325, -0.818 and -1.410 V vs. Ag/AgCl electrode indicating the presence of [Re3Mo3Se8(CN)6]4-/5-/6-/7- transitions. Electronic structure calculations showed that both mer- and fac-isomers of [Re3Mo3Se8(CN)6]n- clusters undergo great distortion when the number of CVE decreases.

Tungsten trioxide has been found to be a convenient precursor for the synthesis of metal cluster compounds with new types of cluster cores. The reaction between WO3 and KCN led to the formation of the cluster complex [{W6(μ4-O)2(μ3-CCN)4}(CN)16]10−. Unexpectedly, it includes the fully deprotonated form of acetonitrile, the CCN3− anion, as a μ3-bridging ligand coordinated to the trigonal faces of the bitetrahedral W6 metallocluster. A similar complex [{W6(μ4-O)2(μ3-As)4}(CN)16]10− containing μ3-As3− ligands instead of μ3-CCN3− ones has been synthesized by the reaction between WO3, As and KCN.

Selective substitution of μ-SO22- groups by either O2- or Se2- ions occurs upon heating the bioctahedral rhenium cluster complex K6[Re12CS14(μ-SO2)3(CN)6] in air atmosphere or in the presence of a Se source, respectively, manifesting the remarkable lability of SO22- ligands bound to a transition-metal cluster. A series of compounds based on the new mixed-ligand anions, [Re12CS14(μ-O)3(CN)6]6-, [Re12CS14(μ-Se)3(CN)6]6-, and [Re12CS14(μ-O)3(OH)6]6-, were isolated and their solid-state structures were elucidated by single-crystal X-ray diffraction analysis. Along with the previously reported μ-sulfide clusters, the new species constitute a series of rhenium anionic complexes with the common formula [Re12CS14(μ-Q)3L6]6- (Q = O, S, Se, L = CN-; Q = O, S, L = OH-), within which the total charge and number of cluster valence electrons (CVEs) are constant. The article presents insights into the mechanistic and synthetic aspects of the substitution process, and it comprehensively discusses the influence of inner ligand environment on the structure, spectroscopic characteristics, and electrochemical behavior of the novel compounds.

Three new polymeric compounds of general formula {[Ln(phen)(H2O)3Ln(phen)(H2O)2(μ-OH)2][Re4Te4(CN)12]}·H2O (Ln = Dy, Ho, Er) were obtained by self-assembly reaction of [Re4Te4(CN)12]4– cluster anions, Ln3+ cations and 1,10-phenthroline (phen) in a solvothermal conditions. Single-crystal X-Ray diffraction showed that structure of compounds consist of non-charged ladder-type chains formed by [Re4Te4(CN)12]4− cluster anions and dimeric cationic complexes [Ln(phen)(H2O)3Ln(phen)(H2O)2(μ-OH)2]4+. Chains are packed parallel and linked with each other by a system of hydrogen bonds. The magnetic susceptibility of compounds is determined by exchange coupled Ln3+ ions in dimeric cationic fragments. The anisotropy effects take place and cause non-linear field dependencies of magnetization for the complexes.

The first luminescent twelve-nuclear rhenium cluster complexes were obtained. Three new clusters, namely, [Re12CS14(μ-Cl)3Cl6]5-, [Re12CS14(μ-Br)3Cl6]5- and [Re12CS14(μ-Br)3Br6]5-, were synthesized using the non-isovalent substitution of μ-O ligands within the {Re12CS14(μ-O)3}0 cluster core by halide anions. The geometry of the new clusters was investigated by X-ray structural analysis, and the electronic structures were evaluated by the use of DFT calculations. It was found that compounds based on these anions showed red luminescence in both the solid state and solution that was never observed before for previously studied twelve-nuclear rhenium clusters.

Influence of the metal core composition and geometry on the structure, spectroscopic properties and redox potentials was investigated for the first time for heterometallic (Re/Mo)

Three new polymeric compounds with general formula {[Gd(phen)(H2O)3Gd(phen)(H2O)2(μ-OH)2][Re4Q4(CN)12]}·nH2O (Q = S0.84Te0.16, n = 0.25 for compound 1; Q = Se, Te, n = 1 for compounds 2, 3, respectively) were obtained by self-assembly reaction of [Re4Q4(CN)12]4− cluster anions, Gd3+ cation and 1,10-phenthroline (phen) in a solvothermal conditions. Compounds were investigated by single-crystal X-ray diffraction, magnetic measurements and thermogravimetric analysis. Structure of compounds consist of non-charged ladder chains formed by alternating [Re4Q4(CN)12]4− cluster anions and dimeric cationic complex [{Gd(phen)(H2O)3Gd(phen)(H2O)2(μ-OH)2}]4+ connected through –C N–Gd–N C– covalent bonds. Chains are packed parallel and linked with each other by a system of hydrogen bonds. The magnetic susceptibility of compounds is determined by spins of Gd3+ ions that weakly antiferromagnetic coupled in dimeric cationic fragments.

Self-assembly reaction of [Re 4 Te 4 (CN) 12 ] 4– tetrahedral rhenium chalcocyanide cluster anions, Tm 3+ cations and 1,10-phenanthroline in an H 2 O/EtOH medium was investigated at different temperatures. Slow mixing of reagent solutions at the room temperature lead to formation of cluster compound ( 1 ) containing unique trimeric anionic fragment [{Tm(phen) (H 2 O) 4 }{Tm(phen) 2 (H 2 O) 3 }{Tm(phen) 2 (H 2 O) 2 }{Re 4 Te 4 (CN) 12 } 3 ] 3− ( A1 , phen = 1,10-phenanthroline). Oligomeric anion A1 shows an unusual U-shaped structure build from three cluster anions and three {Tm(phen) n (H 2 O) m } 3+ ( n = 1, 2; m = 2–4) complex cations linked to each other by C N Tm N C covalent bonds and two couples of short OH…N hydrogen bonds. At the elevated (80–100 °C) temperatures the initial reaction products were dissolved, however, further increase of temperature up to 150 °C resulted in formation of layered (2D) coordination polymer K[{Tm(phen) (H 2 O) 3 }{Re 4 Te 4 (CN) 12 }]·0.5H 2 O ( 2 ). In addition to the experimental and X-Ray structural analysis data, thermal decomposition of compounds is also discussed.

Tungsten trioxide has been found to be a convenient precursor for the synthesis of metal cluster compounds with new types of cluster cores. The reaction between WO3 and KCN led to the formation of the cluster complex [{W6(μ4-O)2(μ3-CCN)4}(CN)16]10-. Unexpectedly, it includes the fully deprotonated form of acetonitrile, the CCN3- anion, as a μ3-bridging ligand coordinated to the trigonal faces of the bitetrahedral W6 metallocluster. A similar complex [{W6(μ4-O)2(μ3-As)4}(CN)16]10- containing μ3-As3- ligands instead of μ3-CCN3- ones has been synthesized by the reaction between WO3, As and KCN.

Cluster compounds based on a new {Re

The redox-active rhenium octahedral cluster unit [Re6Se8(CN)6]4– was combined with Gd3+ ions and dicarboxylate linkers in novel types of metal–organic frameworks (MOFs) that display a set of functi...

Compounds with general formula (bipyH2)[{Ln(H2O)6}{Re4Te4(CN)12}]2·10H2O (Ln = Gd (1), Dy (2), Tb (3), Ho (4), Er (5)) were obtained by evaporation of acidic aqueous solution containing salts of [Re4Te4(CN)12]4− cluster anion, respective lanthanide cation and 4,4′-bipyridine. Structures of compounds 1–5 consist of dimeric cluster fragments [{Ln(H2O)6}{Re4Te4(CN)12}]22−, forming supramolecular ionic structure with outer-sphere 4,4′-bipyridinium cations and H2O molecules. Magnetic susceptibility of all compounds in the range of temperature 80–300 K was measured; thermal stability was also investigated.

International audience; Control of covalent coordination polymer structures using non-covalent interactions is a promising way for obtaining functional materials by self-assembly in solution. Here we report the crucial role of halide anions in the formation of interpenetrating frameworks based on cyanometalate clusters. It was found that the interaction of [Re3Mo3Se8(CN)(6)](5-) cluster anions and Cd2+ cations in aqueous ammonia led to the formation of the 1D polymeric compound {[Cd(NH3)(5)](2)[Cd(NH3)(4)](3)[Re3Mo3Se8(CN)(6)](2)}5H(2)O (1). Compound 1 is unstable outside the mother liquor due to the rapid loss of NH3 and H2O molecules. Addition of KX (X = Cl, Br, I) to the reaction mixture led to selective formation of 3D framework compounds {[Cd(NH3)(4)](3)[Re3Mo3Se8(CN)(6)]}X (2-4 for X = Cl, Br, I, respectively) stabilized by N-HX hydrogen bonding. Compounds 2-4 demonstrate high thermal stability as well as reversible loss of ammonia and reversible oxidation in the solid state.

Three new salts of tetrahedral rhenium chalcocyanide cluster anions [Re4Q4(CN)12]4− (Q = S, Se, Te) and 1,10-phenanthroline-1-ium cations, (phenH)4[Re4S4(CN)12]·6H2O (1), (phenH)4[Re4Se4(CN)12]·6H2O (2), and (phenH)4[Re4Te4(CN)12]·10H2O (3), have been synthesized by reactions of K4[Re4Q4(CN)12]·nH2O with 1,10-phenanthroline in the presence of Nd3+ in an acidic aqueous medium (pH 4). 1 and 2 exhibit similar 2-D layered supramolecular architectures based on hydrogen bonds between water molecules, CN-groups of cluster anions, and phenH+ cations. The latter are involved in π–π and C–H⋯π stacking interactions, connecting the adjacent layers with each other. Complex 3 demonstrates a 3-D framework based on hydrogen bonds between water molecules and CN-groups, π–π and C–H⋯π interactions. Notably short O···Te contacts of 3.40 and 3.50 Å are found in the structure of 3. The thermal properties of 1–3 have been investigated by TG-DTG.

The reaction between ZnCl2 and an aqueous solution of CaK4[Re3Mo3S8(CN)6]·8H2O is controlled by the concentration of NH3. High concentration of NH3 favors the formation of [Zn(NH3)4]8{Zn[Re3Mo3S8(CN)6]3}·9H2O with an ideal primitive cubic 3D network of Zn2+ cations joined by cyanocluster anions acting as unprecedented bulky linear spacers. The low concentration of NH3 leads to the formation of the usual Prussian blue structure [Zn(NH3)4]2[ZnRe3Mo3S8(CN)6]·2H2O with alternating octahedral Zn2+ and cyanocluster nodes. Both compounds contain a paramagnetic cluster anion with g = 2.279 and 2.280, respectively. Powder diffraction studies prove that the former compound transforms into the latter after the exposure of a polycrystalline sample to air.

Selective substitution of μ-SO

The first example of dodecanuclear chalcohalide rhenium cluster complex, (Et4N)4(Me2NH2)2[Re12CS17Br6] (1), has been synthesized by reaction of polymeric cluster solid Re12CS17 with excess of Et4NBr in boiling DMF. The compound was characterized by a set of methods, including IR and UV–Vis spectroscopy, elemental analysis, EDS, mass-spectrometry, single-crystal X-ray diffraction analysis, and quantum-chemical calculations. The crystal structure presents an interesting case of 1D supramolecular architecture based on notably short Br⋯Br interactions of 3.432 A between the terminal bromide trans-ligands of adjacent [Re12CS17Br6]6− cluster anions. The DFT calculations performed for the [Re12CS17Br6]6− anion showed good agreement between calculated and experimental data.

The unique dodecanuclear cluster compound Re12CS17 was prepared and studied by X-ray, complex impedance method and density functional theory (DFT). The compound is amorphous, possesses semiconducting properties. Computer simulations showed that the Re and S atoms at the external borders of the neighboring molecules Re12CS17 can form sufficiently strong Re•••S intermolecular bonds, similar to the Mo•••S intermolecular bonds of cuboctahedron Mo6S8 molecules in the Chevrel phases. (doi: 10.5562/cca1973)

The reaction of the cluster salt K4[Re4Te4(CN)12]·5H2O with NdCl3·6H2O was studied in either an acidic medium (HCl) or in a water solution in the presence of the following organic agents: hexafluoroacetylacetonate, 2,2′-bipyridine or 1,10-phenanthroline (phen). The crystal structures of four new compounds have been solved by single crystal X-ray diffraction analysis: (H)[{Nd(H2O)5}{Re4Te4(CN)12}]·5.5H2O (1) (space group P21/c, framework structure), K2[{Nd(H2O)7}2{Re4Te4(CN)12}2]·8H2O (2) (space group С2/c, isolated structure), K0.5H0.5[{Nd(H2O)5}{Re4Te4(CN)12}]·3H2O (3) (space group Сmcm, layered structure) and (phenH)[{Nd(H2O)2(phen)2}{Re4Te4(CN)12}]·11H2O (4) (space group С2/c, chain structure). 1,10-Phenanthroline was found to have been incorporated into the structure of compound 4, whilst hexafluoroacetylacetonate and 2,2′-bipyridine did not enter the structures of 2 and 3. It was shown that the structures of compounds 2–4 differ dramatically from that found for compound 1, which was obtained in the absence of the organic agents.