Binuclear Cation Research Articles

Double Pseudo-Polymeric Gold(III)-Mercury(II) Complexes [Au(S2CNR2)2]nX [R2 = (CH2)6, (CH2)4O] Containing ([HgCl3]−)n, [HgCl4]2− and [Hg2Cl6]2− Anions: Chemisorption Synthesis, Principles of Supramolecular Self-Assembly, and Thermal Behavior

Novel pseudo-polymeric complexes of gold(III)-mercury(II) with cyclic alkylene dithiocarbamate ligands: ([Au{S2CN(CH2)6}2][HgCl3])n, ([Au{S2CN(CH2)6}2]2[HgCl4]·H2O)n, and ([Au{S2CN(CH2)4O}2]2[Hg2Cl6])n have been obtained and structurally characterized. The sophisticated supramolecular structure of the obtained compounds is realized due to secondary non-valent Au⋯S interactions and includes mononuclear and binuclear cations and anions as structural units as well as cationic and anionic polymer chains. The thermal behavior of the obtained complexes has been studied by means of simultaneous thermal analysis. The products of thermal transformations of the complexes are reduced elemental gold and HgCl2.

Low-temperature selective oxidation of methane over distant binuclear cationic centers in zeolites

Highly active oxygen capable to selectively oxidize methane to methanol at low temperature can be prepared in transition-metal cation exchanged zeolites. Here we show that the α-oxygen stabilized by the negative charges of two framework aluminum atoms can be prepared by the dissociation of nitrous oxide over distant binuclear cation structures (M(II)…M(II), M = cobalt, nickel, and iron) accommodated in two adjacent 6-rings forming cationic sites in the ferrierite zeolite. This α-oxygen species is analogous to that known only for iron exchanged zeolites. In contrast to divalent iron cations, only binuclear divalent cobalt cationic structures and not isolated divalent cobalt cations are active. Created methoxy moieties are easily protonated to yield methanol, formaldehyde, and formic acid which are desorbed to the gas phase without the aid of water vapor while previous studies showed that highly stable methoxy groups were formed on isolated iron cations in iron exchanged ZSM-5 zeolites.

Binuclear Mercury(I) Complex with D-Gluconic Acid

Mercury(II) oxide has been reacted with D-gluconic acid (Gl) in an aqueous solution at a molar ratio of the reagents equal to 1: 2 to obtain mercury complex Hg2(C6H11O7)2 (I). The product isolated has been studied by elemental analysis, molar conductivity, IR, electronic, and NMR spectroscopy, and X-ray diffraction. The data obtained indicate that the compound contains the binuclear cation (Hg2)2+. It has been found that the complex has a chelate structure. Each mercury atom in I is connected with two oxygen atoms: one from the carbon atom of the carboxyl group and another from the hydroxyl group at the second carbon atom in the Gl molecule. Two gluconate ions in the complex have different configurations. Toxicity of I is ten times less than the toxicity of the starting mercury compound. Reacting Gl with the oxide of divalent mercury in an aqueous medium decreased he toxicity of the mercury compound due to its reduction to a formally monovalent state. The results can be useful for studying mercury detoxification and the application of Gl.

Synthesis and Structure of Ruthenium Complexes $$\rm[{Ph_{3}PR]_2^+[RuCl_6]^{2-}}$$ [ P h 3 P R ] 2 + [ R u C l 6 ] 2 − (R = C2H5, CH=CHCH3, CH2CH=CHCH3, CH2OCH3), and $$\rm[{Ph_{3}PCH_2CH=CHCH_2{PPh_3}]_2^{2+}[Ru_2Cl_{10}O]^{4-}}$$ [ P h 3 P C H 2 C H = C H C H 2 P P h 3 ] 2 2 + [ R u

Complexes \(\rm[{Ph_{3}PR]_2^+[RuCl_6]^{2-}}\), where R = C2H5 (I), CH=CHCH3 (II), CH2CH=CHCH3 (III), and CH2OCH3 (IV), have been prepared by the reaction between ruthenium(III) chloride hydrate and triphenylorganylphosphonium chlorides in dimethylsulfoxide in the presence of hydrochloric acid. A hydrochloric acid solution of ruthenium(III) chloride hydrate when mixed with an aqueous solution of 2-butylene-1,4- bis(triphenylphosphonium dichloride) followed by recrystallization from dimethylsulfoxide results in complex \(\rm[{Ph_{3}PCH_2CH=CHCH_2{PPh_3}]_2^{2+}[Ru_2Cl_{10}O]^{4-}}\)· 4H2O (V). According to X-ray diffraction data, phosphorus atoms in mono- and binuclear cations have slightly distorted tetrahedral coordination (CPC 105.54(13)°−113.00(8)°, P−C 1.758(9)−1.839(7) A). In slightly distorted octahedral anions [RuCl6]2− of complexes I–IV, the Ru−Cl bond lengths vary in the range 2.3222(6)−2.340(2) A; the cis-ClRuCl and trans-ClRuCl angles are 89.133(18)°–90.867(18)° and 179.53(13)°–180°, respectively. In the binuclear [(RuCl5)2O]4− anion of complex V, RuCl5 fragments are bonded by a bridging oxygen atom. The Ru–Cl bond lengths fall in the range 2.3375(8)−2.3957(8) A; the Ru–O bond length is 1.7832(2) A. The cis-ClRuCl, trans-ClRuCl, cis-ORuCl, and trans-ORuCl angles are 86.67(3)°−91.28(3)°, 174.60(3)°−174.83(3)°, 91.49(2)°−93.65(2)°, and 178.39(2)°, respectively. In crystals I–V, interionic hydrogen bonds Cl···Hcation (2.63−2.95 A), Cl··· \({\rm{H}_{{H_2}O}}\) (2.35−2.79 A), and Hcation···\({\rm{O}_{{H_2}O}}\) (1.72−1.93 A) (for V) are found.

Binding of Gold(III) from Solutions with Thallium(I) Dibutyldithiocarbamate: Synthesis, Supramolecular Self-Organization, and Thermal Behavior of the Complex ([Au{S2CN(C4H9)2}2][TlCl4])n

The binding of gold(III) from solution in a 2 M HCl with thallium(I) dibutyl dithiocarbamate leads to the formation of ion-polymeric complex ([Au{S2CN(C4H9)2}2][TlCl4])n, which was studied by (13С, 15N) MAS NMR spectroscopy and X-ray diffraction analysis. In the complex comprising the nonequivalent cations [Au{S2CN(C4H9)2}2]+ (A and B) and anions [TlCl4]–, the supramolecular self-assembly is provided by secondary bonds Au···S and S···Cl. The former are involved in the formation of isomeric binuclear cations [А···А] and [В···В] that build the (···[А···А]···[В···В]···)n polymeric chain; the latter selectively combine the thallium(III) anions and the dimeric cations. Thermolysis of the complex is accompanied by gold recovery and release of TlCl.

Theoretical Analysis of Oxidative Carbonylation of Methanol: Saegusa’s Scheme of Dimethylcarbonate Synthesis over Binuclear Cationic Oxo-Clusters in CuNaX Zeolite

Possible mechanism of oxidative carbonylation of methanol via >Cu(OCH3)2Cu< binuclear cationic oxo-clusters in the CuNaX zeolite with Cu2+ cations is analyzed theoretically within the scope of periodic boundary conditions with VASP. Such scheme was first derived by Saegusa et al. (J. Org. Chem.1970, 35, 2976) and was never tested by theoretical modeling to our best knowledge. For the CO attack we have computed the activation energy value that is close to experimental values obtained in Cu-zeolites. We suppose that this scheme can correctly describe the oxidative carbonylation at medium and high Cu loading when the copper oxo-clusters can be formed.

Ultrafast Wiggling and Jiggling: Ir2(1,8-diisocyanomenthane)42.

Binuclear complexes of d8 metals (PtII, IrI, RhI,) exhibit diverse photonic behavior, including dual emission from relatively long-lived singlet and triplet excited states, as well as photochemical energy, electron, and atom transfer. Time-resolved optical spectroscopic and X-ray studies have revealed the behavior of the dimetallic core, confirming that M-M bonding is strengthened upon dσ* → pσ excitation. We report the bridging ligand dynamics of Ir2(1,8-diisocyanomenthane)42+ (Ir(dimen)), investigated by fs-ns time-resolved IR spectroscopy (TRIR) in the region of C≡N stretching vibrations, ν(C≡N), 2000-2300 cm-1. The ν(C≡N) IR band of the singlet and triplet dσ*pσ excited states is shifted by -22 and -16 cm-1 relative to the ground state due to delocalization of the pσ LUMO over the bridging ligands. Ultrafast relaxation dynamics of the 1dσ*pσ state depend on the initially excited Franck-Condon molecular geometry, whereby the same relaxed singlet excited state is populated by two different pathways depending on the starting point at the excited-state potential energy surface. Exciting the long/eclipsed isomer triggers two-stage structural relaxation: 0.5 ps large-scale Ir-Ir contraction and 5 ps Ir-Ir contraction/intramolecular rotation. Exciting the short/twisted isomer induces a ∼5 ps bond shortening combined with vibrational cooling. Intersystem crossing (70 ps) follows, populating a 3dσ*pσ state that lives for hundreds of nanoseconds. During the first 2 ps, the ν(C≡N) IR bandwidth oscillates with the frequency of the ν(Ir-Ir) wave packet, ca. 80 cm-1, indicating that the dephasing time of the high-frequency (16 fs)-1 C≡N stretch responds to much slower (∼400 fs)-1 Ir-Ir coherent oscillations. We conclude that the bonding and dynamics of bridging di-isocyanide ligands are coupled to the dynamics of the metal-metal unit and that the coherent Ir-Ir motion induced by ultrafast excitation drives vibrational dephasing processes over the entire binuclear cation.

Preparation, characterization and biological evaluation of two chiral binuclear copper(II) complexes

Two chiral Cu(II) complexes of [Cu2(R‐L)2](PF6)2·2C2H5OH (1) and [Cu2(S‐L)2](PF6)2·2C2H5OH (2) (HL = 2‐(Bis(quinolin‐2‐ylmethyl)amino)‐1‐propanol) were designed and synthesized to serve as chemical nucleases and anticancer drugs. X‐ray crystallography revealed that two complexes contain chiral binuclear cations and PF6− anions. The interaction of two complexes with CT‐DNA was researched via various spectroscopic techniques and viscosity measurement, indicating that the complexes were bound to CT‐DNA by a classical intercalation binding mode. In addition, the two complexes exhibited remarkable DNA cleavage activity with an optimal dosage of 10 μM in the absence of any exogenous oxidant agent. Both of the complexes showed excellent in vitro cytotoxicity on A549 cell lines with IC50 values in the low micromolar range. Moreover, complex 2 could damage DNA of A549 cells into fragmentation and then induced cell apoptosis in a dose‐dependent manner, which was demonstrated by comet assay and Hoechst 33342 staining experiment. Further research showed that complex 2 could also induce G2 and S phase cell cycle arrest.

Crystal structure of meso-di-μ-chlorido-bis-[bis-(2,2'-bi-pyridine)-cadmium] bis-(1,1,3,3-tetra-cyano-2-ethoxy-propenide) 0.81-hydrate.

The hydrated title salt, [Cd2Cl2(C10H8N2)4](C9H5N4O)2·0.81H2O, was obtained from the hydro-thermal reaction between 2,2'-bi-pyridine, cadmium(II) chloride and potassium 1,1,3,3-tetra-cyano-2-eth-oxy-propenide. The binuclear cation lies across a centre of inversion in the space group P21/c, with the other components in general positions. The cation has approximate, but non-crystallographic 2/m symmetry and each of the CdII atoms is a stereogenic centre, one having the Δ configuration and the other the Λ configuration. In the anion, one of the C(CN)2 units is disordered over two sets of atomic sites having occupancies 0.75 (2) and 0.25 (2). The cations are linked by two independent C-H⋯Cl hydrogen bonds to form a sheet of R22(14) and R42(24) rings.

Effect of the counterion and guest molecules on the crystal structures of the coordination compounds with the Cu2(HL) 2 2+ cation (H2L = 4,4’-[2-(3-hydroxyiminobutyl)imino]biphenyl): Syntheses, structures, and magnetic properties

The molecular and crystal structures of complexes [Cu2(HL)2(CH3OH)2](BF4)2 ∙ C6H3Cl3 (I), [Cu2(HL)2(H2O)2](1,4-O2CС6Н4CO2) (II), and [Cu2(HL)2(H2O)2](4,4’-O2CС6Н4С6Н4CO2) (III) (H2L is 4,4’-[2-(3-hydroxyiminobutyl)imino]biphenyl, C6H3Cl3 is 1,2,4-trichlorobenzene) are determined by X-ray diffraction analyses. The crystalline lattices of complexes I and II contain discrete binuclear cations Cu2(HL) 2 2+ , whereas the crystalline lattice of compound III contains both discrete cations Cu2(HL) 2 2+ and polymer chains [Cu2(HL) 2 2+ ]n. In compounds I–III, the crystalline lattice units are joined by hydrogen bonds. The analysis of the temperature dependence of the magnetic susceptibility shows that the magnetic properties of compound III are determined only by antiferromagnetic interactions of the Cu2+ ions within the cations Cu2(HL) 2 2+

μ-N,N,N′,N′-Tetrakis(pyridin-2-ylmethyl)butane-1,4-diamine]bis[(dimethanol-κO)(perchlorato-κO)copper(II)] bis(perchlorate)

The binuclear cation of the title compound, [Cu2(ClO4)2(C28H32N6)(CH3OH)4](ClO4)2, is located on an inversion centre. The CuIIatom adopts a distorted octahedral coordination geometry due to the Jahn–Teller effect. The equatorial plane consists of one methanol molecule and three N atoms from theN,N,N′,N′-tetrakis(pyridin-2-ylmethyl)butane-1,4-diamine ligand. The Cu—N bond lengths are in the range 1.975 (3)–2.041 (2) Å and the Cu—O bond length is 2.008 (2) Å. The axial coordination sites of the CuIIatom are occupied by the O atoms of one methanol molecule and one perchlorate anion, with Cu—O bond lengths of 2.385 (3) and 2.565 (3) Å, respectively. In the crystal, the cations and the perchlorate anions are connectedviaO—H...O hydrogen bonds. In addition, weak C—H...O interactions stabilize the structure.

Crystal structure of bis-(μ-2-benzoyl-benzoato-κ(2) O:O')bis-[bis-(2,2'-bi-pyridine-κ(2) N,N')manganese(II)] bis-(perchlorate).

The title compound, [Mn2(C6H5COC6H4COO)2(C10H8N2)4](ClO4)2, comprises a centrosymmetric binuclear cation and two perchlorate anions. In the complex cation, two MnII atoms are bridged by two O atoms of two different 2-benzoyl­benzoate ligands, each MnII atom being further coordinated by two 2,2′-bi­pyridine (bipy) ligands in a distorted octa­hedral environment. Within the binuclear mol­ecule, the Mn⋯Mn separation is 4.513 (7) Å. Inter­molecular C—H⋯O and C—H⋯ π inter­actions link the mol­ecules into a three-dimensional network.

Individual forms of gold(III) binding from solutions with zinc N,N-cyclo-hexamethylenedithiocarbamate: Structural self-organization and thermal behavior of gold complexes of composition [Au{S2CN(CH2)6}2][AuCl4] and ([Au{S2CN(CH2)6}2]3[AuCl4][AuCl2]2) n

A reaction of binuclear zinc N,N-cyclo-hexamethylenedithiocarbamate with [AuCl4]− anions in 2 M HCl solution was studied. Two types of crystals, plates and needles, were obtained from acetone solution of products of the heterogeneous reaction; the crystals are complexes of composition [Au{S2CN(CH2)6}2][AuCl4] (I) and ([Au{S2CN(CH2)6}2]3[AuCl4][AuCl2]2)n (II). Crystal and supramolecular structures of the prepared compounds were established by X-ray diffraction analysis. The structure of ionic complex I is built of alternating discrete [Au{S2CN(CH2)6}2]+ cations and [AuCl4]− anions. A complex supramolecular structure II, which includes isomeric [Au{S2CN(CH2)6}2]+ cations (A and B) with different structur functions, is formed due to secondary Au⋯S and Au⋯Cl bonds. Non-centrosymmetric cations B unite via pairs of secondary Au⋯S bond to form binuclear species [Au2{S2CN(CH2)6}4]2+ which together with centrosymmetric cations A participate in formation of polymeric chains (⋯[B⋯B]⋯A⋯)n. Moreover, each cation A binds a pair of [AuCl2]− anions due to secondary Au⋯S bonds. In its turn, [AuCl4]− anions unite the chains into 2D polymeric network to produce pairs of secondary Cl⋯Au bonds with gold atoms of binuclear cations [Au2{S2CN(CH2)6}4]2+ of neighboring chains. Thermal behavior of the complexes was studied by simultaneous thermal analysis and conditions of recovery of bound gold were revealed. The thermal destruction of I and II proceeds via intermediate stages of formation of Au2S and AuCl. Reduced elemental gold is the final product of thermal transformations of the complexes.

Bi-Nuclear Metal Complexes of 2,6-Bis(1,4,7-triazacyclonon-1-yl-methylene)pyridine with Zinc(II), Copper(II), and Nickel(II)

The coordination chemistry of 2,6-bis(1,4,7-triazacyclonon-1-ylmethyl)pyridine (Lpyx, 1) has been investigated and shown to yield bi-nuclear metal complexes in the presence of zinc(ii), copper(ii), or nickel(ii) ions. The reaction of (Lpyx)·7HCl (2) with Zn(NO3)2 gave the monomeric [Zn2(μ-Cl)2(Lpyx)(H2O)](ClO4)2 (3) in which the ligand encapsulates a Zn2(μ-Cl)2 moiety. Similar treatment of 2 with Cu(NO3)2 gave a bi-nuclear complex cation which exists as a 1 : 1 co-crystal {[Cu(Cl)(Lpyx)Cu(μ-Cl)(Cl)](BF4)(H2O)}2 and {[Cu(Cl)(Lpyx)Cu(μ-Cl)(H2O)](BF4)2(H2O)}2 (4) with two discrete CuII centres bridged by the Lpyx ligand and dimerised through an unsymmetrical Cu2(μ-Cl)2 interaction. Similarly, reaction of 2 with Ni(NO3)2 also gave a dimeric complex {[Ni(Cl)(μ-Cl)(Lpyx)Ni(NO3)(H2O)](PF6)}2 (5) containing two discrete NiII centres with dimerisation occurring through a symmetrical Ni2(μ-Cl)2 interaction. In all cases, the Lpyx ligand binding is unsymmetrical between the two metal centres being tridentate to one and tetradentate to the other through an additional coordination of the pyridyl linker.

Broken symmetry approach to density functional calculation of zero field splittings including anisotropic exchange interactions

The broken symmetry approach to the calculation of zero field splittings (or magnetic anisotropies) of multinuclear transition metal complexes is further developed. A procedure is suggested how to extract spin Hamiltonian parameters for anisotropic exchange from a set of broken symmetry density functional calculations. For isotropic exchange coupling constants Jij, the established procedure is retrieved, and anisotropic (or pseudodipolar) exchange coupling tensors Dij are obtained analogously. This procedure only yields the sum of the individual single-ion zero field splitting tensors Di. Therefore, a procedure based on localized orbitals has been developed to extract the individual single-ion contributions. With spin Hamiltonian parameters at hand, the zero field splittings of the individual spin multiplets are calculated by an exact diagonalization of the isotropic part, followed by a spin projection done numerically. The method is applied to the binuclear cation [LCr(OH)3CrL](3 +) (L = 1,4,7-trimethyl-1,4,7-triazanonane) for which experimental zero field splittings for all low-energy spin states are known, and to the single-molecule magnet [Fe4(CH3C(CH2O)3)2(dpm)6] (Hdpm = 2,2,6,6-tetramethylheptane-3,5-dione). In both these 3d compounds, the single-ion tensors mainly come from the spin-orbit interaction. Anisotropic exchange is dominated by the spin-dipolar interaction only for the chromium compound. Despite the rather small isotropic exchange couplings in the iron compound, spin-orbit and spin-dipolar contributions to anisotropic exchange are of similar size here.

Synthesis, crystal structure and magnetic properties of a new cyanide-bridged mixed-valence copper(I)/copper(II) clathrate

Abstract A unique cyanide-bridge mixed-valence CuI/CuII clathrate of formula [CuI2(CN)3][{CuII(tren)}2(μ-CN)](CF3SO3)2 [tren = tris(2-aminoethyl)amine] containing cyanide-bridged [{CuII(tren)}2(μ-CN)]3 + binuclear cations stacked between anionic honeycomb layered copper(I) cyanide networks, was synthesized and structurally characterized by single crystal X-ray diffraction. Variable-temperature magnetic susceptibility studies showed that the cyanide bridge mediates a strong antiferromagnetic interaction between the copper(II) centers (J = − 160 cm− 1, the spin Hamiltonian being defined as H = −J SA⋅SB).

Crystal structure of hexakis(thiourea)-bis((μ-perchlorato-O,O’)-(perchlorato-O)-bismuth) diperchlorate

The complex[Bi2(Tu)6(ClO4)4](ClO4)2 (I) (Tu is thiourea) was synthesized and studied by X-ray diffraction. The crystallographic data of I are: a = 14.205(1) A, b = 13.083(1) A, c = 22.078(2) A, β = 96.182(1)°, V = 4079.1(7) A3, space group C2/c, Z = 4. The molecule is located on a twofold axis and consists of the binuclear cation [Bi2(Tu)6(ClO4)4]2+ and two outer-sphere anions Cl 4 − . The Bi-S bond lengths are 2.61–2.62 A. For each terminal and bridging ClO 4 − ion, one Bi-O distance varies from 2.744 to 3.048 3.269 structure contains a hydrogen bond network involving all hydrogen atoms. The IR and Raman spectroscopy data confirm the thiourea coordination by the sulfur atom.

Bis[μ-(3-acetyl-2-hy-droxy-6-methyl-4H-pyran-4-one-κ(3)O:O',O'')]diaqua-tetra-kis-(pyridine-κN)dicopper(II) diperchlorate.

In the centrosymmetric binuclear cation of the title compound, [Cu(C8H7O4)(H2O)(C5H5N)2]2(ClO4)2, the CuII atoms are bridged by a pair of two dehydro­acetate anions in a bis-/monodentate mode. The distorted octa­hedral N2O4 coordination sphere of the metal cation is completed by two pyridine N atoms and one O atom of a water mol­ecule. The complex cations and the perchlorate counter anions are arranged in layers parallel to (100). O—H⋯O hydrogen bonds between the coordinating water mol­ecules and the perchlorate anions constitute ribbons parallel to [10-1]. C—H⋯O hydrogen bonds are also observed.

Oxidative Dimerization of Aryldiynyl–Ruthenium Complexes

Chemical oxidation of Ru(C≡CC≡CR)(dppe)Cp with [FeCp2]PF6 affords the binuclear cations [{Ru(dppe)Cp}2C8R2]2+(PF6–)2 (R = Ph, 72+(PF6–)2; R = Fc, 82+(PF6–)2) by radical coupling at electron-rich sites involving the inner and outer C≡C triple bonds, to give cyclobutenediylidene derivatives. In each case, mixtures of symmetrical and asymmetrical isomers were obtained (2:1 for 72+(PF6–)2, 1:1 for 82+(PF6–)2), shown by single-crystal X-ray diffraction structure determinations of 72+-asym(PF6–)2 and 82+-sym(AsF6–)2. 82+-sym consists of a central C4 ring with two ═C═C═Ru(dppe)Cp groups in the 1,2-positions and two Fc substituents in the 3,4-positions, whereas for 72+-asym the substituent ═Ru(dppe)Cp is in the 1-position, ═C═C═Ru(dppe)Cp is in the 2-position, Ph is in the 3-position, and −C≡CPh is in the 4-position. DFT calculations reveal that the precursor cationic diynyl complexes show important electron density on Cβ and Cδ, suggesting that radical coupling (Cδ + Cδ) or (Cβ + Cδ) affords the sym and asym iso...

Fixation modes of gold(III) from solutions using cadmium(II) dithiocarbamates. Preparation, supramolecular structure and thermal behaviour of polynuclear and heteropolynuclear gold(III) complexes: Bis(N,N-dialkyldithiocarbamato-S,S′)gold(III) polychlorometallates, [Au(S2CNR2)2]nX (n = 1: X = [AuCl4]−; n = 2: X = [CdCl4]2−, [Cd2Cl6]2−)

Four novel heteropolynuclear and polynuclear complexes of the general formulae [Au(S2CNR2)2]2X (X=[CdCl4]2−, R=CH3 (1); X=[Cd2Cl6]2−, R=C3H7 (2)) and [Au(S2CNR2)2][AuCl4] (R=iso-C3H7 (3); R=iso-C4H9 (4)) were prepared using heterogeneous reactions between appropriate freshly precipitated binuclear cadmium(II) dialkyldithiocarbamates and AuCl3 in 2M hydrochloric acid. The isolated complexes were studied by 13C CP/MAS NMR spectroscopy, single-crystal X-ray diffraction and simultaneous thermal analysis (STA) under an argon atmosphere. In all molecular structures (1–4), one of the gold atoms coordinates two dialkyldithiocarbamate ligands in the S,S′-bidentate mode, forming a square-planar coordination polygon [AuS4], while the other gold atom (in 3 and 4) has four neighbouring chlorine atoms [AuCl4]. At the supramolecular level, compounds 1 and 2 comprise binuclear cations, [Au2{S2CN(CH3)2}4]2+ and polynuclear chains, ([Au{S2CN(C3H7)2}2]+)n in a combination with [CdCl4]2− and [Cd2Cl6]2− anions, respectively. Unexpected structural distinctions at the supramolecular level were discovered for the chemically related compounds 3 and 4. In these ionic complexes, there are either cationic trinuclear formations, {[Au{S2CN(iso-C3H7)2}2]2[AuCl4]}+, or polynuclear chains, ([Au{S2CN(iso-C4H9)2}2]+)n, both combined with [AuCl4]− anions, in the structural basis of compounds 3 and 4, respectively.