Bridging Acetate Research Articles

Crystal structure of poly[[di-μ3-acetato-tetra-aqua-bis-(μ2-cyclo-hexane-1,4-di-carboxyl-ato)dilanth-an-um(III)] dihydrate

The title compound, {[La2(CH3COO)2(C8H10O4)2(H2O)4]·2H2O} n or [La2(ac)2(e,a-cis-1,4-chdc)2(H2O)4]·2H2O, where ac is acetate and 1,4-chdc is cyclo-hexane-1,4-di-carboxyl-ate anion, is a binuclear lanthanum(III) complex. Each metal atom is deca-coordinated by four O atoms from two distinct 1,4-chdc2- ligands, four O atoms from three acetate groups and two O atoms from coordinated water mol-ecules to form a distorted bicapped square-anti-prismatic geometry. Two non-coordinated water mol-ecules are also present in the formula unit. The most remarkable feature of this compound is that it possesses a only cis conformation for cyclo-hexane-1,4-di-carb-oxy-lic acid, although the raw material consists of a mixture of cis and trans isomers. The μ3-η2:η2 coordination mode of the bridging acetate group and the flexible di-carboxyl-ate fragments of 1,4-chdc2- results in the formation of infinite two-dimensional lanthanide-carboxyl-ate layers within the crystal structure. The directionality of strong inter-molecular O-H⋯O and weak C-H⋯O inter-actions provides robustness to the layers, which leads to the construction of a three-dimensional supra-molecular network. The crystal studied was refined as a two-component twin.

Effect of ligand exchange on the one-electron oxidation process of alkoxo or phenoxo bridged binuclear copper(II) complexes

In the present paper, we report on the influence of methanol/methoxide on the structure and the mono-electronic oxidation process of two different dicopper(II,II) complexes: a binuclear µ-alkoxo µ-acetato dicopper(II,II) complex obtained with a tetraamide-containing ligand (1) or a new unsymmetric µ-phenoxo, µ-hydroxo dicopper(II,II) complex based on a ligand bearing one bis(2-pyridylmethyl)aminomethyl arm (BPA) and one thiosemicarbazone (2). Structural data obtained from X-ray diffraction analysis showed that, in the case of complex 2, bridging hydroxide was replaced by a methoxide bound in a bridging mode (2-OMe). Concerning complex 1, redox properties were investigated by electrochemistry and rationalized using theoretical calculations. Our studies indicate that (i) the acetate bridge of 1 is decoordinated from the copper ions after mono-oxidation (ii) in presence of methoxide, acetate is released and a complex with two pendant exogen ligands (one methoxide and one solvent, 1-OMe-DMF) is a plausible structure although bridging methoxide cannot be excluded. In the case of 2 the anodic potentials are not influenced by the nature of the bridge (hydroxo in 2 or methoxo in 2-OMe). Finally, the computed redox potentials using DFT calculations are in good agreement with the experimental ones and indicates that in the case of the complexes derived from 1, oxidation is copper-centered therefore leading to Cu(II)Cu(III) species although oxidation is ligand-centered in the case of 2 and 2-OMe.

Synthesis and Structural Characterization of Trimanganese‐Containing Polyoxovanadates with Carboxylate Ligands

A trimanganese core containing polyoxovanadate {Et4N}5[Mn3(OAc)(H2O)V10O30] (I; OAc = acetate) was synthesized by the reaction of {Et4N}[VO3] with Mn(OAc)2 (0.3 equiv.) in acetonitrile. The trimanganese core possesses a bridging acetate ligand. To demonstrate the ligand‐exchange properties of I, its reaction with benzoic acid (1 equiv.) was conducted and {Et4N}5[Mn3(OBz)(H2O)V10O30] (II; OBz = benzoate) was formed quantitatively. By using a dicarboxylate, the inorganic–organic–inorganic hybrid {Et4N}10[{Mn3(H2O)V10O30}2{OOC(CH2)nCOO}] [n = 3 (III) and n = 4 (IV)] compounds were synthesized. To compensate the negative–negative repulsion between the anionic groups with a 5– charge, tetraethylammonium cations are sandwiched between the anionic groups in the crystallographic packing. Despite the differences in the bridging carbon numbers, both complexes have the same orientation in the crystal state except for the conformation of the alkyl chains, which suggests the presence of a unique interaction with an anion–cation–anion motif to form V‐shaped dimer configurations.

Rational design of triple-bridged dinuclear ZnIILnIII-based complexes: a structural, magnetic and luminescence study

Twelve novel dinuclear ZnII–LnIII complexes of general formula [Zn(μ-L)(μ-OAc)Ln(NO3)2] (LnIII = Y (1), Pr (2), Nd (3), Sm (4), Eu (5), Gd (6), Tb (7), Dy (8), Ho (9), Er (10), Tm (11), Yb (12)) have been prepared from the symmetric compartmental Mannich base ligand N,N′-dimethyl-N,N′-bis(2-hydroxy-3-methoxy-5-methylbenzyl)-ethylenediamine (H2L). Structural determinations indicate that in all these complexes, ZnII ions are pentacoordinated in the inner position of the ligand, linked to two nitrogen and two oxygen atoms from L2− and a bridging syn–syn acetate group. The LnIII ions are nonacoordinated in the outer position, linked to four oxygen atoms from L2−, two bidentate nitrate anions and the bridging acetate. Complexes 3, 6, 7, 8, 10 and 12 exhibit field induced slow relaxation of the magnetization. It should be remarked that this behaviour is very infrequent in GdIII and NdIII coordination compounds. For compounds 8 and 12, it was possible to extract the effective energy barrier (Ueff) for the reversal of the magnetization, with a value of 27.5 K (52.6 K considering the Raman relaxation process in addition to the Orbach mode) and 13.2 K for DyIII and YbIII compounds, respectively. Moreover, the photophysical properties of these complexes have been studied at different temperatures and show that L2− is able to sensitize luminescence emission of many lanthanide ions. SmIII, EuIII, TbIII, DyIII and TmIII-based compounds show fluorescence in the visible region, whereas the YbIII-based one is sensitized in the near-infrared (NIR) region. Therefore, complexes 7, 8 and 12 may be considered as dual magneto-luminescent materials.

New Heterodinuclear Zn/Ln (Ln = Gd, Tb, Er, Yb) Complexes of Hexadentate N,N′-Bis(3-alkoxy-2-hydroxybenzyl)cyclohexane-1,2-diamines: Synthesis and Structure

Two N,N′-bis(3-alkoxy-2-hydroxybenzyl)cyclohexane-1,2-diamine proligands, H2L1 (R = OCH3) and H2L2 (R = OC2H5), and five heterodinuclear ZnII/LnIII complexes, [Zn(L)(µ-CH3COO)Ln(NO3)2], containing [L1]2– and Gd3+, Tb3+, Er3+, or Yb3+ and [L2]2– and Yb3+ have been synthesised and structurally characterised. The complexes are isostructural and crystallise in the P21/n monoclinic space group. Zinc(ii) is coordinated by the inner N2O2 donor set of the ligand and an oxygen of the bridging acetate anion; the lanthanide(iii) ions possess an O9 coordination environment involving the interaction with the ligand’s outer O4 donor set, two bidentate nitrate ions, and the bridging acetate.

Synthesis, Electronic, Magnetic and Structural Characterization of New Trinuclear Mixed‐Valence CoIII‐CoII‐CoIII Complex.

AbstractThe structural, electronic, magnetic and theoretical study of the complex [Co3(HL)2(μ‐AcO)2(AcO)2], 1, (HL is the dianion obtained by deprotonation of N,N’‐bis(salicylidene)‐2‐hydroxy‐1,3‐propanediamine and AcO is acetate) shows that 1 crystallizes with two independent molecules in the asymmetric unit. Each molecule is a trinuclear complex. Both molecules have similar geometry, and correspond to a spin system based on trapped mixed valences on six‐coordinate metal centres, CoIII(s=0)‐CoII(s=3/2)‐CoIII(s=0). The rigid framework formed by the tetradentate Salen‐type ligands HL and the syn‐syn bridging acetate anions is a characteristic feature observed in other related complexes. However, the here reported compound is the first one in this family having Z’>1. UV‐Vis spectrum shows a broad band in the visible region where d‐d transition for ions CoIII and CoII are. EPR spectra and the electronic energy estimations of the ground state show the presence of two conformers s=3/2. The χMT product at 300 K is 3.24 emu mol−1K per trinuclear unit, this product is expected for CoII where the contribution of orbital angular moment is taken into account (3.38 emu mol−1K for L=3).

Two cadmium coordination polymers with bridging acetate and phenyl-enedi-amine ligands that exhibit two-dimensional layered structures.

Poly[tetra-μ2-acetato-κ8O:O'-bis-(μ2-benzene-1,2-di-amine-κ2N:N')dicadmium], [Cd2(CH3COO)4(C6H8N2)2] n , (I), and poly[[(μ2-acetato-κ2O:O')(acetato-κ2O,O')(μ2-benzene-1,3-di-amine-κ2N:N')cadmium] hemihydrate], {[Cd(CH3COO)2(C6H8N2)]·0.5H2O} n , (II), have two-dimensional polymeric structures in which monomeric units are joined by bridging acetate and benzenedi-amine ligands. Each of the CdII ions has an O4N2 coordination environment. The coordination geometries of the symmetry-independent CdII ions are distorted octa-hedral and distorted trigonal anti-prismatic in (I) and distorted anti-prismatic in (II). Both compounds exhibit an intra-layer hydrogen-bonding network. In addition, the water of hydration in (II) is involved in inter-layer hydrogen bonding.

Water inclusion mediated structural diversity and the role of H-bonds in molecular assemblies of manganese(III) bicompartmental Schiff-base complexes

Six new manganese(III) derivatives using the ligand H2MeOsalen: N,N′-ethylenebis(3-methoxysalicylaldiimine), have been synthesized and structurally characterized. In all cases the manganese ion is six-coordinated and occupies the internal cavity of the bicompartmental salen ligand. The manganese ion completes its coordination environment with one axial water molecule and one additional ligand, either water, ethanol or one acetate anion. The molecular unit is dimerized by the insertion of the coordinated water molecule into the external MeOsalen cavity of one neighbouring complex. This supramolecular dimer constitutes the structural basis for these compounds, the differences arising from the intermolecular hydrogen bonds involving the counter anions and crystallization solvent molecules. In this way, examples of pseudopolymorphism, cocrystallization and water/anion tapes held by the interaction with the complex dimers are described. The compound [{Mn(MeOsalen)K(H2O)0.5}2(μ-OOCMe)](PF6)3·HOCH2CH2OH is a heterometallic Mn/K derivative where the potassium ion occupies the external cavity, while the coordination of the manganese ion is completed by bridging acetate and ethyleneglycol ligands. The formation of ethyleneglycol is attributed to a stoichiometric oxidation of the ethanol solvent, attributed to the presence of the potassium ion in the complex.

Ln2Ga[B3O6(OH)]2[B7O9(OH)2](CH3CO2)2 (Ln = Y, Sm, Eu, Gd, Dy): A Series of Lanthanide Galloborates Decorated by Acetate Anions.

The first examples of mixed-anion lanthanide galloborates, namely, Ln2Ga[B3O6(OH)]2[B7O9(OH)2](CH3CO2)2 [Ln = Y (1), Sm (2), Eu (3), Gd (4), Dy (5)], have been obtained through hydrothermal synthesis. The title compounds are isomorphic and belong to monoclinic space group C2/c (No. 15). Their structures possess [B7O13(OH)2] borate layers further bridged with [B3O7] clusters to give a three-dimensional (3D) borate framework displaying two types of rhombus-like B14O14 14-membered-ring (14-MR) channels along the b axis. The Ga(3+) ions are octahedrally coordinated and located at one end of the B14O14 14-MR channels, forming small tunnels of B7Ga 8-MRs, which are filled by the Ln(III) ions. The Ln ions and Ga cations are further held together by bridging acetate anions. It is worth noting that in these compounds there are two different types of borate clusters and two types of anions that are uncommon in the borates reported. Luminescent studies revealed the characteristic emission bands of Ln ions for compounds 2-5, and the luminescent lifetimes are 3.6, 0.86, and 3.05 ns for compounds 2, 3, and 5, respectively. Magnetic measurements suggest that there are antiferromagnetic interactions between magnetic centers for compounds 2-5.

An Unusual 3D Zinc‐Organic Framework Constructed from Paddle‐Wheel‐Based Carboxylate Sheets Bridged by Acetate Ions

AbstractA zinc‐2,6‐naphthalenedicarboxylate metal‐organic framework, (H2NEt2)[Zn2(AcO)(NDC)2]·nDEF (1) (DEF = N,N‐diethylformamide, AcO = acetate), was solvothermally synthesized in the presence of small amounts of acetic acid and characterized by single‐crystal and powder X‐ray diffraction and thermogravimetric analysis. Compound 1 is an anionic 3D paddle‐wheel MOF, in which the zinc‐naphthalenedicarboxylate sheets are linked together by bridging acetate ions. Compound 1 exhibits large square channels (13 × 13 Å), which contain DEF molecules and, alternatively, charge‐balancing diethylammonium cations in situ generated by the hydrolysis of DEF under the solvothermal conditions used. The anionic host framework of 1 is unstable upon removal of guest DEF molecules suggesting that host‐guest hydrogen bond interactions are crucial for maintaining the structural integrity of this compound.

Ferromagnetic Polarization: The Quantum Picture of Switching On/Off Single-Molecule Magnetism.

The mixed 3d-4f pentanuclear complex (Bu4N)[Mn(III)4Y(III)(shi)4(OAc)4(CH3OH)4]·CH3OH·H2O (1) (H3shi = salicylhydroxamic acid) was synthesized by the direct reaction of Y(NO3)3·6H2O, Mn(OAc)2·4H2O, and H3shi. When an additional ligand, (NHBu3)3[W(CN)8]·2H2O, was added, the mixed 3d-4f-5d hexanuclear complex (Et4N)5[Mn(III)4Y(III)(shi)4(OAc)4W(V)(CN)8](WO4)0.5 (2) was obtained. X-ray crystallographic analysis shows that the 3d-4f complex 1 represents a 12-metallacrown-4 (12-MC-4) structure, in which the metallacrown ring [Mn-N-O]4 connection captures one Y(III) ion with four bridging acetate anions, completing the eight-coordinated environment around Y(III) ion, while four methanol molecules each coordinate to the Mn(III) ions on the other side of the Y(III) ion. After octacyanotungstate is introduced, the [W(V)(CN)8] group substitutes for four methanol molecules of 1 to form complex 2. Magnetic studies indicate the overall antiferromagnetic coupling present within the MC ring of complex 1. However, interestingly, the dominant ferromagnetic coupling between Mn(III) ions was observed in complex 2. A susceptibility analysis shows that the natural spin alignments in 12-MC-4 metallacrowns are tuned from overall antiferromagnetic to dominant ferromagnetic fashions by magnetic coupling between Mn(III) ions and the W(V) ion. Complex 1 [Mn(III)4Y(III)] retains an S = 0 ground state, and complex 2 [Mn(III)4Y(III)W(V)] shows obvious single-molecule magnet (SMM) behavior with an ST = 11/2 ground state, respectively, before and after introduction of the octacyanotungstate group. The spin frustration geometrical structure constructed by four Mn(III) ions and one W(V) ion was considered as the key factor for switching on the SMM properties of the 12-MC-4 system.

Structurally Diverse Diazafluorene-Ligated Palladium(II) Complexes and Their Implications for Aerobic Oxidation Reactions

4,5-Diazafluoren-9-one (DAF) has been identified as a highly effective ligand in a number of Pd-catalyzed oxidation reactions, but the mechanistic basis for its utility has not been elucidated. Here, we present the complex coordination chemistry of DAF and palladium(II) carboxylate salts. Multiple complexes among an equilibrating mixture of species have been characterized by (1)H and (15)N NMR spectroscopy and X-ray crystallography. These complexes include monomeric and dimeric Pd(II) species, with monodentate (κ(1)), bidentate (κ(2)), and bridging (μ:κ(1):κ(1)) DAF coordination modes. Titration studies of DAF and Pd(OAc)2 reveal the formation of two dimeric DAF/Pd(OAc)2 complexes at low [DAF] and four monomeric species at higher [DAF]. The dimeric complexes feature two bridging acetate ligands together with either a bridging or nonbridging (κ(1)) DAF ligand coordinated to each Pd(II) center. The monomeric structures consist of three isomeric Pd(κ(1)-DAF)2(OAc)2 complexes, together with Pd(κ(2)-DAF)(OAc)2 in which the DAF exhibits a traditional bidentate coordination mode. Replacing DAF with the structurally related, but more-electron-rich derivative 9,9-dimethyl-4,5-diazafluorene (Me2DAF) simplifies the equilibrium mixture to two complexes: a dimeric species in which the Me2DAF bridges the two Pd centers and a monomeric species with a traditional κ(2)-Me2DAF coordination mode. The use of DAF in combination with other carboxylate ligands (CF3CO2(-) or tBuCO2(-)) also results in a simplified collection of equilibrating Pd(II)-DAF complexes. Collectively, the results highlight the ability of DAF to equilibrate rapidly among multiple coordination modes, and provide valuable insights into the utility of DAF as a ligand in Pd-catalyzed oxidation reactions.

Crystal structure of a tetranuclear Cu(II) complex with an O,N,N'-donor Schiff base ligand: hexa-μ2-acetato-bis-(2-{[(2,2,6,6-tetra-methyl-piperidin-4-yl)imino]-meth-yl}phenolato-κ(3) O,N,N')tetra-copper(II).

The title compound, [Cu4(CH3COO)6(C16H23N2O)2], lies across a twofold rotation axis. The asymmetric unit contains two independent Cu(II) ions. The symmetry-unique terminal Cu(II) ion is O,N,N'-coordinated by a 2-{[(2,2,6,6-tetra-methyl-piperidin-4-yl)imino]-meth-yl}phenolate ligand and an O atom from an acetate group in a slightly distorted square-planar coordination environment. The symmetry-unique central Cu(II) ion is coordinated by a different O atom from the same acetate group and by four bridging acetate ligands, which connect the asymmetric unit into a dimeric complex and form a distorted square-pyramidal coordination environment. Within the complex there are two symmetry-equivalent intra-molecular N-H⋯O hydrogen bonds. In the crystal, weak C-H⋯O hydrogen bonds link the complex mol-ecules, forming a three-dimensional network.

Factors Controlling Stability and Reactivity of Dimeric Pd(II) Complexes in C–H Functionalization Catalysis

We have systematically explored the factors impacting the stability and reactivity of the [Pd(O2CR)2]2 and [Pd(OAc)(DG-Ar)]2 dimers in Pd(OAc)2-catalyzed and directing group (DG)-assisted C–H functionalization using density functional theory (DFT) calculations. It was shown that the palladium acetate dimer stability (vs the monomer) predominantly arises from interactions between the paddlewheel ligands and the Pd centers. R-substitution in Pd(O2CR)2 leading to an increase (or decrease) in the electron density of the ligand orbitals polarizes the Pd–ligand interaction and weakens (or strengthens) the stability of the [Pd(O2CR)2]2 dimer relative to the monomer. The nature of the substrate/ligand-Pd interaction is shown to be another factor contributing to the nuclearity and reactivity of the Pd-acetates in directing group-assisted C–H functionalization. For the [Pd(OAc)(DG-Ar)]2 dimer, we have found that the major interactions contributing to the stability of the dimer are the bridging acetate interactions ...

Destructive interactions of dirhodium(II) tetraacetate with β metallothionein rh1a.

Metal-based therapeutics are vital tools in medicine. Metal-chelating proteins can dramatically decrease drug efficacy. Dirhodium(II) tetraacetate, a potential anticancer compound, binds in vitro to 8 cysteines of the human metallothionein 1a β-fragment. Electrospray ionization mass spectrometry shows that the final product is the Rh2(4+) core encapsulated by the β fragment of the metallothionein protein protein.

β,β'-Bipyrrole Fusion-Driven cis-Bimetallic Complexation in Isomeric Porphyrin.

An unprecedented cis-bimetallic complex of dinaphthoporphycene (DNP), namely [Pd2(μ-DNP)(μ-OAc)2], is reported. The most striking feature of this complex is that two palladiums coordinate to the macrocycle on the same side and are closely held together (Pd-Pd: 2.67 Å) by two bridging acetate ligands exhibiting significant metal-metal bonding interaction (bond order 0.18 evaluated by NBO analysis). Interestingly, replacing acetate with acetylacetonate (acac) could stabilize an unusual mono-palladium complex of DNP, where Pd coordinates unsymmetrically to two ring Ns above the macrocyclic plane, as well as coordinating with two Os of the acac ligand. Remarkably, the rigid DNP core displays enhanced complexation induced aromaticity (as per NICS and HOMA analysis), despite undergoing severe core deformation during complexation with metal ion(s) as noticed from their solid-state structures.

β,β′‐Bipyrrole Fusion‐Driven cis‐Bimetallic Complexation in Isomeric Porphyrin

AbstractAn unprecedented cis‐bimetallic complex of dinaphthoporphycene (DNP), namely [Pd2(μ‐DNP)(μ‐OAc)2], is reported. The most striking feature of this complex is that two palladiums coordinate to the macrocycle on the same side and are closely held together (PdPd: 2.67 Å) by two bridging acetate ligands exhibiting significant metal–metal bonding interaction (bond order 0.18 evaluated by NBO analysis). Interestingly, replacing acetate with acetylacetonate (acac) could stabilize an unusual mono‐palladium complex of DNP, where Pd coordinates unsymmetrically to two ring Ns above the macrocyclic plane, as well as coordinating with two Os of the acac ligand. Remarkably, the rigid DNP core displays enhanced complexation induced aromaticity (as per NICS and HOMA analysis), despite undergoing severe core deformation during complexation with metal ion(s) as noticed from their solid‐state structures.

Effects of Halogen Bonding in Chemical Activity of Lead(II) Electron Pair: Sonochemical Synthesis, Structural Studies, and Thermal Analysis of Novel Lead(II) Nano Coordination Polymer

Abstract The nanoflower lead(II) coordination compound {[Pb(phen)(μ‐CH3COO)][PF6]}n (1) (phen = 1,10‐phenanthroline) was synthesized by a sonochemical method. The nanostructure was characterized by using scanning electron microscopy (SEM), X‐ray powder diffraction, elemental analysis, and thermal analysis. The single‐crystal X‐ray structure shows that the overall structure of 1 is a 1D coordination polymer. Complex 1 has a bridging acetate pathway. Three halogen bonds observed in the structure and the strong halogen bonding of F–Pb causes chemical activity of the lead electron pair. This is further extended into a 3D supramolecular structure by weak π–π intermolecular interactions. The coordination number of the lead(II) ions is six, resulting in PbN2O4. PbO nanoparticles were obtained by the thermolysis of 1 at 180 °C with oleic acid as a surfactant. The morphology and size of the prepared PbO nanoparticles were further observed using scanning electron (SEM) and transmission electron microscopy (TEM), and were analyzed by X‐ray photoelectron spectroscopy (XPS).

Tuning the Magnetic Interactions and Relaxation Dynamics of Dy2 Single-Molecule Magnets.

Efficient modulation of single-molecule magnet (SMM) behavior was realized by deliberate structural modification of the Dy2 cores of [Dy2(a'povh)2(OAc)2(DMF)2] (1) and [Zn2Dy2(a'povh)2(OAc)6]⋅4 H2O (2; H2a'povh = N'-[amino(pyrimidin-2-yl)methylene]-o-vanilloyl hydrazine). Compound 1 having fourfold linkage between the two dysprosium ions shows high-performance SMM behavior with a thermal energy barrier of 322.1 K, whereas only slow relaxation is observed for compound 2 with only twofold connection between the dysprosium ions. This remarkable discrepancy is mainly because of strong axiality in 1 due to one pronounced covalent bond, as revealed by experimental and theoretical investigations. The significant antiferromagnetic interaction derived from bis(μ2-O) and two acetate bridging groups was found to be crucial in leading to a nonmagnetic ground state in 1, by suppressing zero-field quantum tunneling of magnetization.

Reactions of Cd(OAc)2·2H2O with variously substituted pyridines. Efforts to unravel the factors that determine structure/nuclearity of the products

The reactions of Cd(OAc)2·2H2O with variously substituted pyridines in methanol afforded unique one-dimensional coordination polymers (1D CPs), [Cd2(μ2-κ2:κ1-OAc)2(μ2-κ1:κ1-OAc)2L2] (L=NC5H5 (1), NC5H4Me-3 (2), and NC5H3Me2-3,5 (3)) and [Cd3(μ3-κ1:κ2-OAc)3(μ2-κ2-OAc)(μ2-κ2:κ1-OAc)2(NC5H3Me2-3,4)2] (4), and discrete and bimolecular complexes, [(Cd(OAc)2(NC5H3Me2-3,4)2(H2O)2] (5), [Cd(κ2-OAc)2(NC5H4Me-4)2(H2O)]·[Cd(κ2-OAc)2(H2O)2)] (6), [Cd(κ2-OAc)2L2L′]·xH2O (x=0, L′=H2O, L=NC5H4(OMe)-4 (7); NC5H4tBu-4 (8); x=2, L=L′=NC5H4(NMe2)-4 (9·2H2O)). The products were characterised by elemental analysis, IR, solution NMR (1H and 13C), solid-state CP-MAS 13C{1H} and 113Cd NMR, TGA/DTA analyses, and single crystal X-ray diffraction. Phase purity of 1–4 was verified by powder X-ray diffraction (PXRD). Plausible mechanisms of formation of the products are proposed based on a point zero charge model. 4 represents the first cadmium containing 1D CP that possesses a tridentate bridging (μ3-κ1:κ2) acetate coordination mode and 6 represents the first structurally characterised bimolecular cadmium(II) complex containing two different neutral cadmium(II) coordination species per formula unit. 9·2H2O was calcined at 500°C to afford CdO as confirmed by PXRD and the morphology of CdO was studied by scanning electron microscopy.