Trickier than It Looks: Isomerization between Five- and Six-Coordinated Zinc in Heterometallic Li2Zn2 Molecule.

This report describes the synthesis and characterization of two heterobimetallic Li-Zn coordination isomers [Li2Zn2(tbaoac)6] (tbaoac = tert-butyl acetoacetato) that have been isolated separately by the same stoichiometric reaction run in different organic solvents. The 6-coordinated zinc isomer (6-Zn) was synthesized in acetone with high yield, while the 5-coordinated one (5-Zn) was readily obtained from ethanol. The 5-Zn isomer has a low solubility in organic solvents such as alkanes and haloalkanes, while its 6-Zn counterpart exhibits a good solubility in almost all common solvents. Two isomeric molecules feature similar centrosymmetric tetranuclear cyclic assemblies, which are different in their arrangement of tbaoac ligands. While all ligands act as µ2-type in the structure of 5-Zn, the two tbaoac groups chelating Li appear as µ3-type in 6-Zn, thus providing an additional coordination for Zn ions. However, the real structural transformation between these isomers was shown to be more complex than simply making or breaking a couple of Zn-O bonds. X-ray single-crystal structure analysis, powder X-ray diffraction, multinuclear NMR, DART mass spectrometry, ICP-OES analysis, and TGA have been employed for the characterization of the isomers. The combination of powder X-ray diffraction and 1H NMR investigation revealed that 6-Zn isomer can be quantitatively transformed to 5-Zn in ethanol, while the reverse conversion instantly takes place in acetone.

Multi-functional Single-Source Molecular Precursors for Carbon-Coated Mixed-Metal Phosphates.

We introduce a new synthetic concept that can be broadly adopted for the low-temperature preparation of mixed-metal energy storage materials, such as phosphates, silicates, fluorides, fluorophosphates, and fluorosulfates that exhibit intrinsic low electronic conductivity and thus require a carbon modulation. The development of novel low-temperature approaches for assembling energy-related materials with a complex core-shell microstructure is of great importance for expanding their application scope. The traditional definition of single-source precursors refers to their ability to yield a phase-pure material upon thermal decomposition. We have developed a new way for the utilization of heterometallic molecular precursors in synthesis that goes beyond its common delineation as a single-phase maker. The utility of this approach has been demonstrated upon the low-temperature synthesis of lithium-iron phosphate@C, which represents a celebrated cathode material for Li-ion batteries. The first atomically precise carbonaceous molecular precursors featuring a desired Li:Fe:P ratio of 1:1:1, divalent iron, and sufficient oxygen content for the target LiFeIIPO4 phosphate were shown to enable a spontaneous formation of both the olivine core and conductive carbon shell, yielding a carbon-coated mixed-metal phosphate.

Synthesis, Structure, and Characterizations of a Volatile/Soluble Heterometallic Hexanuclear Precursor [NaMn2(thd)4(OAc)]2.

The paper describes a heterobimetallic mixed-ligand hexanuclear precursor [NaMn2(thd)4(OAc)]2 (1) (thd = 2,2,6,6-tetramethyl-3,5-heptadionate; OAc = acetate) that was designed based on its lithium homoleptic analogue, [LiMn2(thd)5], by replacing one of the thd ligands with an acetate group in order to accommodate 5-coordinated sodium instead of tetrahedral lithium ion. The complex, which is highly volatile and soluble in a variety of common solvents, has been synthesized by both the solid-state and solution methods. The unique "dimer-of-trimers" heterometallic structure consists of two trinuclear [NaMnII2(thd)4]+ units firmly bridged by two acetate ligands. X-ray diffraction techniques, DART mass spectrometry, ICP-OES analysis, and IR spectroscopy have been employed to confirm the structure and composition of the hexanuclear complex. Similar to the Li counterpart forming LiMn2O4 spinel material upon thermal decomposition, the title Na:Mn = 1:2 compound was utilized as the first single-source precursor for the low-temperature preparation of Na4Mn9O18 tunnel oxide. Importantly, four Mn sites in the hexanuclear molecule can be potentially partially substituted by other transition metals, leading to heterotri- and tetrametallic precursors for the advanced quaternary and quinary Na-ion oxide cathode materials.

Intermetallic Compound Re2Ga9Ge with Re- and Ge-Embedded Gallium Clusters: Synthesis, Crystal Structure, Chemical Bonding, and Physical Properties.

Transition metal-based endohedral cluster intermetallic compounds are interesting electron phases, which frequently exhibit superconductivity with a peculiar interplay between the critical temperature and valence electron count. We present a new Re-based endohedral gallium cluster compound, Re2Ga9Ge. Its unique crystal structure (P42/mmc space group, a = 8.0452(3) Å, c = 6.7132(2) Å) is built by two types of gallium polyhedra: monocapped Archimedean antiprisms centered by rhenium atoms and tetrahedra containing a main-group element inside. The analysis of chemical bonding shows the presence of localized pairwise interactions between the p-block elements and the formation of multicenter bonds with the participation of d-orbitals of rhenium. In the electronic band structure, the Fermi level is located in a narrow pseudogap indicating the optimum band filling and thus explaining the virtual absence of a homogeneity range. The compound exhibits Pauli paramagnetism and metallic properties with unexpectedly low thermal conductivity. A sharp anomaly observed on the magnetic susceptibility and resistivity curves presumably indicates the electronic phase transition accompanied by charge ordering at the characteristic temperature of T * = 271 K in zero magnetic field.

Molecular and Supramolecular Structures of Triiodides and Polyiodobismuthates of Phenylenediammonium and Its N,N-dimethyl Derivative.

Despite remarkable progress in photoconversion efficiency, the toxicity of lead-based hybrid perovskites remains an important issue hindering their applications in consumer optoelectronic devices, such as solar cells, LED displays, and photodetectors. For that reason, lead-free metal halide complexes have attracted great attention as alternative optoelectronic materials. In this work, we demonstrate that reactions of two aromatic diamines with iodine in hydroiodic acid produced phenylenediammonium (PDA) and N,N-dimethyl-phenylenediammonium (DMPDA) triiodides, PDA(I3)2⋅2H2O and DMPDA(I3)I, respectively. If the source of bismuth was added, they were converted into previously reported PDA(BiI4)2⋅I2 and new (DMPDA)2(BiI6)(I3)⋅2H2O, having band gaps of 1.45 and 1.7 eV, respectively, which are in the optimal range for efficient solar light absorbers. All four compounds presented organic-inorganic hybrids, whose supramolecular structures were based on a variety of intermolecular forces, including (N)H⋅⋅⋅I and (N)H⋅⋅⋅O hydrogen bonds as well as I⋅⋅⋅I secondary and weak interactions. Details of their molecular and supramolecular structures are discussed based on single-crystal X-ray diffraction data, thermal analysis, and Raman and optical spectroscopy.

Heterotrimetallic Precursor with 2:2:1 Metal Ratio Requiring at Least a Pentanuclear Molecular Assembly.

This work represents an important step in the quest to make heteromultimetallic molecules featuring specific metal types and complicated metal ratios. The rational design, synthesis, and characterization of a complex heterotrimetallic single-source molecular precursor for the next generation sodium-ion battery cathode material, Na2Mn2FeO6, is described. A unique pentametallic platform [MnII(ptac)3-Na-MnIII(acac)3-Na-MnII(ptac)3] (1) was derived from the known polymeric structure of [NaMnII(acac)3]∞, through a series of elaborate design procedures, such as mixed-ligand, unsymmetric ligand, and mixed-valent approaches. Importantly, the application of those techniques results in a molecule with distinctively different transition metal positions in terms of ligand environment and oxidation states. An isovalent substitution of FeIII for the central MnIII ion forms the target heterotrimetallic precursor [MnII(ptac)3-Na-FeIII(acac)3-Na-MnII(ptac)3] (3) with an appropriate metal ratio of Na:Mn:Fe = 2:2:1. The arrangement of metal ions and ligands in this pentametallic assembly was confirmed by single crystal X-ray investigation. The unambiguous assignment of the positions and oxidation states of the Periodic Table neighbors Fe and Mn in 3 has been achieved by a combination of investigative techniques that include synchrotron resonant diffraction, X-ray multiwavelength anomalous diffraction, X-ray fluorescence spectroscopy, Mössbauer spectroscopy, and gas-phase DART mass spectrometry. The heterotrimetallic single-source precursor 3 was shown to exhibit a clean decomposition pattern yielding the phase-pure P2-Na2Mn2FeO6 quaternary oxide with high uniformity of metal ion distribution as confirmed by electron microscopy.

Electron-Precise Semiconducting ReGa2Ge: Extending the IrIn3 Structure Type to Group 7 of the Periodic Table.

Intermetallic compounds with semiconducting properties are rare, but they give rise to advanced materials for energy conversion and saving applications. Here, we present ReGa2Ge, a new electron-precise narrow-gap intermetallic semiconductor. The compound crystallizes in the IrIn3 structure type (space group P42/mnm, a = 6.5734(3) Å, c = 6.7450(8) Å, and Z = 4), where Re atoms occupy the Ir site, while Ga and Ge jointly populate the In sites. 69,71Ga nuclear quadrupole resonance spectroscopy indicates nonstatistical partially ordered distribution of Ga and Ge over two available crystallographic sites; however, the Ga:Ge ratio is exactly 2:1 without noticeable homogeneity range. The stoichiometry of ReGa2Ge ensures its precise valence electron count, which is 17 e- per formula unit. Accordingly, a narrow energy gap opens up at the Fermi energy in the electronic structure. Electrical resistivity, Seebeck coefficient, and thermal conductivity are in agreement with the semiconducting behavior deduced from the electronic structure calculations and point to prospective thermoelectric properties at high temperatures. Bonding analysis reveals dominant covalency in Re-E (E = Ga, Ge) and Re-Re interactions.

Assembling Polyiodides and Iodobismuthates Using a Template Effect of a Cyclic Diammonium Cation and Formation of a Low-Gap Hybrid Iodobismuthate with High Thermal Stability.

Exploiting a template effect of 1,4-diazacycloheptane (also known as homopiperazine, Hpipe), four new hybrid iodides, (HpipeH2)2Bi2I10·2H2O, (HpipeH2)I(I3), (HpipeH2)3I6·H2O, and (HpipeH2)3(H3O)I7, were prepared and their crystal structures were solved using single crystal X-ray diffraction data. All four solid-state crystal structures feature the HpipeH22+ cation alternating with Bi2I104-, I3-, or I- anions and solvent water or H3O+ cation. HpipeH22+ assembles anionic and neutral building blocks into polymer structures by forming four strong (N)H···I and (N)H···O hydrogen bonds per cation, with the H···I distances ranging from 2.44 to 2.93 Å and H···O distances of 1.88-1.89 Å. These hydrogen bonds strongly affect the properties of compounds; in particular, in the case of (HpipeH2)2Bi2I10·2H2O, they ensure narrowing of the band gap down to 1.8 eV and provide high thermal stability up to 240 °C, remarkable for a hydrated molecular solid.

Heterotrimetallic Mixed-Valent Molecular Precursors Containing Periodic Table Neighbors: Assignment of Metal Positions and Oxidation States.

A known trinuclear structure was used to design the heterobimetallic mixed-valent, mixed-ligand molecule [CoII (hfac)3 -Na-CoIII (acac)3 ] (1). This was used as a template structure to develop heterotrimetallic molecules [CoII (hfac)3 -Na-FeIII (acac)3 ] (2) and [NiII (hfac)3 -Na-CoIII (acac)3 ] (3) via isovalent site-specific substitution at either of the cobalt positions. Diffraction methods, synchrotron resonant diffraction, and multiple-wavelength anomalous diffraction were applied beyond simple structural investigation to provide an unambiguous assignment of the positions and oxidation states for the periodic table neighbors in the heterometallic assemblies. Molecules of 2 and 3 are true heterotrimetallic rather than a statistical mixture of two heterobimetallic counterparts. Trinuclear platform 1 exhibits flexibility in accommodating a variety of di- and trivalent metals, which can be further utilized in the design of molecular precursors for the NaMM'O4 functional oxide materials.

Crystal Growth of Intermetallics from the Joint Flux: Exploratory Synthesis through the Control of Valence Electron Count.

In this study, we modify the flux-growth method for the purpose of exploratory synthesis of ternary intermetallic compounds. Our concept is based on the assumption that valence electron count plays a crucial role in the stability of polar intermetallic compounds of different structure types. Control of the valence electron count parameter is made possible through the use of an excess of two metals having a different number of valence electrons. By gradually changing the ratio between these metals in the joint flux, we scan the gross number of valence electrons and explore the crystallization of new compounds. In the ternary system Re-Ga-Zn, we detect compounds belonging to three structure types, ReGa5, PtHg4, and V8Ga41, while gradually increasing the content of Zn metal in the flux. Two new compounds, ReGa3Zn and Re8Ga41- xZn x with x = 21.2(5), are obtained in the form of high-quality single crystals, and the former compound shows the narrow-gap semiconducting behavior favorable for high thermoelectric performance.

Endohedral Cluster Superconductors in the Mo-Ga-Sn System Explored by the Joint Flux Technique.

Endohedral Ga cluster compounds feature nontrivial superconducting states including the two-gap superconductivity similar in nature to MgB2. We use the joint flux synthetic technique to introduce Sn into the Ga matrix and tune the valence electron count in the two new endohedral cluster superconductors Mo8Ga41-xSnx and Mo4Ga21-x-δSnx with critical temperatures of Tc = 8.7 and 5.85 K, respectively. While the former compound is a derivative of the previously known Mo8Ga41 superconductor, where Sn atoms are enclosed inside the Sn@Ga6 octahedral clusters, the latter is a new architecture built upon Mo@Ga9Sn clusters, Ga@Ga12 cuboctahedra, and Sn4 squares. We show that this novel Mo4Ga21-x-δSnx superconductor features strong electron-phonon coupling with the large ratio of 2Δ(0)/(kBTc) = 4.1 similar to that of the Mo8Ga41 superconductor with the closely related crystal structure.

Expanding the Structural Motif Landscape of Heterometallic ß-Diketonates: Congruently Melting Ionic Solids.

The first example of ionic ß-diketonates in which both the cation and anion are octahedral coordinatively saturated metal diketonate moieties are reported. Heterometallic tin-transition-metal heteroleptic diketonates were obtained through solid-state redox reactions and are formulated as {[SnIV(thd)3]+[MII(hfac)3]-} (MII = Mn (1), Fe (2), Co (3); thd = 2,2,6,6-tetramethyl-3,5-heptanedionate, hfac = hexafluoroacetylacetonate). X-ray single-crystal structural investigations along with DART mass spectrometry, multinuclear NMR, and magnetic susceptibility measurements have been used to confirm an assignment of metal oxidation states in compounds 1-3. Ionic compounds were found to melt congruently at temperatures below the decomposition point. As such, they represent prospective materials that can be utilized as ionic liquids as well as reagents for the soft transfer of diketonate ligands. An unexpected volatility of ionic compounds 1-3 was proposed to occur through a transport reaction, in which the transport agent is one of the products of their partial decomposition in the gas or condensed phase.

Position Assignment and Oxidation State Recognition of Fe and Co Centers in Heterometallic Mixed-Valent Molecular Precursors for the Low-Temperature Preparation of Target Spinel Oxide Materials.

A series of mixed-valent, heterometallic (mixed-transition metal) diketonates that can be utilized as prospective volatile single-source precursors for the low-temperature preparation of MxM'3-xO4 spinel oxide materials is reported. Three iron-cobalt complexes with Fe/Co ratios of 1:1, 1:2, and 2:1 were synthesized by several methods using both solid-state and solution reactions. On the basis of nearly quantitative reaction yields, elemental analyses, and comparison of metal-oxygen bonds with those in homometallic analogues, heterometallic compounds were formulated as [FeIII(acac)3][CoII(hfac)2] (1), [CoII(hfac)2][FeIII(acac)3][CoII(hfac)2] (2), and [FeII(hfac)2][FeIII(acac)3][CoII(hfac)2] (3). In the above heteroleptic complexes, the Lewis acidic, coordinatively unsaturated CoII/FeII centers chelated by two hexafluoroacetylacetonate (hfac) ligands maintain bridging interactions with oxygen atoms of acetylacetonate (acac) groups that chelate the neighboring FeIII metal ion. Preliminary assignment of Fe and Co positions/oxidation states in 1-3 drawn from X-ray structural investigation was corroborated by a number of complementary techniques. Single-crystal resonant synchrotron diffraction and neutron diffraction experiments unambiguously confirmed the location of Fe and Co sites in the molecules of dinuclear (1) and trinuclear (2) complexes, respectively. Direct analysis in real time mass spectrometry revealed the presence of FeIII- and CoII-based fragments in the gas phase upon evaporation of precursors 1 and 2 as well as of FeIII, FeII, and CoII species for complex 3. Theoretical investigation of two possible "valent isomers", [FeIII(acac)3][CoII(hfac)2] (1) and [CoIII(acac)3][FeII(hfac)2] (1'), provided an additional support for the metal site/oxidation state assignment giving a preference of 6.48 kcal/mol for the experimentally observed molecule 1. Magnetic susceptibility measurements data are in agreement with the presence of high-spin FeIII and CoII magnetic centers with weak anti-ferromagnetic coupling between those in molecules of 1 and 2. Highly volatile heterometallic complexes 1-3 were found to act as effective single-source precursors for the low-temperature preparation of iron-cobalt spinel oxides FexCo3-xO4 known as important materials for diverse energy-related applications.

Volatile Single-Source Precursors for the Low-Temperature Preparation of Sodium-Rare Earth Metal Fluorides.

Heterometallic single-source precursors for the preparation of sodium-rare earth metal fluorides are reported. Fluorinated ß-diketonates NaRE(hfac)4 (RE = Y (1), Er (2), and Eu (3); hfac = hexafluoroacetylacetonate) have been obtained on a large scale, in high yield, via one-pot reaction that utilizes commercially available starting reagents. The solid-state structures of the title complexes consist of 1D polymeric chains with alternating [Na] and [RE(hfac)4] units. Compounds 1-3 are highly volatile and exhibit a fair stability in open air. Mass spectrometric investigation indicates the presence of heterometallic fragments in the gas phase. The presence of heterometallic species in solutions of coordinating solvents has also been confirmed. Decomposition of heterometallic precursors in argon atmosphere was shown to yield phase-pure sodium-rare earth metal fluorides. Low decomposition temperature effectively allows for a high degree of control over the formation of both kinetic α-phases and thermodynamic ß-phases of target NaREF4 (RE = Y, Er, and Eu) materials.

Mixed-Ligand Approach to Changing the Metal Ratio in Bismuth-Transition Metal Heterometallic Precursors.

A new series of heteroleptic bismuth-transition metal ß-diketonates [BiM(hfac)3(thd)2] (M = Mn (1), Co (2), and Ni (3); hfac = hexafluoroacetylacetonate, thd = tetramethylheptanedionate) with Bi:M = 1:1 ratio have been synthesized by stoichiometric reactions between homometallic reagents [Bi(III)(hfac)3] and [M(II)(thd)2]. On the basis of analysis of the metal-ligand interactions in heterometallic structures, the title compounds were formulated as ion-pair {[Bi(III)(thd)2](+)[M(II)(hfac)3](-)} complexes. The direct reaction between homometallic reagents proceeds with a full ligand exchange between main group and transition metal centers, yielding dinuclear heterometallic molecules. In heteroleptic molecules 1-3, the Lewis acidic, coordinatively unsaturated Bi(III) centers are chelated by two bulky, electron-donating thd ligands and maintain bridging interactions with three oxygen atoms of small, electron-withdrawing hfac groups that chelate the neighboring divalent transition metals. Application of the mixed-ligand approach allows one to change the connectivity pattern within the heterometallic assembly and to isolate highly volatile precursors with the proper Bi:M = 1:1 ratio. The mixed-ligand approach employed in this work opens broad opportunities for the synthesis of heterometallic (main group-transition metal) molecular precursors with specific M:M' ratio in the case when homoleptic counterparts either do not exist or afford products with an incorrect metal:metal ratio for the target materials. Heteroleptic complexes obtained in the course of this study represent prospective single-source precursors for the low-temperature preparation of multiferroic perovskite-type oxides.

Iodobismuthates Containing One-Dimensional BiI4(-) Anions as Prospective Light-Harvesting Materials: Synthesis, Crystal and Electronic Structure, and Optical Properties.

Four iodobismuthates, LiBiI4·5H2O (1), MgBi2I8·8H2O (2), MnBi2I8·8H2O (3), and KBiI4·H2O (4), were prepared by a facile solution route and revealed thermal stability in air up to 120 °C. Crystal structures of compounds 1-4 were solved by a single crystal X-ray diffraction method. 1: space group C2/c, a = 12.535(2), b = 16.0294(18), c = 7.6214(9) Å, ß = 107.189(11)°, Z = 4, R = 0.029. 2: space group P21/c, a = 7.559(2), b = 13.1225(15), c = 13.927(4) Å, ß = 97.14(3)°, Z = 2, R = 0.031. 3: space group P21/c, a = 7.606(3), b = 13.137(3), c = 14.026(5) Å, ß = 97.14(3)°, Z = 2, R = 0.056. 4: space group P21/n, a = 7.9050(16), b = 7.7718(16), c = 18.233(4) Å, ß = 97.45(3)°, Z = 4, R = 0.043. All solid state structures feature one-dimensional (BiI4)(-) anionic chains built of [BiI6] octahedra that share two opposite edges in such a fashion that two iodine atoms in cis-positions remain terminal. The calculated electronic structures and observed optical properties confirmed that compounds 1-4 are semiconductors with direct band gaps of 1.70-1.76 eV, which correspond to their intense red color. It was shown that the cations do not affect the optical properties, and the optical absorption is primarily associated with the charge transfer from the I 5p orbitals at the top of the valence band to the Bi 6p orbitals at the bottom of the conduction band. Based on their properties and facile synthesis, the title compounds are proposed as promising light-harvesting materials for all-solid solar cells.

Mixed-ligand approach to design of heterometallic single-source precursors with discrete molecular structure.

Heterometallic single-source precursors for the Pb/Fe = 1:1 oxide materials, PbFe(ß-dik)4 (ß-dik = hexafluoroacetylacetonate (hfac, 1), acetylacetonate (acac, 2), and trifluoroacetylacetonate (tfac, 4)), have been isolated by three different solid-state synthetic methods. The crystal structures of heterometallic diketonates 1, 2, and 4 were found to contain polymeric chains built on alternating [Fe(ß-dik)2] and [Pb(ß-dik)2] units that are held together by bridging M-O interactions. Heterometallic precursors are highly volatile, but soluble only in coordinating solvents, in which they dissociate into solvated homometallic fragments. In order to design the heterometallic precursor with a proper metal/metal ratio and with a discrete molecular structure, we used a combination of two different diketonate ligands. Heteroleptic complex Pb2Fe2(hfac)6(acac)2 (5) has been obtained by optimized stoichiometric reaction of an addition of homo-Fe(acac)2 to heterometallic Pb2Fe(hfac)6 (3) diketonate that can be run in solution on a high scale. The combination of two ligands with electron-withdrawing and electron-donating groups allows changing the connectivity pattern within the heterometallic assembly and yields the precursor with a discrete tetranuclear structure. In accord with its molecular structure, heteroleptic complex 5 is soluble even in noncoordinating solvents and was found to retain its heterometallic structure in solution. Thermal decomposition of heterometallic precursors in air at 750 °C resulted in the target Pb2Fe2O5 oxide, a prospective multiferroic material. Prolonging the annealing time or increasing the decomposition temperature leads to another phase-pure lead-iron oxide PbFe12O19 that is a representative of the important family of magnetic hexaferrites.

Volatile heterometallic precursors for the low-temperature synthesis of prospective sodium ion battery cathode materials.

Heterometallic single-source precursors with a proper sodium:transition-metal ratio for nonoxide sodium ion battery cathode materials are reported. Heterometallic fluorinated ß-diketonates NaM(hfac)3 (M = Mn (1), Fe (2), Co (3), and Ni (4); hfac = hexafluoroacetylacetonate) have been obtained on a large scale, in high yield using a one-step reaction that employs commercially available reagents. The complexes are stable in open air and highly volatile. The mass spectrometric investigation indicates the existence of heterometallic molecules in the gas phase. The presence of heterometallic species in solutions of several solvents has been unambiguously confirmed. Heterometallic precursors were shown to exhibit clean, low-temperature decomposition in argon atmosphere that results in phase-pure perovskite fluorides NaMF3, the prospective cathode materials for sodium ion batteries.

Bis(1,1,1,5,5,5-hexafluoropentane-2,4-dionato)tetrakis(µ4-1,1,1,5,5,5-hexafluoropentane-2,2,4,4-tetraolato)copper(II)octatin(II): a prospective precursor for Cu-doped SnO2 films.

The crystal structure of a tin-rich heterometallic supramolecular product, [CuSn8(C5HF6O2)2(C5H2F6O4)4] or [Sn4(hfpt)2-Cu(hfac)2-Sn4(hfpt)2], (I), is reported (hfpt is the tetraanion of 1,1,1,5,5,5-hexafluoropentane-2,2,4,4-tetraol and hfac is the anion of 1,1,1,5,5,5-hexafluoropentane-2,4-dione). Reaction between tin(II) tetraolate, [Sn4(hfpt)2], and copper(II) ß-diketonate, [Cu(hfac)2], was utilized for the preparation of (I). The asymmetric unit consists of the whole [Sn4(hfpt)2] unit and half of a [Cu(hfac)2] unit, with the Cu atom lying on an inversion center. Intermolecular Cu···O interactions from the axial positions of copper in [Cu(hfac)2] and O atoms of the hfpt ligand in [Sn4(hfpt)2] mediate the formation of a sandwich-type structure for (I). Additional intermolecular Sn···O interactions between neighbouring [Sn4(hfpt)2] units complete a two-dimensional network.

Volatile single-source molecular precursor for the lithium ion battery cathode.

The first single-source molecular precursor for a lithium-manganese cathode material is reported. Heterometallic ß-diketonate LiMn(2)(thd)(5) (1, thd = 2,2,6,6-tetramethyl-3,5-heptanedionate) was obtained in high yield by simple one-step solid-state reactions employing commercially available reagents. Substantial scale-up preparation of 1 was achieved using a solution approach. The crystal structure of the precursor contains discrete Li:Mn = 1:2 trinuclear molecules held together by bridging diketonate ligands. The complex is relatively stable in open air, highly volatile, and soluble in all common solvents. It was confirmed to retain its heterometallic structure in solutions of non-coordinating solvents. The heterometallic diketonate 1 was shown to exhibit clean, low-temperature decomposition in air/oxygen that results in nanosized particles of spinel-type oxide LiMn(2)O(4), one of the leading cathode materials for lithium ion batteries.