Crystal structure evolution of an energetic compound dihydroxylammonium 5,5′-bistetrazole-1,1′-diolate induced by solvents

Recently, energetic ionic salts have become a research hotspot due to their attractive properties, such as high density, high heat of formation, and environmental friendliness. Dihydroxylammonium 5,5′-bistetrazole-1,1′-diolate (TKX-50) is a typical nitrogen-rich energetic ionic salt, which has broad application prospects. However, the research on the stability and crystal structure evolution of TKX-50 in different solvent systems is insufficient. Herein, we investigated the crystal structure transformations and searched for new solid forms of TKX-50 under different conditions via a solvent induction method. The phase composition of all screened samples was analyzed by powder or single-crystal X-ray diffraction. Three new solid forms of [NH₂(CH₃)₂⁺][BTO⁻], [NH₂(CH₃CH₂)₂⁺]₂[BTO²⁻], [NHOH(CH₃CCH₃)⁺][BTO⁻] H₂O were obtained from DMAC, DEF and AC/MT, respectively. Furthermore, the energetic properties were evaluated through EXPLO5.

Three new solvent compounds obtained by dihydroxylammonium 5,5′-bistetrazole-1,1′-diolate recrystallized from three solvents.     

Reactive molecular dynamics simulation of the high-temperature pyrolysis of 2,2′,2′′,4,4′,4′′,6,6′,6′′-nonanitro-1,1′:3′,1′′-terphenyl (NONA)

2,2′,2′′,4,4′,4′′,6,6′,6′′-Nonanitro-1,1′:3′,1′′-terphenyl (NONA) is currently recognized as an excellent heat-resistant explosive. To improve the atomistic understanding of the thermal decomposition paths of NONA, we performed a series of reactive force field (ReaxFF) molecular dynamics simulations under extreme conditions of temperature and pressure. The results show that two distinct initial decomposition mechanisms are the homolytic cleavage of the C–NO₂ bond and nitro–nitrite (NO₂ → ONO) isomerization followed by NO fission. Bimolecular and fused ring compounds are found in the subsequent decomposition of NONA. The product identification analysis under finite time steps showed that the gaseous products are CO₂, N₂, and H₂O. The amount of CO₂ is energetically more favorable for the system at high temperature or low density. The carbon-containing clusters are a favorable growth pathway at low temperatures, and this process was further demonstrated by the analysis of diffusion coefficients. The increase of the crystal density accelerates the decomposition of NONA judged by the analysis of reaction kinetic parameters and activation barriers. In the endothermic and exothermic stages, a 20% increase in NONA density increases the activation energies by 3.24 and 0.48 kcal mol⁻¹, respectively. The values of activation energies (49.34–49.82 kcal mol⁻¹) agree with the experimental data in the initial decomposition stage.

The bimolecular and fused ring compounds are found in the high-temperature pyrolysis of NONA using ReaxFF molecular dynamics simulations.     

The modulation effect of pi–pi interactions on the electronic and photochromic properties of viologen complexes containing N,N′-bis(carboxyethyl)-4,4′-bipyridinium

Two viologen complexes containing N,N′-bis(carboxyethyl)-4,4′-bipyridinium (BCEbpy) were prepared, namely [Zn(H₂O)₆]·(BCEbpy)·(p-BDC)·3H₂O (1) and [Co(H₂O)₆]·(BCEbpy)·(p-BDC)·3H₂O (2) (p-H₂BDC = 1,4-benzenedicarboxylic acid), and their crystal structures, photochromism, frontier molecular orbitals, Hirshfeld surfaces and 2D fingerprint plots were investigated. The modulation effects of pi–pi interactions were explored on the electronic and photochromic properties of compounds 1 and 2. Due to the existence of photo-response viologen radicals, both complexes 1 and 2 display excellent photo-response properties in the sequence 1 < 2. The results indicate that compound 1 exhibits intramolecular electron transfer; compound 2 exhibits both intramolecular and intermolecular electron transfer, which is mainly due to the change of electronic and steric structures caused by pi–pi interactions with a faster photo-response rate than that of compound 1. The donor–acceptor modes, matching principles and inter/intramolecular atom–atom close contacts were illustrated by the density functional theory (DFT)-B3LYP/6-311(d,p) method.

Two viologen complexes containing BCEbpy were prepared and displayed excellent photo-response properties by the modulation effect of pi–pi interactions.     

Structures and photocatalytic properties of two new Zn(ii) coordination polymers based on semi-rigid V-shaped multicarboxylate ligands

Two new metal–organic coordination polymers (CPs), aqua-2,2′-bipyridine-5-(4′-carboxylphenoxy)isophthalatezinc(ii) polymer [Zn(HL)(2,2′-bipy)(H₂O)]_n (1) and tris-4,4′-bipyridine-bis-5-(4′-carboxylphenoxy)isophthalatetrizinc(ii) polymer [Zn₃(L)2(4,4′-bipy)₃]_n (2) (H₃L = 5-(4′-carboxylphenoxy)isophthalic acid, 4,4′-bipy = 4,4′-bipyridine and 2,2′-bipy = 2,2′-bipyridine), were obtained under hydrothermal conditions and characterized by microanalysis, FTIR spectroscopy and single crystal X-ray diffraction. The single crystal X-ray diffraction indicated that in both the CPs the coordination networks exhibited varied topologies and coordination modes around the Zn(ii) centers. CP 1 exhibits a one-dimensional (1D) chain structure, which further forms a 3D supramolecular architecture via intermolecular π⋯π and hydrogen bonding interactions, while 2 possesses a 3D framework generated from a 2D layered motif comprising zinc and tripodal carboxylate subunits pillared by 4,4′-bpy ligands. Apart from the structural investigation, the photocatalytic performances of both the coordination polymers to photodecompose an aqueous solution of methyl violet (MV) were examined. The results indicated that both the CPs displayed the potential to photodecompose aromatic dyes and in particular 2 showed good photocatalytic activity for dye degradation under light irradiation. The photocatalytic mechanism through which these CPs executed degradation of dyes has been explained with the assistance of band gap calculations using density of states (DOS) and its decomposed partial DOS calculations.

Two new Zn(ii) coordination polymers having semi-rigid V-shaped polycarboxylate ligands were synthesized and their photocatalytic performances to photodegrade methyl violet were assessed.     

Cu(ii)/Ni(ii)–organic frameworks constructed from the homometallic clusters by 5-(2-carboxyphenoxy)isophthalic acid and N-ligand: synthesis,structures and visible light-driven photocatalytic properties

Four new complexes, namely, Cu₂(O-cpia)(btb)_0.5·(OH) (1), Cu₃(O-cpia)₂(bpy)₂ (2), [Ni₂(O-cpia)(phen)·(OH)·H₂O]·2H₂O (3) and [Ni₃(O-cpia)₂(bpy)₃·2H₂O]·2H₂O (4) (O-cpia = 5-(2-carboxyphenoxy)isophthalic acid, btb = 1,4-bis(1,2,4-triazol-1-yl)butane, bpy = 4,4′-bipyridine) were successfully isolated under hydrothermal conditions. The four complexes exhibit different architectures constructed from different homometallic clusters varying from mononuclear, binuclear to tetranuclear metal(ii) polyhedra as Second Building Blocks (SBUs). 1 features a 3D framework constructed from the tetranuclear clusters [Cu₄(μ₃-OH)₂] as SBUs, linked with Cu(1)O₄N and Cu(2)O₅ polyhedra by O-cpia/btb mixed linkers. 2 also exhibits a 3D structure based on trinuclear clusters [Cu₃(COO)₄] SBUs, bridged with Cu(1)O₃N₂ and Cu(2)O₄ polyhedra via O-cpia/bpy mixed ligands. 3 shows a 2D network consisting of tetranuclear clusters [Ni₄(μ₃-OH)₂] SBUs, which are bridged with Ni(1)O₄N₂ and Ni(2)O₆ through O-cpia ligands. It is worth noting that 4, with a 3D structure, is generated from the binuclear clusters [Ni₂(COO)₄] (Ni(1)O₄N) and mononuclear metal Ni(2) cores (Ni(2)O₄N₂) as SBUs, and bridged by O-cpia/bpy mixed ligands. Meanwhile, the degradation of dyes (RhB) by the complexes under visible light irradiation was studied. 1–4 are semiconducting in nature, with E_g of 1.30 eV (1), 1.78 eV (2), 2.85 eV (3) and 2.14 eV (4). Cu(ii) complexes 1 and 2 are highly efficient photocatalysts for the degradation of RhB under visible light irradiation.

Four Cu(ii)/Ni(ii)-metal–organic frameworks were constructed from different homometallic clusters by O-cpia/N-ligands. Cu(ii)-complexes show highly efficient photocatalysts for the degradation of RhB under visible light irradiation.     

Three new metal coordination polymers of bifunctional imidazolate/tetrazolate bridges: the only example of a three-dimensional framework based on rare [Co4(μ3-OH)2(μ2-Cl)2]4+ mixed oxo-chloro-clusters

Three new metal coordination polymers [Ni(μ₂-L)₂(H₂O)₂]_n(1, HL = 1-tetrazole-4-imidazole-benzene), [Co(μ₂-L)₂]_n (2), and [Co₄(μ₃-OH)₂(μ₂-Cl)₂(μ₅-L)₂(μ₂-L)₂]_n·7nH₂O (3) were hydrothermally synthesized and structurally characterized. 1 displays a neutral [Ni(μ₂-L)₂(H₂O)₂]_n chain built up from the Ni²⁺ ions bridged by deprotonated L⁻ ligands, while 2 shows another rare neutral [Co(μ₂-L)₂]_n chain based on Co²⁺ ions connected by two different coordination modes of the L⁻ ligand. 3 exhibits a rare [Co₄(μ₃-OH)₂(μ₂-Cl)₂]⁴⁺ mixed oxo-chloro-cluster-based three-dimensional framework with large elliptical channels, which are filled by unprecedented chilopod [(H₂O)₇]_n chains. Both 1 and 2 show antiferromagnetic behavior, while 3 exhibits unusual spin-canting.

The interconnection of rare [Co₄(μ₃-OH)₂(μ₂-Cl)₂]⁴⁺ mixed oxo-chloro-clusters and bifunctional bridges gives a new three-dimensional framework with unusual spin-canting behavior.     

Transformation of the coordination nanostructures of 4,4′,4′′-(1,3,5-triazine-2,4,6-triyl) tribenzoic acid molecules on HOPG triggered by the change in the concentration of metal ions

The modulation effects of Cu²⁺/Fe³⁺ ions on the hydrogen-bonded structure of 4,4′,4′′-(1,3,5-triazine-2,4,6-triyl) tribenzoic acid (TATB) on a HOPG surface have been investigated at the liquid–solid interface by scanning tunneling microscopy (STM). STM observations directly demonstrated that the self-assembled honeycomb network of TATB has been dramatically transformed after introducing CuCl₂/FeCl₃ with different concentrations. The metal–organic coordination structures are formed due to the incorporation of the Cu²⁺/Fe³⁺ ions. Interestingly, a Cu²⁺ ion remains coordinated to two COOH groups and only the number of COOH groups involved in coordination doubles when the concentration of Cu²⁺ ions doubled. A Fe³⁺ ion changes from coordination to three COOH groups to two COOH groups after increasing the concentration of Fe³⁺ ions in a mixed solution. Such results suggest that the self-assembled structures of TATB molecules formed by metal–ligand coordination bonds can be effectively adjusted by regulating the concentration of metal ions in a mixed solution, which has rarely been reported before. It explains that the regulatory effect of concentration leads to the diversity of molecular architectures dominated by coordination bonds.

A Cu²⁺ ion maintains coordination with two COOH groups, while a Fe³⁺ ion changes from coordination with three to two COOH groups after increasing the concentration of Cu²⁺/Fe³⁺ ions.     

Syntheses,characterization and properties of three coordination polymers with interpenetrating structures comprising 4,4′-(1H-1,2,4-triazol-1-yl)methylene-bis(benzonic acid)

Three new coordination polymers (CPs), {[Pb(tmdb)](H₂O)}_n (1), {[Zn(tmdb)(bimb)_0.5]}_n (2) and {[Zn₃(tmdb)₃(bpmb)_1.5](H₂O)₆}_n (3) (H₂tmdb = 4,4′-(1H-1,2,4-triazol-1-yl)methylene-bis(benzonic acid), where bpmb = 1,4-bis(pyridin-4-ylmethoxy)benzene and bimb = 1,4-bis(imidazoly-1-yl)benzene), have been solvothermally or hydrothermally synthesized. Compound 1 is a 2D network with the point symbol (4·6·8)(4·6²) and compound 2 is a 4-fold interpenetrating 3D network with spiral chains. The topological type of 2 is dmc (topos&RCSR.ttd) with the point symbol (4·8²)(4·8⁵). Compound 3 is a 3-fold interpenetrating 3D network with the point symbol (6³)₂(8·6⁵)₂(10·6²)(8·10·6⁴). The electrochemiluminescence (ECL) behaviors of 2 and 3 were studied. The applications of CP 2 and 3 in detecting ions were explored, and the results show that they can be used as fluorescent probes to selectively detect and identify Fe³⁺ ions in water. In addition, the applications of CP 2 and 3 in the adsorption and separation of dyes were researched. Furthermore, the gas adsorption of 3 was studied.

The synthesis and characterization of three compounds with H₂tmdb ligands is reported. The polymers were analyzed using PXRD, IR, TGA and fluorescence spectrometry.     

Two-dimensional square-grid iron(ii) coordination polymers showing anion-dependent spin crossover behavior

Two Fe(ii)-based coordination polymers [Fe(tpmd)₂(NCS)₂]·5.5H₂O (1) and [Fe(tpmd)₂(NCSe)₂]·7H₂O (2) with the framework of square-grid type have been assembled from FeSO₄·7H₂O, N,N,N′,N′-tetrakis(pyridin-4-yl)methanediamine (tpmd), and KNCS/KNCSe in methanol and characterized. By utilizing two pyridine groups of a tpmd ligand, 1 and 2 are formed in two-dimensional layered structures through coordination of octahedral iron(ii) ions with the tpmd to NCS⁻/NCSe⁻ ligands in which they have a supramolecular isomorphous conformation. 1 shows a paramagnetic behavior between 2 and 300 K, while 2 exhibits two-step spin crossover (ca. 145 and 50 K) in the temperature range due to the coordination of NCSe⁻ ligands. At 300 K 2 is fully high-spin state. However, at 100 K 2 becomes ca. 50% high spin and 50% low spin iron(ii) ions, which is verified by magnetic moments. In the structural analysis of 2 at 100 K, two different layers are observed with different bond distances around iron(ii) ions in which the layers are stacked alternately.

Two-dimensional Fe-based coordination polymers with square-grid shapes were prepared by self-assembly and exhibited an interesting spin crossover behavior depending on the coordinated counter ions.     

Anti-inflammatory butenolide derivatives from the coral-derived fungus Aspergillus terreus and structure revisions of aspernolides D and G,butyrolactone VI and 4′,8′′-diacetoxy butyrolactone VI

Chemical investigation of the coral-derived fungus Aspergillus terreus led to the discovery of ten butenolide derivatives (1–10), including four new ones (1–4). The new structures were characterized on the basis of comprehensive spectroscopic analysis, including 1D and 2D NMR and HRESIMS data. Compounds 1 and 2 were a pair of rare C-8′′ epimers with vicinal diol motifs. The absolute configurations of 1–4 were determined via [Mo₂(AcO)₄] induced circular dichroism (ICD) spectra and comparison of their experimental ECD spectra. Importantly, the structures of reported aspernolides D and G, butyrolactone VI and 4′,8′′-diacetoxy butyrolactone VI have been correspondingly revised via a combined strategy of experimental validations, ¹³C NMR predictions by ACD/Labs software, and ¹³C NMR calculations. Herein we provide valuable referenced ¹³C NMR data (C-7′′, C-8′′, and C-9′′) for the structure elucidations of butenolide derivatives with 1-(2-hydroxyphenyl)-3-methylbutane-2,3-diol, 2-(2,3-dihydrobenzofuran-2-yl)propan-2-ol, or 2,2-dimethylchroman-3-ol motifs. Additionally, all the isolates (1–10) were assessed for anti-inflammatory activity by measuring the amount of NO production in lipopolysaccharide (LPS)-induced RAW 264.7 mouse macrophages, and compound 10 showed an even stronger inhibitory effect than the postive control indomethacin, presenting it as a promising lead compound for the development of new anti-inflammatory agents.

Chemical investigation of the coral-derived fungus Aspergillus terreus led to the discovery of ten butenolide derivatives (1–10), including four new ones (1–4).     

Synthesis,crystal structures,and luminescent properties of Zn(ii), Cd(ii), Eu(iii) complexes and detection of Fe(iii) ions based on a diacylhydrazone Schiff base

Acylhydrazone Schiff bases are rich in N and O atoms to coordinate with metal ions to form multidentate complexes. In this study, a novel diacylhydrazone Schiff base (N′¹E,N′⁴E)-N′¹,N′⁴-bis(2-hydroxy-5-nitrobenzylidene)succinohydrazide (H₄L) was synthesized from the condensation of nitrosalicylaldehyde and succinic dihydrazide. The interactions of H₄L with common monovalent, divalent and trivalent metal ions were investigated by ultraviolet spectroscopy and fluorescence spectroscopy. The results showed that H₄L had no obvious effect on the monovalent metal ions (Li⁺, Na⁺, K⁺), but reacted with most divalent and trivalent metal ions, and showed single selectivity in the fluorescence recognition of Fe³⁺ ions. More importantly, three kinds of binuclear molecular structures, [Zn₂(H₂L)₂]·5DMF (Zn-L), [Cd₂(H₂L)₂]·DMF·H₂O (Cd-L) and [Eu₂(H₂L)₃]·6DMSO (Eu-L), have been studied to further illustrate the interaction mode of diacylhydrazone Schiff base and metal ions. In addition, the optical properties of these crystallized complexes have been studied in DMF solution.

Acylhydrazone Schiff bases are rich in N and O atoms to coordinate with metal ions to form multidentate complexes.     

Investigating the reactivity of neutral water-soluble Ru(ii)–PTA carbonyls towards the model imine ligands pyridine and 2,2′-bipyridine

As a continuation of our strategy for preparing new Ru(ii) precursors to be exploited as building blocks in the construction of metal-mediated supramolecular assemblies with improved solubility in water, here we describe the reactivity of selected neutral Ru(ii)–PTA carbonyls (PTA = 1,3,5-triaza-7-phosphaadamantane) towards the model imine ligands pyridine (py) and 2,2′-bipyridine (bpy) and the preparation and characterization of several neutral and cationic water-soluble derivatives: trans,trans,trans-[RuCl₂(CO)(py)(PTA)₂] (7), cis,cis,trans-[RuCl₂(CO)₂(py)(PTA)] (9), cis,trans-[Ru(bpy)Cl(CO)(PTA)₂]Cl (10), mer-[Ru(bpy)(CO)(PTA)₃](Cl)₂ (12), cis,trans-[Ru(bpy)(CO)₂Cl(PTA)]Cl (13), cis,trans-[Ru(bpy)(CO)₂(PTA)₂](NO₃)₂ (14NO₃). In addition, we found that light-induced isomerization in some bpy compounds could be induced. The following species, either side-products isolated in low yield or compounds obtained exclusively in solution, were also unambiguously identified: cis,cis,trans-[RuCl₂(CO)(py)(PTA)₂] (8), trans-[RuCl₂(bpy)(CO)(PTA)] (11), cis,cis-[Ru(bpy)Cl(CO)(PTA)₂]Cl (15) and cis,cis-[Ru(bpy)(CO)₂Cl(PTA)]Cl (16). The X-ray structures of 7, 11·H₂O, and 12·7H₂O are also reported. All compounds are new and – with few exceptions – show a good solubility in water.

The reactivity of selected Ru(ii)-PTA carbonyls with potentially labile ligands (i.e. H₂O, dmso and/or Cl) towards the model imine ligands pyridine and 2,2′-bipyridine was investigated, yielding several neutral and cationic water-soluble derivatives.     

Structural diversity in the coordination compounds of cobalt,nickel and copper with N-alkylglycinates: crystallographic and ESR study in the solid state

Reactions of N-methylglycine (HMeGly), N-ethylglycine-hydrochloride (H₂EtGlyCl) and N-propylglycine-hydrochloride (H₂PrGlyCl) with cobalt(ii), nickel(ii) and copper(ii) ions in aqueous solutions resulted in ten new coordination compounds [Co(MeGly)₂(H₂O)₂] (1), [{Co(MeGly)₂}₂(μ-OH)₂]·2H₂O (1d), [Cu(MeGly)₂(H₂O)₂] (2α), [Co(EtGly)₂(H₂O)₂] (3), [Ni(EtGly)₂(H₂O)₂] (4), [Cu(μ-EtGly)₂]_n (5p), [Co(PrGly)₂(H₂O)₂] (6), [Ni(PrGly)₂(H₂O)₂] (7), and two polymorphs of [Cu(PrGly)₂(H₂O)₂] (8α and 8β). Compounds were characterized by single-crystal and powder X-ray diffraction, infrared spectroscopy, thermal analysis and X-band electron spin resonance (ESR) spectroscopy. These studies revealed a wide range of structural types including monomeric, dimeric and polymeric architectures, as well as different polymorphs. In all monomeric compounds, except 2α, and in the coordination polymer 5p hydrogen bonds interconnect the molecules into 2D layers with the alkyl chain pointing outward of the layer. In 2α and in the dimeric compound 1d hydrogen bonds link the molecules into 3D structures. 1d with cobalt(iii), and 4 and 7 with nickel(ii) are ESR silent. The ESR spectra of 1, 3 and 6 are characteristic for paramagnetic high-spin cobalt(ii). The ESR spectra of all copper(ii) coordination compounds show that the unpaired copper electron is located in the d_x²−y² orbital, being in agreement with the elongated octahedral geometry.

Interactions in copper, nickel and cobalt complexes with N-methyl-, N-ethyl- and N-propylglycinate: monomers, dimer and polymers.     

P-stereocontrolled synthesis of oligo(nucleoside N3′→O5′ phosphoramidothioate)s – opportunities and limitations

3′-N-(2-Thio-1,3,2-oxathiaphospholane) derivatives of 5′-O-DMT-3′-amino-2′,3′-dideoxy-ribonucleosides (_NOTP-N), that bear a 4,4-unsubstituted, 4,4-dimethyl, or 4,4-pentamethylene substituted oxathiaphospholane ring, were synthesized. Within these three series, _NOTP-N differed by canonical nucleobases (i.e., Ade^Bz, Cyt^Bz, Gua^iBu, or Thy). The monomers were chromatographically separated into P-diastereomers, which were further used to prepare N_NPSN′ dinucleotides (3), as well as short P-stereodefined oligo(deoxyribonucleoside N3′→O5′ phosphoramidothioate)s (NPS-) and chimeric NPS/PO- and NPS/PS-oligomers. The condensation reaction for _NOTP-N monomers was found to be 5–6 times slower than the analogous OTP derivatives. When the 5′-end nucleoside of a growing oligomer adopts a C3′-endo conformation, a conformational ‘clash’ with the incoming _NOTP-N monomer takes place, which is a main factor decreasing the repetitive yield of chain elongation. Although both isomers of N_NPSN′ were digested by the HINT1 phosphoramidase enzyme, the isomers hydrolyzed at a faster rate were tentatively assigned the R_P absolute configuration. This assignment is supported by X-ray analysis of the protected dinucleotide ^DMTdG^iBu_NPSMeT_OAc, which is P-stereoequivalent to the hydrolyzed faster P-diastereomer of dG_NPST.

Separated P-diastereomers of 3′-N-(2-thio-1,3,2-oxathiaphospholane) derivatives of 5′-O-DMT-3′-amino-2′,3′-dideoxy-ribonucleosides were used to prepare P-stereodefined N_NPSN′ dinucleotides and short NPS-, NPS/PO- and NPS/PS-oligomers.     

Turning over on sticky balls: preparation and catalytic studies of surface-functionalized TiO2 nanoparticles

We have investigated the reactivity of rhodium(iii) complex-functionalized TiO₂ nanoparticles and demonstrate a proof-of-principle study of their catalytic activity in an alcohol oxidation carried out under aqueous conditions water in air. TiO₂ nanoparticles (NPs) have been treated with (4-([2,2′:6′,2′′-terpyridin]-4′-yl)phenyl)phosphonic acid, 1, to give the functionalized NPs (1)@TiO₂. Reaction between (1)@TiO₂ NPs and either RhCl₃·3H₂O or [Rh₂(μ-OAc)₄(H₂O)₂] produced the rhodium(iii) complex-functionalized NPs Rh(1)₂@TiO₂. The functionalized NPs were characterized using thermogravimetric analysis (TGA), matrix-assisted laser desorption ionization (MALDI) mass spectrometry, ¹H NMR and FT-IR spectroscopies; the single crystal structures of [Rh(1)₂][NO₃]₃·1.25[H₃O][NO₃]·2.75H₂O and of a phosphonate ester derivative were determined. ¹H NMR spectroscopy was used to follow the reaction kinetics and to assess the recyclability of the NP-supported catalyst. The catalytic activity of the Rh(1)₂@TiO₂ NPs was compared to that of a homogeneous system containing [Rh(1)₂]³⁺, confirming that no catalytic activity was lost upon surface-binding. Rh(1)₂@TiO₂ NPs were able to withstand reaction temperatures of up to 100 °C for 24 days without degradation.

A proof-of-principle investigation of the reactivity of functionalized NPs Rh(1)₂@TiO₂ (1 = (4-([2,2′:6′,2′′-terpyridin]-4′-yl)phenyl)phosphonic acid, 1) is reported, using their catalytic activity in an alcohol oxidation in aqueous conditions water.     

Lanthanide induced variability in localised CoII geometries of four triangular L3Co3IILnIII complexes

Four tetranuclear heterobimetallic triangle complexes [L₃Co₃Dy(NO₃)₂(H₂O)(MeOH)₅](NO₃) (C1), [L₃Co₃Gd(NO₃)₃(MeOH)₄] (C2), [L₃Co₃La(NO₃)₂(H₂O)₆](NO₃)(H₂O) (C3), and [L₃Co₃TbCl(NO₃)₂(H₂O)_0.5(MeOH)_3.5] (C4), where H₂L = 1,4-bisformylnaphthalene-2,3-diol, have been synthesised and structurally characterised. Each complex crystallises with a complete molecule in the asymmetric unit (Z′ = 1) and displays near perfect octahedrality in two out of three Co^II centres. The third Co^II ion assumes a different coordination geometry in each complex: six-coordinate octahedral in C1, six-coordinate with a distortion towards trigonal prismatic in C2, five-coordinate trigonal bipyramidal in C3, and five-coordinate square pyramidal in C4; which has been attributed to increasing lanthanide cation size, coupled with a non-macrocyclic coordination environment. Continuous Shape Measurement (CShM) calculations and octahedral distortion parameter calculations were performed, using the SHAPE and OctaDist software packages, respectively, in order to aid in the assessment of each metal centre''s local coordination geometry. The preliminary magnetic investigation of C3 found χ_mT = 9.4 cm³ K mol⁻¹ at 300 K and M = 7.1 μ_B at 1.8 K, which are approximately two thirds the maximum theoretical values for three Co^II ions and indicates the presence of a relatively large zero-field splitting parameter (D/k_B = 65 K) operative in each Co^II ion rather than exchange coupling between the Co^II centres.

Four acyclic Co^II–₃Ln^III triangle complexes are reported in which two Co ions in each complex are octahedral while the third Co exhibits a lanthanide dependent coordination geometry. Magnetic analysis of the La complex shows a large ZFS effect for Co.     

Molybdenum imidazole citrate and bipyridine homocitrate in different oxidation states – balance between coordinated α-hydroxy and α-alkoxy groups

Oxo and thiomolybdenum(iv/vi) imidazole hydrocitrates K₂{Mo^IV₃O₄(im)₃[Mo^VIO₃(Hcit)]₂}·3im·4H₂O (1), (Him)₂{Mo^IV₃SO₃(im)₃[Mo^VIO₃(Hcit)]₂}·im·6H₂O (2), molybdenum(v) bipyridine homocitrate trans-[(Mo^VO)₂O(H₂homocit)₂(bpy)₂]·4H₂O (3) and molybdenum(vi) citrate (Et₄N)[Mo^VIO₂Cl(H₂cit)]·H₂O (4) (H₄cit = citric acid, H₄homocit = homocitric acid, im = imidazole and bpy = 2,2′-bipyridine) with different oxidation states were prepared. 1 and 2 are the coupling products of [Mo^VIO₃(Hcit)]³⁻ anions and incomplete cubane units [Mo^IV₃O₄]⁴⁺ ([Mo^IV₃SO₃]⁴⁺) with monodentate imidazoles, respectively, where tridentate citrates coordinate with α-hydroxy, α-carboxy and β-carboxy groups, forming pentanuclear skeleton structures. The molybdenum atoms in 1 and 2 show unusual +4 and +6 valences based on charge balances, theoretical bond valence calculations and Mo XPS spectrum. The coordinated citrates in 1 and 2 are protonated with α-hydroxy groups, while 3 and 4 with higher oxidation states of +5 and +6 are deprotonated with α-alkoxy group even under strong acidic condition, respectively. This shows the relationship between the oxidation state and protonation of the α-alkoxy group in citrate or homocitrate, which is related to the protonation state of homocitrate in FeMo-cofactor of nitrogenase. The homocitrate in 3 chelates to molybdenum(v) with bidentate α-alkoxy and monodentate α-carboxy groups. Molybdenum(vi) citrate 4 is only protonated with coordinated and uncoordinated β-carboxy groups. The solution behaviours of 1 and 2 are discussed based on ¹H and ¹³C NMR spectroscopies and cyclic voltammograms, showing no decomposition of the species.

Oxo and thiomolybdenum(iv/vi) citrates, molybdenum(v) homocitrate and molybdenum(vi) citrate were obtained, showing the influence of coordinated α-hydroxy and α-alkoxy groups with different oxidation states.     

A family of 3d metal clusters based on N–N single bonds bridged quasi-linear trinuclear cores: the Mn analogue displaying single-molecule magnet behavior

The reactions of the diacylhydrazine ligands N,N′-bisalicyl-2,6-pyridine dicarbohydrazide (H₆sphz) and N,N′-bis(3-methoxysalicyl)-2,6-pyridine dicarbohydrazide (H₆msphz) with various 3d metal salts, afforded a series of coordination clusters, namely, [Mn^III₂Mn^II(sphz)(acac)₂(CH₃OH)₄] (1, acac⁻ = acetylacetone anions), [Ni^II₃(msphz)(Py)₄] (2, Py = pyridine), [Cu^II₆(sphz)₂(Py)₄] (3) and [Cu^II₆(msphz)₂(Py)₄]·2DMF·2H₂O (4). Cluster 1 and 2 are single ligand assembled quasi-linear trinuclear structures. Both 3 and 4 consist a pair of quasi-linear {Cu₃} cores, which are linked together by two crossed ligands. The adjacent 3d metal ions in all trinuclear cores of 1–4 are bridged by N–N single bonds of ligands, which convey ferromagnetic (FM) interactions between 3d metal centers of 1, and antiferromagnetic (AFM) interactions between those of 2–4. In particular, the FM interactions and linear arrangement of mixed-valence Mn centers in 1 result in a large spin ground states value (S_T) of 13/2, as well as single-molecule magnet (SMM) behavior of slow relaxation and hysteresis of magnetization.

A family of 3d metal clusters featuring N–N single bonds bridged quasi-linear trinuclear cores were designed and synthesized. The Mn analogue represents a very rare case of quasi-linear 3d SMM using N–N single bonds as magnetic coupling pathways.     

Thermochemistry of cation disordered Li ion battery cathode materials, (M′ = Nb and Ta,M′′ = Mn and Fe)

High temperature oxide melt solution calorimetry studies on (M′ = Nb⁵⁺, M′′ = Mn³⁺ and Fe³⁺ and x = 0.20, 0.30 and 0.40) oxides and a new family of Ta containing Li excess disordered cathode materials, (M′ = Ta⁵⁺, M′′ = Fe³⁺ and x = 0.20, 0.30 and 0.40), synthesized by a rapid quenching method, are reported in this study. The enthalpies of formation determined from high temperature calorimetry studies reveal that the stability of compounds increases with the increasing Li content per formula unit. The reaction between more basic Li₂O and acidic transition metal oxides results in the more negative enthalpies of formation for these compounds. The work reveals that the formation enthalpy term plays a more important role in the stabilization of such disordered Li ion materials at room temperature whereas configurational entropy along with lattice entropy (vibrational and magnetic) contributes to the stabilization at high temperature from which the samples are quenched.

Enthalpies of formation from oxides (ΔH_f,ox) of novel disordered Li_1+xTa_xFe_1−2xO₂ and reported (M′′ = Mn³⁺ and Fe³⁺).     

Synthesis,structure and the Hirshfeld surface analysis of three novel metal-tiron coordination complexes

Three novel metal-tiron (4,5-dihydroxy-1,3-benzenedisulfonic acid disodium salt) and other pillared ligand bpy (4,4′-bipyridyl)-centered coordination polymers of the formulae [Cd(tiron)(bpy)₂(H₂O)₂]·0.5(H₂O), 1, [Co₃(tiron-bpy)₂(bpy)(H₂O)₈]·(H₂O)₂, 2, and [Ba₂(tiron-bpy)₂(H₂O)₄][solvent], 3, were successfully synthesized under hydrothermal conditions. The as-synthesized materials were well characterized by complimentary techniques such as single-crystal X-ray diffraction, powder X-ray diffraction, Fourier-transform infrared spectroscopy and thermogravimetric analysis techniques. The as-synthesized coordination polymers of 1 and 2 featured 1D chains, while 3 shows a layered structure. Co-based 2 shows linear trinuclear Co(ii) ions and these Co(ii) ions have antiferromagnetic interactions among themselves. The structure of 1 features a zig-zag chain formed by the linkage between monodentate tiron ligands and octahedral Cd(ii) ions, interconnected by a twisted bpy ligand, 2 shows a linear chain constructed from corner-sharing trinuclear octahedral Co(ii) ions and coordinated with a tridentate tiron-bpy adduct ligand, whereas 3 shows nona-coordinated Ba(ii) ions sharing edges with other Ba(ii) ions and connected by hexadentate tiron-bridged structures resulting in a layered structure. In 2 and 3, the bpy nitrogen attacks at the ortho position of the tiron ligand and forms an in situ ligand adduct. The central metal ions show an octahedral geometry in 1 (Cd(ii) ions) and 2 (Co(ii) ions), but nona-coordination of Ba(ii) ions in 3. The short interatomic interactions in the crystal structures were evaluated by mapping the Hirshfeld surface process using pseudo-mirrored 2D fingerprint plots. The major short interatomic interactions H⋯H, O⋯H and C⋯H cover the Hirshfeld surfaces.

Three novel metal-tiron (4,5-dihydroxy-1,3-benzenedisulfonic acid disodium salt) and other pillared ligand bpy (4,4-bipyridyl) centered coordination polymers were successfully synthesized and characterized.