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Ligating properties of a tripodal, potentially tetradentate aminetris(phenol) ligand, tris(2-hydroxy-3,5-di-tert-butylbenzyl)amine, H3L, containing [N,O,O,O] donor atoms toward the vanadium ions in +iiiand ivoxidation states have been studied. The structures of complexes 1[LVIII(CH3OH)]0, 2[LVIV(OCH3)]0and 3[LVIV(acac)]0were determined by X-ray diffraction methods as having five-coordinate V(iii), 1, five-coordinate non-oxo-vanadium(iv), 2, and six-coordinate non-oxo-vanadium(iv) 3, respectively. Compounds 1–3were also studied with electrochemical methods, variable-temperature (2–295 K) magnetic susceptibility measurements and X-band electron paramagnetic resonance (EPR) spectroscopy. The electrochemical results of 2and 3suggest metal-centered oxidation, i.e.the generation of a VV-phenolate species. EPR investigations indicate a (dxy)1ground state showing a considerable increase in the in-plane π-bonding, as is expected for a phenolate ligand. [ABSTRACT FROM AUTHOR]

Trialkyl imido niobium and tantalum complexes [MR3(NtBu)] (M = Nb, R = Me 2, CH2CMe33, CH2CMe2Ph 4, CH2SiMe35; M = Ta, R = Me 6, CH2CMe2Ph 7, CH2SiMe38) have been prepared by treatment of solutions containing [MCl3(NtBu)py2] (M = Nb 1a, Ta 1b) with three equivalents of magnesium reagent. By an unexpected hydrolysis reaction of the tris-trimethylsilylmethyl imido tantalum compound 8a, a μ-oxo derivative [(Me3SiCH2O)(Me3SiCH2)3Ta(μ-O)Ta(CH2SiMe3)2(NtBu)] (8a) was formed and its structure was studied by X-ray diffraction methods. Reactions of trialkyl imido compounds with two equivalents of isocyanide 2,6-Me2C6H3NC result in the migration of two alkyl groups, leading to the formation of a series of alkyl imido bisiminoacyl derivatives [MR(NtBu){C(R)NAr}2] (Ar = 2,6-Me2C6H3; M = Nb, R = Me 9, CH2CMe310, CH2CMe2Ph 11, CH2SiMe312, CH2Ph 13; M = Ta, R = CH2CMe314, CH2CMe2Ph 15, CH2SiMe316). All compounds were studied by IR and NMR (1H, 13C and 15N) spectroscopy. [ABSTRACT FROM AUTHOR]

Two isomorphous 3D Mn(II) and Co(II) coordination polymers with a dicarboxylate inner salt and cyanate as coligands were synthesized and structurally characterized, and their magnetic properties have been studied. In the compounds, [M(L)(NCO)]n·nH2O (M = Mn, Co, L = 1-carboxymethylpyridinium-4-carboxylate), neighboring metal ions are linked by the 3-fold bridges of an end-on cyanate and two syn–syncarboxylate bridges to give an anionic chain of [M(µ-NCO)(µ–COO)2]n, and each chain is interlinked to four other chains by the cationic 1-methylpyridinium spacers to generate a 3D structure with the 42· 63· 8 net topology. They are the first compounds with mixed cyanate and carboxylate bridges. Magnetic studies reveal that the 3-fold mixed bridge propagates antiferromagnetic coupling in the Mn(II) compound but ferromagnetic coupling in the Co(II) compound. The rather complex magnetic behaviors of the Co(II) compound are analyzed taking into account the first-order spin-orbital coupling and the intrachain ferromagnetic interactions. [ABSTRACT FROM AUTHOR]

The ligand [(1,3-phenylene)bis(methylene)]bis(1-ethyl-imidazol-2-ylidene) (2) (abbreviated as EtCNHCCHCNHCwith CH = central aromatic ring, = CH2spacer) has been synthesised, and isolated, by deprotonation of [(1,3-phenylene)bis(methylene)]bis(1-ethyl-imidazolium) dichloride, Et(CHimid.CHCHimid.)Cl2(1) with LiN(SiMe3)2. This new, remarkably stable NHC dicarbene ligand is quantitatively protonated with HBr to form [(1,3-phenylene)bis(methylene)]bis(1-ethyl-imidazolium) dibromide Et(CHimid.CHCHimid.)Br2(3) and reprotonated slowly enough in MeOH to allow observation of the monoprotonated intermediate 4. Dicarbene 2reacts with S8to give the dithione compound [(1,3-phenylene)bis(methylene)]bis(1-ethyl-imidazol-2-thione) Et[(SC)CH(CS)] (6). Reaction of 2with [IrCl(CO)(PPh3)2] and [Ir(μ-Cl)(cod)]2yielded the mononuclear [Ir(CO)(PPh3)2Et(CHimid.CHCNHC)(PF6)](PF6) (8) and [IrCl(cod)Et(CHimid.CHCNHC)](PF6) (10) complexes, respectively, and the dinuclear complexes [{Ir(CO)(PPh3)2}2Et(μ-CNHCCHCNHC)](PF6)2(7) and [{IrCl(cod)}2Et(μ-CNHCCHCNHC)] (9), respectively, in which 2acts as a bridging, non-pincer type ligand. Only one other Ir(i) complex has been reported before containing a CNHCCHCNHCligand. The structures of 6and 9were determined by X-ray diffraction and depict different conformations of the (1,3-phenylene)bis(methylene) (or xylylene) moiety. The mononuclear Ir complex 9reacted smoothly with [Rh(μ-Cl)(cod)]2and Cs2CO3to generate a rare example of a heteronuclear NHC complex, [IrRhCl2(cod)2Et(μ-CNHCCHCNHC)] (11). [ABSTRACT FROM AUTHOR]

The combination of a [1111]metacyclophane blocked in 1,3-alternate conformation and bearing four imidazole units with MX2(M = Co, Cu, Zn and Hg; X = Cl or Br) complexes leads to the formation of a series of analogous neutral metallamacrotricycles. In all cases, the structure of the binuclear complexes has been studied by X-ray diffraction methods on single crystals. [ABSTRACT FROM AUTHOR]

Gold complexes of 4-isocyanobenzoic acid, [AuX(CNC6H4CO2H)] (X = CC–C6H4–C9H19, C6F5, C6F4OC6H13, C6F4C6F4Br) and [(μ-4,4′-C6F4C6F4){Au(CNC6H4CO2H)}2], have been isolated. These metallo-acids are luminescent. The single crystal X-ray diffraction study of [Au(C6F5)(CNC6H4CO2H)]∞confirms a rod-like structure of the molecule, with a linear coordination around the gold atom, which extends into a supramolecular entity supported by hydrogen bond, gold-gold, and fluorophilic (ForthoFmeta) interactions. The carboxylic acid group of the gold isocyanide complexes acts also as a hydrogen donor towards the hydrogen acceptor decyloxystilbazole, affording some hydrogen-bonded supramolecular liquid crystals. [ABSTRACT FROM AUTHOR]

This paper explores the findings on the structures and physicochemical properties of titanium-oxo complexes (TOCs) stabilized by 9-hydroxy-9-fluorenecarboxylate ligands. Two complexes, with the overall formulas [Ti4O(OiPr)10(O3C14H8)2] (1) and [Ti6O4(OiPr)2(O3C14H8)4(O2CEt)6] (2), have been synthesized. The structures of the isolated crystals (1 and 2) were determined using single-crystal X-ray diffraction. Molecular structure analysis of the crystals also employed vibrational spectroscopic techniques (IR and Raman), UV--Vis diffuse reflectance spectroscopy (UV-Vis-DRS), and powder X-ray diffraction (XRD). Density functional theory (DFT) was utilized to elucidate the electronic structures of these complexes. Furthermore, the theoretical charge distribution in 1 and 2 and their reactivity were calculated. The results of these investigations suggest that the reactivity of 2 is significantly greater than that of 1. [ABSTRACT FROM AUTHOR]

Herein, gold nanoparticle-decorated amorphous carbon (Au/AC) was prepared by reducing chloroauric acid and layering it on amorphous carbon. The characteristics of Au/AC were examined using FT-IR, XRD, TGA, SEM, EDS, and XPS. To assess its catalytic activity, Au/AC was tested in a reaction involving anthranilamide and benzyl alcohol at 110 °C for 24 hours. This reaction yielded various 2-phenylquinazolin-4(3H)-one derivatives in moderate to good yields (44–80%). Furthermore, control experiments were conducted to demonstrate the oxidation and cyclization functions of Au/AC. Noteworthy aspects of this approach included the ease of isolating Au/AC (via recrystallization) and the ability to recycle it. [ABSTRACT FROM AUTHOR]

[MoV2 O2S2]2+-based thiosemicarbazone complexes appear as very promising molecules for biological applications due to the intrinsic properties of their components. This paper deals with the synthesis and characterization of six coordination complexes obtained by the reaction of [MoV2 O2S2]2+ clusters with bisthiosemicarbazone ligands that contain flexible or rigid spacers between the two thiosemicarbazone units. Interestingly, structural characterization by single-crystal X-ray diffraction, MALDI-TOF MS technique and NMR spectroscopy revealed that the nuclearity of the complex is controlled by the nature of the spacer between the thiosemicarbazone units. Binuclear complexes, namely [MoV2 O2S2(L1-3)], are isolated with flexible spacers while tetranuclear complexes [(MoV² O2S2)2(L4-6)2] are formed when the bisthiosemicarbazone ligands are built on rigid spacers. [ABSTRACT FROM AUTHOR]

The diagnosis and treatment of Chagas disease (CD) in the chronic phase remains a challenge. With that in mind, a potential theranostic device based on the trypanocidal agent known as megazol and the fac-M(CO)3+ (M = Re or 99mTc) fragment is proposed in the present work. The peripheral structure of megazol (LH,H) was modified to obtain the compounds LR1,R2 (R1 = H, R2 = Me and R1 = R2 = Me), which were used in the syntheses of complexes of composition [ReBr(CO)3LR1,R2]. These compounds were studied by elemental analysis, FTIR, UV-vis, NMR (1H and 13C), HR-ESI-MS, HPLC/UPLC and single-crystal XRD. The trypanocidal activity of the rhenium complexes was evaluated in vitro against the intracellular form of Trypanosoma cruzi. With exception of the [ReBr(CO)3LMe,Me] complex, all compounds are more active than the standard drug, benznidazole (Bzn), while [ReBr(CO)3LH,H] also exhibited a much higher selectivity index. In addition, the interaction of megazol and its ReI complex was evaluated with the T. cruzi Old Yellow Enzyme (TcOYE) by both experimental and computational methods. The data showed that megazol as well as its metal complex exhibited a higher affinity for TcOYE compared to Bzn. Finally, the labelling of megazol with 99mTc was successfully carried out. However, the results indicated that the Re complexes used as standards were not homologous with the 99mTc complexes. Despite this discrepancy, this research suggests that the investigation into Re and 99mTc complexes with megazol could lead to the development of a theranostic device for CD in a near future. [ABSTRACT FROM AUTHOR]

Two phosphates, KZnPO4 and NH4ZnPO4, were successfully synthesized using a solid-state reaction method and characterized via single-crystal X-ray diffraction. Both of their structures feature a three-way skeleton composed of isolated PO4 and ZnO4 tetrahedra, with K+/NH4+ cations occupying the spaces within the frameworks to balance charges. These compounds are isostructural and crystallize in the noncentrosymmetric P63 space group. Their structures were compared, revealing that non-centrosymmetric (NCS) KZnPO4 and NH4ZnPO4 exhibit second harmonic generation (SHG) responses of 0.4 × KDP and 1 × KDP, respectively. Furthermore, by combining the electronic structure and SHG density calculations, we examined the effects of ZnO4 tetrahedra on the SHG response of KZnPO4 and NH4ZnPO4. [ABSTRACT FROM AUTHOR]

Anhydrous plutonium tetrafluoride is an important intermediate in the production of metallic Pu. This historically important compound is also known to exist in at least two distinct, yet understudied hydrate forms, PuF4·xH2O(s) (0.5 ≤ x ≤ 2) and PuF4·2.5H2O(s). X-ray diffraction (XRD), thermogravimetric analysis (TGA), and scanning electron microscopy (SEM) are the most common tools used to characterize these materials, often in a context for studying structural and morphological changes that arise from aging or calcination. However, fundamental electronic and vibrational spectroscopic information is rather scarce. Here, we measured the visible and shortwave infrared (SWIR) diffuse reflectance, Fourier transform infrared (FTIR), fluorescence and Raman spectra of PuF4(s) and PuF4·xH2O(s) to obtain a better electronic and vibrational fingerprint. Our work provides clear indication of the polymeric structure of anhydrous PuF4, consistent with the Raman spectrum of UF4(s) and its hydrates. This is supplemented with XRD, TGA and SEM analysis. Findings in this study indicate that the spectra are modified by particle size, which in turn is influenced by synthetic technique. [ABSTRACT FROM AUTHOR]

Biofuels offer significant potential for reducing carbon emissions and enhancing energy sustainability, but their efficient purification remains a significant challenge. In this study, the performance of a hydrophobic zeolitic imidazolate framework, ZIF-71(ClBr)-SE, in the adsorptive separation of butanol from single- and ternary-component systems (acetone, butanol, and ethanol) was investigated and compared with ZIF-8 and ZIF-71. Physicochemical characterization techniques, including XRD, SEM, BET, TGA, and DVS, confirmed that the modified ZIF-71 is hydrophobic, isostructural with ZIF-71, and has a higher surface area. Adsorption tests in aqueous solutions revealed that ZIF-71(ClBr)-SE unexpectedly showed a higher affinity for acetone over butanol. DFT molecular simulations provided insights into solute-ZIF interactions, highlighting preferential sites for ZIF interaction. [ABSTRACT FROM AUTHOR]

A set of antimony(III) compounds containing a ligand (Ar) with a pendant guanidine function (where Ar = 2-[(Me2N)2C N]C6H4) was prepared and characterized. This includes triorgano-Ar3Sb, diorgano-Ar2SbCl and monoorgano-ArSbCl2 compounds and they were characterized by ¹H and 13C NMR spectroscopy and by single-crystal X-ray diffraction analysis (sc-XRD). The coordination capability of Ar3Sb and Ar2SbCl was examined in the reactions with either cis-[PdCl2(CH3CN)2] or PtCl2 and complexes cis-[(κ²-Sb,N-Ar3Sb)MCl2] (M = Pd 1, Pt 2) and [(κ³-N,Sb,N-Ar2SbCl)MCl2] (M = Pd 3, Pt 4) were isolated, while their structures were determined by sc-XRD. Notably, the ligands Ar3Sb and Ar2SbCl exhibit different coordination modes - bidentate and tridentate, respectively - and the antimony exhibits three distinct bonding modes in complexes 1-4, which were also subjected to theoretical studies. [ABSTRACT FROM AUTHOR]

A diprotic bis(β-thioketoimine) ligand precursor featuring a flexible 4,4'-methylbis(aniline) linker, H22, was synthesised via treatment of the corresponding bis(β-ketoimine) with Lawesson's reagent. Lithiation of H22 and coordination with one equivalent of d-block metal(II) chlorides MCl2(THF)x (M = Fe, Co and Zn) yielded a corresponding series of homoleptic dinuclear complexes, [M2(μ-2)2]. X-ray diffraction analysis reveals a tetrahedral geometry for the two metals and a double-stranded helicate structure arising from inter-strand face-face π-stacking. These interactions create a helical 'twist' of ca. 70°. Utilising a bulky mononucleating β-thioketoiminate ligand, [3]-, the analogous series of homoleptic monometallic complexes, [M(3)2] (M = Fe, Co and Zn), were prepared and characterised by spectroscopic and analytical techniques. A comprehensive DFT study of all complexes reveals a stronger M-S bonding compared to M-N due to a higher degree of covalency. Solution magnetic studies and natural bonding orbital calculations on the mono- and dinuclear iron and cobalt complexes are consistent with high-spin tetrahedral Fe(II) and Co(II) centres, and cyclic voltammetry reveals both oxidation and reduction processes are accessible. [ABSTRACT FROM AUTHOR]

The LiNbV(PO4)3 phosphate with the anti-NASICON structure (a = 12.126(1) Å, b = 8.6158(4) Å, c = 8.6959(6) Å, V = 908.5(1) Å3, S.G. Pbcn) has been synthesized using a Pechini sol–gel process. It exhibits reversible multielectron transitions versus Li and Na anodes. In a Li half-cell, it supports a 4e− transfer due to the activation of the Nb5+/Nb3+ and V4+/V2+ redox couples, being the first example of 4d metal redox transitions within the anti-NASICON framework confirmed by XANES measurements. X-ray diffraction performed in ex situ and operando regimes disclosed a single-phase mechanism of lithium (de)intercalation. In a Na half-cell, the material demonstrates reversible uptake of 2.77 Na+ ions. Density functional theory calculations revealed percolation barriers of ∼0.5–0.7 eV for Na+ hopping, thus supporting the activation of Na+ ion diffusion in the NbV(PO4)3 framework. This study introduces a new approach to improve anti-NASICON-structured electrode materials by utilizing redox transitions of 4d elements for energy storage. [ABSTRACT FROM AUTHOR]

Fluorite-type nanocrystalline 5% iron-substituted ceria (Ce0.95Fe0.05O2−δ) was synthesized by the solution combustion method with an average crystallite size of 15 nm. The catalyst was well characterized by SEM, EDX, XPS, XRD, and H2-TPR studies, which confirmed the substitution of Fe3+ in the CeO2 lattice. This precious metal-free catalyst was developed for the selective conversion of various arylboronic acids to the corresponding biphenyls and phenols employing K2S2O8 and H2O2, respectively. This catalyst could be coated on cordierite monolith, which acts as a catalyst cartridge employed efficiently in recycling experiments up to seven cycles. The scale-up reaction was also carried out with a catalyst cartridge, affording a good yield of the desired product. [ABSTRACT FROM AUTHOR]

The redox properties of half-sandwich rhodium complexes supported by 2,2′-bipyridyl (bpy) ligands can be readily tuned by selection of an appropriately substituted derivative of bpy, but the influences of single substituents on the properties of such complexes are not well documented, as disubstituted bpy variants are much more common. Here, the synthesis, characterization, and redox properties of two new [Cp*Rh] complexes (where Cp* is η5-1,2,3,4,5-pentamethylcyclopentadienyl) supported by the uncommon mono-substituted ligands 4-chloro-2,2′-bipyridyl (mcbpy) and 4-nitro-2,2′-bipyridyl (mnbpy) are reported. Single-crystal X-ray diffraction studies and related spectroscopic experiments confirm installation of the single substituents (–Cl and –NO2, respectively) on the bipyridyl ligands; the precursor monosubstituted ligands were prepared via a divergent route from unsubstituted bpy. Electrochemical studies reveal that each of the complexes undergoes an initial net two-electron reduction at potentials more positive than that associated with the parent unsubstituted complex of bpy, and that the complex supported by mnbpy can undergo a third, chemically reversible reduction at −1.62 V vs. ferrocenium/ferrocene. This redox behavior is consistent with inductive influences from the substituent groups on the supporting ligands, although the nitro group uniquely enables addition of a third electron. Spectrochemical studies carried out with UV-visible detection confirm the redox stoichiometry accessible to these platforms, highlighting the rich redox chemistry and tunable behavior of [Cp*Rh] complexes supported by bpy-type ligands. [ABSTRACT FROM AUTHOR]

Two Mn-phosphinophosphinine complexes were synthesised from reaction of the proligand with [MnBr(CO)5] at 80 °C for 2 h; 2-diphenylphosphino-3-methyl-6-trimethylsilylphosphinine manganese tricarbonyl bromide (2TMS) and 2-diphenylphosphino-3-methyl-phosphinine manganese tricarbonyl bromide (2H). 31P{1H} NMR spectroscopy revealed characteristic chemical shifts for the phosphinine and phosphine donors bound to Mn (255.4 and 23.7 ppm for 2TMS; 234.2 and 24.8 ppm for 2H), and single crystal X-ray diffraction established the structure of the chelating complex 2TMS. Rapid reaction of both complexes with water was observed with 2TMS reacting to eventually yield a single product, syn-3TMS, from the syn-1,2-addition of water across the P＝C multiple bond on the bromide face, confirmed by X-ray diffraction for both an unsolvated and solvated structure, where MeOH was found to be H-bonding to the P-OH functionality. The reaction of 2R with dry methanol gave multiple products that were not in equilibrium with each other, and the molecular structure of one isomer was definitively established by X-ray diffraction as an unusual 1,4-addition product (1,4-4TMS). However, reaction of 2R with methanol in the presence of trace water showed that hydrolysis products 3R were formed preferentially. Both phosphinine complexes acted as pre-catalysts for the Guerbet upgrading of methanol/ethanol to isobutanol at 180 °C over 90 h, giving yields of isobutanol (based on moles of ethanol) of 22% for 2TMS and 27% for 2H. This is superior to known Mn dppm complexes [dppm = bis(diphenylphosphino)methane], including the 21% yield recorded for the best derivative [MnBr(κ2-PPh2C(H)PhPPh2)(CO)3] shown to date. [ABSTRACT FROM AUTHOR]

Starting from ClSbRF2 (RF = C2F5, 3,5-(CF3)2C6H3) and H(E)P(tBu)2 (E = O, S), we prepared the oxy- and sulphanediyl-bridged adducts RF2Sb(Cl)–E–(H)P(tBu)2, which are stable against the elimination of HCl. The different electron-withdrawing substituents and chalcogen bridging units influence the size of the Sb–E–P angle. ClSb(C2F5)2 and nBu3SnH react to give HSb(C2F5)2, which seems to interact weakly with H(O)P(tBu)2 in solution as observed via NMR. All products were characterised by NMR spectroscopy and all the stable ones were additionally characterised by X-ray diffraction and elemental analyses. [ABSTRACT FROM AUTHOR]

The tunable molecular scaffold of organic moieties in metallopolymers generates variation in their properties, but what could be the minimal change that can produce variation in the properties of these macromolecules is still untouched. This research has meticulously explored the trivial change in the molecular scaffold of the ligand capable of making a mammoth difference in the nonvolatile memory and coordination pattern in two metallopolymers. The significance of this research lies in the fact that it demonstrates how a slight change in the organic building block can significantly alter the memristive and fluorescence properties of iron(II) metallopolymers, opening up new possibilities for their design and synthesis. Two novel positional isomeric ligands and their corresponding iron(II)-polymers were synthesized and thoroughly characterized using NMR, XRD, ATR-IR, FESEM, AFM and other techniques. Bright orange solid and solution state fluorescence was observed both in the solid and solution states for ligand L2 (3,3′-bis((E)-(pyridin-3-ylimino)methyl)-[1,1′-biphenyl]-4,4′-diol), while ligand L1 (3,3′-bis((E)-(pyridin-2-ylimino)methyl)-[1,1′-biphenyl]-4,4′-diol) showed blue fluorescence in the solution state only. A robust memristive property for Fe(II)-L1-poly with a high current ON/OFF ratio of 104, remarkable random access behaviour, and a long retention time greater than 35 000 seconds was observed while its counterpart was entirely silent. Both polymers showed solution-state electrochromism. These synthesised metallopolymers also showed good specific capacitance in the range of 50–60 F g−1 with a remarkable retention of 98% of the initial value even after 5000 charge–discharge cycles. The AFM and FESEM micrographs revealed the formation of long polymer nano-rods, which correlates with the NMR, ATR-IR, and XRD results. The difference in the properties of polymers generated by such a slight change in the organic building block forces different coordination patterns of these two ligands around the same central metal ion, and this is also evident in all the characterization methods. [ABSTRACT FROM AUTHOR]

A series of heterobimetallic complexes Au/M (M = RhIII, IrIII) were prepared on the basis of two ditopic ligands: a monophosphane ligand L1H and a triphosphane ligand L2H. The complexes were fully characterised, including single-crystal X-ray diffraction studies. Catalytic activity of cationic L1/AuI/IrIII and L2/AuI/IrIII bis(trifluoromethane)sulfonimide was analysed through their capacity to induce allenyl ether rearrangement and cycloisomerisation of N-propargyl benzamide. While cationic L1/AuI/IrIII showed some ability to induce allenyl ether rearrangement, no conversion was observed for cationic L2/AuI/IrIII. Similarly, N-propargyl benzamide could undergo cycloisomerisation in the presence of cationic L1/AuI/IrIII, whereas cationic L2/AuI/IrIII was again inactive. These findings highlight how crucial the surroundings of the metal centre are to the catalytic activity. Catalytic activity is only possible when Au has a free coordination site; the gold complex becomes inactive when the tridentate ligand is present. [ABSTRACT FROM AUTHOR]

Mutual separation of trans-plutonium actinides (Ans) from lanthanides (Lns) or adjacent Ans is challenging as they exhibit great chemical similarity. Selective Am oxidation-based Am–Lns or Am–Cm separation strategies give very high separation factors. There exist several reports on different aspects of Am3+ oxidation by NaBiO3·xH2O (x = 2–3), which suggests that the oxidation mechanism is still not well understood. We, therefore, carefully performed several experiments taking advantage of the difference in the redox chemistry of Eu3+ and Am3+. The ion exchange of Eu3+ with the interlayer Na+ in NaBiO3 was confirmed by an ionic strength variation experiment. The shift in the 001 peak of NaBiO3 in XRD and the appearance of peaks corresponding to the trivalent Ln ions in XRF after Ln3+ loading give direct evidence for Na+ exchange with Ln3+. The stability of the higher oxidation state of Am was monitored spectrophotometrically. The experimental investigations also suggested the role of Am3+ → AmO22+ transformation in NaBiO3·xH2O (x = 2–3) dissolution even at pH ∼ 1, which otherwise is difficult to achieve even with >1 M HNO3. The role of colloidal NaBiO3 particles and dissolved BiO3− in controlling or stabilizing different oxidation states of Am was also discussed. [ABSTRACT FROM AUTHOR]

In this work, an alane, [DNIAlH2] (1) (DNI = 3,3-dimethyl-2-[2-methyl-2-(2,6-diisopropyl-aniline)ethenyl]-3H-indolenine), stabilised by a hybrid ligand was reduced by Jones's Mg(I) ([(MesBDIMg)2]) and Roesky's Al(I) ([DippBDIAl:]). The resulting dialane compound [{DNI(H)Al}2] (2) was characterised using NMR spectroscopy, mass spectrometry, DFT calculations and single-crystal XRD experiments. The reaction of aluminium dihydride [DNIAlH2] (1) with [DippBDIAl:] at high temperatures gives an intramolecular C(sp2)–H bond-activated compound 3. To study the monomeric hybrid ligand-based Al(I), characterisations and computational calculations were performed, which elucidate that compound 5, consisting of two inequivalent aluminium atoms in an Al2CN four-membered ring, resulting from the activation of a carbon–nitrogen bond in the reaction of [DNINa] with [(Cp*Al)4]. [ABSTRACT FROM AUTHOR]

A new cyanido bridged Zn(II)–Mn(II) mixed-metal coordination polymer, {[Zn(μ-L)(μ-CN)2Mn0.5]·(CH3OH)}n (1), has been synthesized by the reaction of Zn(CN)2, Mn(II) salts and a hydrazone ligand (HL = (E)-N′-(phenyl(pyridin-2-yl)methylene)isonicotinohydrazide) in methanol. Compound 1 was characterized using various analytical methods (including elemental analysis, photoluminescence, FT-IR, XRD, SEM, and EDX analyses, and TGA), and its structure was determined by X-ray analysis. These analyses confirmed the formation of a mixed metal Zn(II)–Mn(II) coordination polymer containing both cyanide and hydrazone bridging ligands. This mixed metal coordination polymer exhibits interesting emission spectra by having several emissions via excitation at 230, 270, 375 and 385 nm. The catalytic activity of compound 1 in chemical CO2 fixation was investigated in the presence of epoxides, and the effects of various parameters on its catalytic performance were evaluated. The results of catalytic studies show that compound 1 can efficiently catalyze the chemical CO2 fixation reaction under mild conditions. The amount of co-catalyst, temperature of the reaction, nature of the solvent and also the substituent connected to the epoxide ring are some of the important parameters that have considerable effects on the catalytic activity of 1. [ABSTRACT FROM AUTHOR]

Two o-carborane-hybridized macrocyclic arenes have been synthesized via Friedel–Crafts alkylation of carborane diaryl derivatives. The single-crystal X-ray diffraction analysis clearly revealed their cavity structure and intermolecular interaction force. These novel macrocycles exhibited aggregation-induced luminescence and intramolecular charge transfer properties and also significant selectivity towards nitro explosive compounds. This work provided a method for the synthesis of hybridized macrocyclic arenes. [ABSTRACT FROM AUTHOR]

In this study, a catalyst composite of Co–Cu was prepared from chloride-containing precursor of Co(II) and Cu(II) metals using the milky latex of the Euphorbia neriifolia plant following green principles of synthesis. The catalyst composite was characterized using XRD, EDAX, SEM, HR-TEM, FTIR, XPS and TOF-MS. The crystallinity of the mixed-oxide composite with a distorted octahedral nature was confirmed from analysis. Chemical charge analysis of the Co–Cu mixed phase based on XPS revealed Co2+ and Cu2+ oxidation states. This material was used for synthesizing 2,4,5-triaryl-1H-imidazole (TIMDZOL) derivatives. Analysis of reaction conditions revealed that EtOH : PEG at 8 : 2 ratio under microwave conditions showed better yields with less time and better reusability of the Co–Cu catalyst. [ABSTRACT FROM AUTHOR]

Fumed alumina from the combustion of AlCl3 produced nano particles with specific areas from 30 to 220 m² g-1 (BET) which were characterized by powder X-ray diffraction, 27Al solid-state NMR and transmission electron microscopy. During the short-lived synthesis, highly disordered γ-alumina progressively transforms into a mixture of δ and θ-alumina. For the γ-alumina particles, only for particles with the highest specific area a significant amount of five-coordinated Al can be found which is only partially located in the particle surface. Water can be bound reversibly and increases the coordination number of aluminium atoms in the particle surface. For the well-crystallized mixture of δ and θ-alumina, high resolution and high S/N powder XRD pattern features a large number of superstructure reflections along with the commonly observed diffuse reflections. 27Al MQMAS NMR provides a total of 8 crystallographic sites with an unusually high resolution in the tetrahedral region, with 4 distinct AlO4 sites pertaining to the δ phase alone. The results suggest that the δ-alumina phase produced in this process can be described as an ordered structure. [ABSTRACT FROM AUTHOR]

Transition metal tellurides (TMTes) have received extensive attention for high specific energy sodium-ion batteries (SIBs) due to their high volumetric specific capacity. However, the continuous capacity attenuation arising from the huge volumetric strain during sodiation/desodiation impedes practical applications. Here, we report a "sandwich-type" carbon confinement strategy that entraps cobalt ditelluride (CoTe2) nanocrystals between two carbon layers. Porous cellulose-derived fibres were employed as the inner carbon framework to construct fast conductive circuits and provide an abundant site for anchoring CoTe2 nanocrystals. Polyvinylpyrrolidone (PVP)-derived carbon layers act as carbon armour to encapsulate CoTe2 nanocrystals, inhibiting their volume change and structural pulverization during repeated sodium intercalation/deintercalation. Benefiting from the exquisite structural design, the N-C@CoTe2@C electrode exhibits excellent cycling stability for over 3000 cycles at 2.0 A g−1 and rate performance (113.8 mA h g−1 at 5.0 A g−1). Moreover, ex situ XRD/TEM and kinetic tests revealed a multistep conversion reaction mechanism and a battery-capacitive dual-model Na-storage process. This work provides a new perspective on the development of low-cost and straightforward techniques for fabricating long-life commercial SIB anode materials. [ABSTRACT FROM AUTHOR]

This paper reports two closely related heteropentanuclear manganese complexes, namely, {Na2Mn3(opch)3(μ4-O)(μ2-N3) (μ2-AcO)(μ2-MeO)}·6CH3OH·0.5H2O (1) and {Na2Mn3(opch)3(μ4-O)(μ2-N3)2(μ2-AcO)}·2.5CH3OH·2H2O (2), where H2opch is (E)-N′-(2-hydroxy-3-methoxybenzylidene)pyrazine-2-carbohydrazide. Single-crystal X-ray diffraction analysis reveals that the trigonal bipyramidal skeletons in both complexes are comparable, where a perfect triangular Mn3 motif occupies the equatorial plane. Magnetic investigations suggest that overall antiferromagnetic coupling is present within the triangles of 1 and 2. However, their dynamic magnetic properties are drastically distinct. Indeed, complexes 1 and 2 show two kinds of dual slow magnetic relaxation processes that correspond to anisotropy barriers (Δ) of 9.2 cm−1 (11.4 cm−1 for 2) and 12.8 cm−1 (30.0 cm−1 for 2) for the low- and high-frequency domains, respectively. More importantly, a further comparative study of the structure and magnetism indicates that the coordination sphere of these two model complexes with the homologous hydrazone-based coordination sites undergoes an alteration from methoxide-O to azide-N upon a subtle change of the auxiliary anion accompanied by modulating octahedron geometries, leading to a further influence on different relaxation dynamics. [ABSTRACT FROM AUTHOR]

Five cationic ruthenium(II) chelates with the generic formula [Ru(S2C·NHC)3](PF6)2 were readily obtained upon cleavage of the [RuCl2(p-cymene)]2 dimer with representative imidazol(in)ium-2-dithiocarboxylate zwitterions (NHC·CS2) in the presence of KPF6. The homoleptic complexes were fully characterized by various analytical techniques and the molecular structure of one of them was determined by single-crystal X-ray diffraction analysis. As expected, it featured an octahedral RuS6 core surrounded by three imidazol(in)ium rings and their nitrogen substituents. The robustness of the Ru–S bonds combined with the chelate effect of the κ2-S,S′-dithiocarboxylate units and the steric protection imparted by bulky 1,3-diarylimidazol(in)ium groups most likely accounted for the outstanding stability of these species in solution. Cyclic voltammetry showed that the five homoleptic complexes featured characteristic waves for a monoelectronic redox process corresponding to the RuIII/RuII couple with E1/2 values ranging between 0.97 and 1.27 V vs. Ag/AgCl. This half-wave potential was clearly dependent on the nature of their ancillary ligands as the evolution of the Ep,ox values roughly paralleled the basicity sequence of the NHCs used to prepare them, in line with the trends observed when monitoring the chemical shifts of the CS2− unit on 13C NMR spectroscopy and the CS2− asymmetric stretching vibration wavenumbers on IR spectroscopy. [ABSTRACT FROM AUTHOR]

Ferrocene-substituted carbenes have emerged as attractive, redox-active ligands. However, among the compounds studied to date, ferrocenylated 1,2,4-triazol-5-ylidenes, which are closely related to the archetypal imidazol-2-ylidenes, are still unknown. Here, we demonstrate that the triazolium salt [CHN(Me)NCHN(Fc)]I (2; Fc = ferrocenyl), obtained by alkylation of 4-ferrocenyl-4H-1,2,4-triazole (1) with MeI, reacts selectively with metal alkoxide/hydroxide precursors [(cod)Rh(OMe)]2 and [(IPr)Au(OH)] (cod = cycloocta-1,5-diene, IPr = 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene) to produce the ferrocene-substituted 1,2,4-triazol-5-ylidene complexes [(cod)RhI{CN(Me)NCHN(Fc)}] and [(IPr)Au{CN(Me)NCHN(Fc)}]I in good yields. The complexes were characterised by NMR and IR spectroscopy, mass spectrometry, cyclic voltammetry, and single-crystal X-ray diffraction analysis. Density function theory (DFT) calculations were used to rationalise the electrochemical behaviour of the carbene complexes and to elucidate the bonding situation in these compounds. An analysis using intrinsic bond orbitals (IBOs) revealed that the 1,2,4-triazol-5-ylidene ligand exerted a strong trans influence and showed a synergistic stabilisation by the negative inductive and positive π-donor effects of the nitrogen atoms adjacent to the carbene carbon atom; these effects were enhanced by conjugation with the CH＝N bond at the exterior, similar to that in imidazol-2-ylidenes. [ABSTRACT FROM AUTHOR]

By introducing the d0 metal cation Mo6+ into phosphates, two new molybdophosphates, K2MgMoP2O10 and K3Mg2MoP3O14, were synthesized by spontaneous crystallization, and their structures were determined by single-crystal X-ray diffraction. K2MgMoP2O10 shows a two-dimensional layer composed of the uncommon eight-membered ring [Mo2P2O16] formed by [MoO6] and [PO4], while K3Mg2MoP3O14 shows isolated [MoP3O14] clusters composed of [MoO5] and [PO4]. K2MgMoP2O10 and K3Mg2MoP3O14 have UV cut-off wavelengths of 277 and 271 nm, respectively, which are significantly shorter than those of most recently published molybdophosphates. To the best of our acknowledge, K2MgMoP2O10 exhibits the largest birefringence (a calculated value of 0.187 at 546 nm) among reported alkali metal or alkaline earth metal molybdophosphates, which provides a way to explore new birefringent materials. First-principles analysis of the electronic structure shows that the large birefringence of K2MgMoP2O10 mainly originates from the [MoO6] units. [ABSTRACT FROM AUTHOR]

A rigid pentadentate chelating ligand (H2L) has been utilized to synthesize a series of octacoordinate mononuclear complexes, [Dy(L)(Ph3PO)(OOCR)] (where R = C6H5 (1), C(CH3)3 (2), CF3 (3)) and a dinuclear complex, [Dy2(L)2(Ph3PO)2{(OOC)2C6H4}] (4) based on the highly anisotropic Dy(III) ion. All the complexes were structurally characterized by single-crystal X-ray diffraction studies. The complexes were formed by the coordination action of the dianionic pentadentate ligand [L]2−, one phosphine oxide, and carboxylate ligands. DC and AC magnetic measurements were performed on 1–4. Complexes 1–4 show SMM behaviour, under zero DC field for 1 and 4, and under 500 Oe and 1000 Oe DC fields for 2 and 3 respectively, with thermally activated, Raman, and Raman and quantum tunnelling dominant relaxation mechanisms for 1 and 2, 3 and 4, respectively. [ABSTRACT FROM AUTHOR]

The second near-infrared window (NIR-II) in the range of 1000–1400 nm is ideal for in vivo imaging and sensing through reduced scattering, absorption, and autofluorescence. However, there are only a few nanophosphor systems with emission in the NIR-II region. Here, we report on Mn5+-doped Ba5(PO4)3Cl nanoparticles (BPCl:Mn5+ NPs, d < 50 nm) toward NIR-II temperature sensing. BPCl:Mn5+ NPs are made by a two-step (hydrothermal and anion exchange) method. XRD, SEM, and TEM results showed that the as-prepared BPCl:Mn5+ NPs show high crystallinity, uniform size, and sphere-like morphology. The nanoparticles exhibit a broad excitation band of 500–850 nm and a temperature-sensitive peak emission at 1175 nm in the NIR-II range. NIR-II temperature sensing by 1E emission intensity is demonstrated with good linear fitting (R2 = 0.9895), high sensitivity (2.30% at 373 K), and good repeatability (99.0%). Thus, our study provides a path to develop a new NIR-II thermometer based on tetrahedral Mn(V) coordination. [ABSTRACT FROM AUTHOR]

A new Co4-added polyoxometalate (CoAP) Cs4[(Co(H2O)5)2{(μ2-Co(H2O)4)2Co4(H2O)2(B-α-GeW9O34)2}]·6H2O (1) has been made using a lacunary directing strategy under hydrothermal conditions. Single-crystal X-ray diffraction analysis demonstrated that 1 is a one-dimensional (1D) chain, in which CoAP is linked by cobalt-oxygen octahedra to form a 1D structure with excellent chemical stability. The visible light-driven H2 evolution test demonstrated that 1 has high activity, with an H2 evolution rate of 1485.95 μmol h−1 g−1. PXRD and FT-IR tests demonstrated that compound 1 exhibits excellent heterogeneous catalytic stability. [ABSTRACT FROM AUTHOR]

Six organotin(IV) compounds (1–6) have been synthesized by reaction of the polydentate pro-ligands H3L and H2L, respectively, with the corresponding diorganotin chlorides. All of the compounds were characterized by FT-IR spectroscopy, 1H, 13C{1H}, and 119Sn (1H) NMR spectroscopy, HRMS spectrometry, and single-crystal X-ray diffraction. The solid-state structures show that all of the compounds are monomeric (except compound 3) and contain a penta-coordinated tin atom. Compound 3 is a dimer with two hexa-coordinated tin atoms. Compounds 1–3 contain a non-coordinated hydroxymethyl group. All of the compounds have been screened for their catalytic efficacy in the synthesis of 1,2 disubstituted benzimidazoles using o-phenylenediamine and aldehyde derivatives. It has been observed that both the Lewis acidic Sn(IV) centre and the hydroxymethyl group (hydrogen bond donor) catalyse the reactions with a product yield of up to 92%. [ABSTRACT FROM AUTHOR]

We have found that amines significantly accelerate iodide substitution in CpFe(CO)2I (1) (Cp = η5-cyclopentadienyl) with phosphines and allow the synthesis of new complexes that are not available through reactions carried out without an amine. The reaction of equimolar amounts of 1 and triphenylphosphine in toluene containing DIPA afforded [CpFe(CO)2PPh3]+I− within 5 min at room temperature in 72% yield (90% after 24 h). DIPA and pyrrolidine gave the highest yields of the tested amines. We performed a similar reaction using model bisphosphines 1,3-bis(diphenylphosphino)ethane (dppe) and 1,1′-bis(diphenylphosphino)ferrocene (dppf). The products depended on the reagent ratio and bore the CpFe(CO)2 moiety coordinated to one or two phosphine phosphorus atoms. Chelates [CpFe(CO)(dppe)]+I− (4) and [Cp2Fe2(CO)4(dppe)]2+2I− (5) were formed in 72% and 98% yield, respectively. We also performed the DIPA-catalyzed reaction of 1 with triethyl phosphite and obtained the product of an Michaelis–Arbuzov-like rearrangement, CpFe(CO)2[P(O)(OCH2CH3)2] (11). All complexes were characterized with spectroscopic analysis by NMR, FT-IR, and ESI-MS, and by XRD for three complexes. To clarify the reaction mechanism, we performed theoretical calculations of the intermolecular interactions between 1 and amine molecules. We propose two possible reaction mechanisms to explain the formation of products. [ABSTRACT FROM AUTHOR]

We explored dual precipitating reagents-assisted Ce-based deep blue-emitting borate and near-white oxide-based luminescent materials. The first precipitating reagent (aqueous sodium borohydride) was used until gelation. The second precipitating reagent (ammonia solution) was employed to prepare as-synthesized powders. XRD analysis, FTIR spectroscopy, and Raman spectroscopy of calcined powders ranging from 1000 °C to 1400 °C confirmed the development of a primary borate phase (i.e., nearly polyhedral-shaped YBO3) with secondary phases of (Y,Al)BO3 and oxide. However, the preliminary oxide phase (i.e., elongated/rod-like YAG) and secondary phases of YBO3, Al2O3, and CeO2 were developed at 1500 °C with different holding times. The emission behavior and CIE coordinates confirmed that the borate (i.e., YBO3-based) sample was deep blue. However, the oxide (i.e., YAG-based) sample showed tunable color emissions from light blue to near white with increased holding time. The average lifetime of prepared samples varied between 788 ns and 891 ns, which indicated a long decay time. The quantum yield of the sample calcined at 1400–1500 °C varied between ∼61% and ∼77%. Based on the emission behavior, CIE diagram, CCT, powder color, average lifetime, and quantum yield, the developed deep blue-emitting borate and light blue/near white oxide-based luminescent materials could be used in lighting industries. [ABSTRACT FROM AUTHOR]

Boron compounds have attracted the attention of chemists because of their unique catalytic properties and potential wider material applications. Although group 13 metal compounds, which are based on the bis-(benzoxazol-2-yl)-methane system (Box, ({NCOC6H4}2CH2)), have been reported in the last several years, boron containing Box compounds were still missing. Now we report their successful syntheses and spectroscopic characterisation in this work. The borane compound [({NCOC6H3}2CH)BH2] (1) and haloboranes [({NCOC6H3}2CH)BF2] (2), [({NCOC6H3}2CH)BCl2] (3) and [({NCOC6H3}2CH)BBr2] (4) were characterised in the solid state by single crystal X-ray diffraction and in solution by NMR techniques. In addition, the fluorescence properties of compounds 1–4 are communicated. [ABSTRACT FROM AUTHOR]

Hexadentate poly-Lewis acids (PLA) based on the bowl-shaped tribenzotriquinacene (TBTQ) have been synthesised. The introduction of three n-propyl groups into the benzhydrylic positions of the TBTQ backbone has significantly increased the solubility of the subsequently derived compounds. Semi-flexible PLAs containing boron and aluminium were obtained by hydrometallation of the corresponding 2,3,6,7,10,11-hexaalkynyl-TBTQ. Other rigid hexadentate PLAs were synthesised by stannylation of the corresponding alkyne units with Me3SnNMe2 followed by tin-element exchange reactions. The Lewis acidity of these PLAs was investigated in host–guest experiments with pyridine. Further experiments with bidentate bases showed correlations between their flexibility, their Lewis basicity and the complexation behaviour towards the synthesised PLAs. Addition of bis((dimethylphosphino)methyl)dimethylsilane (BisPhos) to solutions of the rigid alkynyl PLAs led to the formation of 3 : 1 adducts. Single crystal X-ray diffraction was used to further elucidate the host–guest connectivtiy. In addition, a sixfold pnictogen-bonding donor was synthesised by tin-antimony exchange. [ABSTRACT FROM AUTHOR]

The smectite group of clay minerals (smectites) consists of negatively charged clay layers and interlayer exchangeable cations. They are spontaneously delaminated in water to form single clay layers when the interlayer cations are small alkaline cations such as Na+ or Li+. This phenomenon known as osmotic swelling has fundamental importance in constructing novel clay-based nanomaterials. However, osmotic swelling of smectites has not been systematically investigated in organic solvents although this phenomenon should be useful for developing novel clay-organic nanocomposites. We report herein that montmorillonite, a typical smectite, with monovalent and divalent inorganic interlayer cations shows osmotic swelling accompanied by delamination of clay layers in water-acetonitrile and water-2-propanol mixed solvents, although inorganic interlayer cations have been believed to be inappropriate for delamination of smectites in organic solvents. The delamination is confirmed by a combination of macroscopic sample appearances, XRD patterns, and SEM images. Montmorillonite with interlayer Na+ or Li+ ions shows osmotic swelling in pure water and the mixed solvents but not in pure organic solvents. Montmorillonite with alkaline earth dications in the interlayer spaces is swollen in water-organic mixed solvents but not in either pure water or organic solvents alone. Partial delamination in several systems can be clarified from SEM images even though the sample appearances and XRD patterns do not give firm evidence. Such non-uniform swelling behavior of montmorillonite is related to the disordered stacking of the aluminosilicate layers with different morphologies in the clay powders as observed by SEM. [ABSTRACT FROM AUTHOR]

Near-infrared (NIR) emissive probes are becoming increasingly popular in biological sensing and imaging due to the advantages of non-invasiveness and deep tissue-penetrating ability. Herein, a series of complexes of trivalent lanthanide ions (Ln = Yb, Er, and Gd) with the commercially available azo dye chromophore 2R (Na2H2C2R) as ligand and featuring respectively H2O and dimethylsulfoxide (DMSO) as ancillary ligands have been prepared. Formulated as [Ln2(HC2R)2(H2O)10]·8H2O (1-3, Ln = Yb, Er, Gd) and [Ln2(HC2R)2(DMSO)10]·2DMSO (4-6, Ln = Yb, Er, Gd), their structures have been determined by singlecrystal X-ray diffraction studies. Photophysical property studies revealed NIR emissions of the DMSO complexes characteristic of Yb(III) and Er(III), effectively sensitized by the dye ligand arising mainly from the π-π* transition of the chromophore. The long-wavelength excitation of the complexes, covering the whole visible-light range and extending into the NIR region, portends the potential applications of such complexes for flexible bioimaging and sensing. [ABSTRACT FROM AUTHOR]

In this paper, a series of novel energetic compounds based on the backbone of the tetrazine-triazole structure were successfully synthesized. N,N′-((1,2,4,5-Tetrazine-3,6-diyl)bis(1,2-dihydro-3H-1,2,4-triazole-5-yl-3-ylidene))dinitramino (4) was prepared by the nitration of 5,5′-(1,4-dihydro-1,2,4,5-tetrazine-3,6-diyl)bis(1H-1,2,4-triazol-3-amine) (3) with 100% nitric acid and its energetic salts (6–14) were also prepared. All the compounds were fully characterized. The structures of 4 and 5 were further confirmed by single crystal X-ray diffraction analysis. The results show that these compounds have high heats of formation ranging from 2.09 to 3.95 kJ g−1, good detonation pressures and detonation velocities and acceptable sensitivities. Among them, compound 4, with low sensitivities (IS: 20 J and FS: 270 N) and excellent detonation properties (vD = 9100 m s−1; P = 34.1 GPa) shows potential for application in the field of highly energetic and insensitive explosives. The hydroxylammonium salt (7) exhibits promising energetic properties, which, in some cases, are superior to those of octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX). [ABSTRACT FROM AUTHOR]

Reactions between 1,2-di(tetrazol-2-yl)ethane (ebtz), 1,6-di(tetrazol-2-yl)hexane (hbtz) or 1,1′-di(tetrazol-1-yl)methane (1ditz) and Fe(BF4)2 in the presence of adiponitrile (ADN), glutaronitrile (GLN) or suberonitrile (SUN) resulted in the formation of coordination polymers [Fe(μ-ebtz)2(μ-ADN)](BF4)2 (1), [Fe(μ-hbtz)2(μ-ADN)](BF4)2 (2), [Fe(μ-1ditz)2(GLN)2](BF4)2·GLN (3) and [Fe(μ-1ditz)2(μ-SUN)](BF4)2·SUN (4). It was established that the application of dinitriles allows an increase in the dimensionality of the ebtz and hbtz based systems while maintaining the structure of the polymeric units characteristic of previously studied mononitrile based analogues. In 3 and 4, regardless of the type of dinitrile coligand, the motif of 2D polymeric layers constituted by 1ditz molecules remains preserved. However, the dimensionality of 1ditz based networks is governed by the coordination modes of dinitriles. 3, based on a shorter molecule of glutaronitrile, crystallizes as a two-dimensional (2D) coordination polymer. In this compound, dinitriles coordinate monodentately or play the role of guest molecules. The substitution of glutaronitrile with suberonitrile enables the bridging of neighboring polymeric layers, resulting in a 3D network. The intentional selection of bis(tetrazoles) and dinitriles as building blocks has led, as expected, to obtaining systems with the structure of the first coordination sphere consisting of four tetrazole rings and two axially coordinated nitrile molecules. It created the conditions required for the occurrence of thermally induced spin crossover. Magnetic measurements and single crystal X-ray diffraction studies were used for the characterization of the spin crossover properties of 1–4. [ABSTRACT FROM AUTHOR]

We have used high-pressure synthesis to synthesize samples of Ca2-xMnxTi2O6 double perovskite, where x varies between 0.2 and 1. The synthesized materials were structurally characterized with powder X-ray diffraction (XRD). Rietveld refinement of the XRD patterns was used to study the change from CaTiO3 (x = 0) to the composition CaMnTi2O6 (x = 1) where half of the Ca(II) ions are replaced by smaller Mn(II) ions. We analyzed the peak shapes in the XRD patterns, as well as lattice parameters, and it appears that smooth symmetry change from the centrosymmetric space group Pbnm to the non-centrosymmetric space group P42mc occurs between x = 0.3 and x = 0.5. We also confirmed the centrosymmetric to noncentrosymmetric transition by characterizing the dielectric properties of the materials with ferroelectric measurements. [ABSTRACT FROM AUTHOR]

The application of Mg[Ph4Pn] and Li·K[Ph4Pn] in transmetalation reactions to a range of Rh(I) precursors led to the formation of "half-baguette" anti-[Rh I(L) n ]2[μ:η5:η5Ph4Pn] (L = 1,5-cyclooctadiene, norbornadiene, ethylene; n = 1, 2) and syn-[Rh I(CO)2]2[μ:η5:η5Ph4Pn] complexes as well as the related iridium complex anti-[Ir I(COD)]2[μ:η5:η5Ph4Pn]. With CO exclusive syn metalation was obtained even when using mono-nuclear Rh(I) precursors, indicating an electronic preference for syn metalation. DFT analysis showed this to be the result of π overlap between the adjacent M(CO)2 units which overcompensates for dz2 repulsion of the metals, an effect which can be overridden by steric clash of the auxiliary ligands to yield anti-configuration as seen in the larger olefin complexes. syn-[Rh I(CO)2]2[μ:η5:η5Ph4Pn] is a rare example of a twinned organometallic where the two metals are held flexibly in close proximity, but the two d8 Rh(I) centres did not show signs of M–M bonding interactions or exhibit Lewis basic behaviour as in some related mono-nuclear Cp complexes due to the acceptor properties of the ligands. The ligand substitution chemistry of syn-[Rh I(CO)2]2[μ:η5:η5Ph4Pn] was investigated with a series of electronically and sterically diverse donor ligands (P(OPh)3, P(OMe)3, PPh3, PMe3, dppe) yielding new mono- and bis-substituted complexes, with E-syn-[Rh I(CO)(P{OR})3]2[μ:η5:η5Ph4Pn] (R = Me, Ph) characterised by XRD. [ABSTRACT FROM AUTHOR]

The crystalline quality of perovskite films is a key factor that affects the performance of perovskite photovoltaic devices. Polyoxometalates can better match the energy levels of each layer in the devices through their own suitable energy level and band gap, and the good light absorption of POMs can also increase the mobility of photogenerated carriers in the devices. Moreover, POMs with Keggin-type structures can also improve the crystalline quality of perovskite films by eliminating defect sites, which can lead to better crystallization of perovskites with larger grains. In this study, we optimized the crystalline quality of a perovskite layer using the SiW9Co3@rGO composite prepared using POMs and graphene derivatives. XRD and SEM tests show that the crystallization degree of the perovskite layer was improved, the average grain size of which can reach up to 1222.92 nm, which is nearly four times higher than that of a blank perovskite. The photoresponse current of a SiW9Co3@rGO-doped photodetector can reach to 43.94 μA, which is about 226% higher than that of an undoped device. At the same time, the addition of the composite can improve the stability of photodetectors because of the special network structure of graphene. Photodetectors doped with SiW9Co3@rGO can still maintain more than 90% of their high performance for a month. This study proves that POM-based composites have good application prospects in the field of photovoltaic devices. [ABSTRACT FROM AUTHOR]

Polyiodides present high bonding flexibility already at ambient conditions, and undergo significant pressure-induced structural deformations. Resonant Raman spectroscopy has been widely used to study I–I bonds in various polyiodides, but it carries a risk of photodecomposition due to the high visible-light absorption of iodine. In this study, tetraethylammonium (bis)diiodine triiodide (TEAI) has been investigated by resonant Raman spectroscopy up to 12.02(3) GPa. The effect of pressure on the intensities and positions of Raman bands has been evaluated and correlated with the interatomic I–I distances derived from high-pressure X-ray diffraction experiments. Pressure was shown to effectively stabilize TEAI against laser-induced photodecomposition, even after a long course of irradiation with the resonant laser light. Examination of a freshly exposed crystal surface revealed that TEAI superficially passivates with the layer of lower polyiodides, which prevents further iodine loss, and shows distinct pressure-induced behaviour. [ABSTRACT FROM AUTHOR]

Here, a cyclometalated Pt(II) clamshell dimer (complex 2) has been synthesized with the primary ligand of dibenzo(f,h)quinoxaline and an ancillary ligand of N,N′-diphenylformamidine. In addition, a mononuclear Pt(II) complex 1a and a binuclear Pt(II) complex 1b were also prepared. Complex 1a was coordinated by one cyclometalated ligand of dibenzo(f,h)quinoxaline, one chloride ion, and one N,N′-diphenylformamidine. Complex 1b was coordinated by one cyclometalated ligand of dibenzo(f,h)quinoxaline, two chloride ions, and two N,N′-diphenylformamidines. All of these three complexes were characterized by nuclear magnetic resonance (NMR) spectroscopy, high-resolution mass spectrometry (HRMS), elemental analyses, and single-crystal X-ray diffraction (XRD). The Pt–Pt distance in complex 2 was 2.8439(2) Å. It also exhibited a near-infrared (near-IR) emission at 887 nm in the pure solid state. On the other hand, complexes 1a and 1b exhibited triplet emission at 589 and 660 nm, respectively, in the pure solid state. Furthermore, in 2 wt% poly(Me methacrylate) (PMMA) films, complex 1a showed a triplet emission at 548 nm (with Φ = 84% and τ = 5.53 μs) and complex 1b showed an emission at 627 nm (with Φ = 79% and τ = 4.07 μs). Due to its great photophysical properties, complex 1b was deposited onto quartz plates for the detection of organic solvent vapors and it showed unique emission quenching for the vapor of tetrahydrofuran. [ABSTRACT FROM AUTHOR]