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Zinc sulfide (ZnS) is a promising anode material for lithium-ion batteries (LIBs) because of its high theoretical capacity, abundance, cost-effectiveness, and environmental friendliness. Herein, a hydrangea-like ZnS-carbon composite (ZnS-NC) is synthesized through the hydrothermal method and subsequent pyrolysis of a supramolecular precursor guanosine. The resulting composite comprises ultrafine ZnS nanoparticles firmly stabilized on a nitrogen-doped carbon matrix, featuring mesoporous channels and high surface areas. When utilized as an anode material for LIBs, the initial discharge specific capacity of the ZnS-NC electrode reaches an impressive value of 944 mA h g−1 at 1.0 A g−1, and even after 450 cycles, it maintains a reversible capacity of 597 mA h g−1. Compared with pure ZnS, the ZnS-NC composite exhibits significantly improved rate performance and cycling stability. This enhancement in Li-storage performance can be attributed to a synergistic effect within the ZnS-NC composite, which arises from the large exposed active site area, efficient ion/electron transfer, and strong interaction between the ZnS nanoparticles and the carbon framework. Overall, this work presents an eco-friendly approach for developing metal sulfide-carbon composites with exceptional potential for energy storage applications. [ABSTRACT FROM AUTHOR]

Reactions of the seven-membered heterocyclic potassium diamidoalumanyl, [K{Al(SiNDipp)}]2 (SiNDipp = {CH2SiMe2NDipp}2; Dipp = 2,6-di-isopropylphenyl), with a variety of Cu(I), Ag(I) and Au(I) chloride N-heterocyclic carbene (NHC) adducts are described. The resultant group 11-Al bonded derivatives have been characterised in solution by NMR spectroscopy and, in the case of [{SiNDipp}Al–Au(NHCiPr)] (NHCiPr = N,N′-di-isopropyl-4,5-dimethyl-2-ylidene), by single crystal X-ray diffraction. Although similar reactions of LAgCl and LAuCl, where L is a more basic cyclic alkyl amino carbene (CAAC), generally resulted in reduction of the group 11 cations to the base metals, X-ray analysis of [(CyCAAC)AgAl(SiNDipp)] (CyCAAC = 2-[2,6-bis(1-methylethyl)phenyl]-3,3-dimethyl-2-azaspiro[4.5]dec-1-ylidene) provides the first solid-state authentication of an Ag–Al σ bond. The reactivity of the NHC-supported Cu, Ag and Au alumanyl derivatives was assayed with the isoelectronic unsaturated small molecules, N,N′-di-isopropylcarbodiimide and CO2. While these reactions generally provided products consistent with nucleophilic attack of the group 11 atom at the electrophilic heteroallene carbon centre, treatment of the NHC-supported copper and silver alumanyls with N,N′-di-isopropylcarbodiimide yielded less symmetric Cu–C and Ag–C-bonded isomers. In contrast to the previously described copper and silver alumanyl derivatives, [(NON)Al(O2C)M(Pt-Bu3)] (M = Cu or Ag; NON = 4,5-bis(2,6-di-isopropylanilido)-2,7-di-tert-butyl-9,9-dimethylxanthene), which were prone to facile CO extrusion and formation of carbonate derivatives, the NHC-supported dioxocarbene species, [(NHCiPr)M(CO2)Al(SiNDipp)] (M = Cu, Ag, Au), are all stable at room and moderately elevated temperatures. The stabilising role of the NHC co-ligand was, thus, assessed by preparation of the t-Bu3P adducted copper-alumanyl, [(t-Bu3P)CuAl(SiNDipp)]. Treatment of this latter compound, which was also structurally characterised by X-ray analysis, with both N,N′-di-isopropylcarbodiimide and CO2 again provided smooth heteroallene insertion and formation of the relevant Cu–C-bonded products. Although both compounds were quite stable at room temperature, heating of [(t-Bu3P)Cu(CO2)Al(SiNDipp)] at 60 °C induced elimination of CO and formation of the analogous carbonate, [(t-Bu3P)Cu(OCO2)Al(SiNDipp)], which was identified by 13C and 31P NMR spectroscopy. Reflective of the more reliable nucleophilic behaviour of the gold centres in these group 11 alumanyls, computational (QTAIM and NBO) analysis highlighted a lower level of covalency of the Al–Au linkage in comparison to the analogous Al–Cu and Al–Ag interactions. Although substitution of the co-ligand significantly perturbs the charge distribution across the Cu–Al bond of [LCuAl(SiNDipp)] (L = NHCiPr or t-Bu3P), only a negligible difference is observed between the phosphine-coordinated copper systems derived from either the [SiNDipp]- or (NON)-based alumanyl ligands. Computational mapping of the reaction profiles arising from treatment of the various group 11 alumanyls with N,N′-di-isopropylcarbodiimide indicates that the observed formation of the Cu–N and Ag–N bound isomers do not provide the thermodynamic reaction outcome. In contrast, examination of the CO2-derived reactions, and their potential toward CO extrusion and subsequent carbonate formation, implies that the identity of the co-ligand exerts a greater influence on this aspect of reactivity than the architecture of the diamidoalumanyl anion. [ABSTRACT FROM AUTHOR]

The design and synthesis of crystalline materials have been a subject of intensive research because of their interesting structures, physicochemical properties, and potential applications. However, the crystalline structure of organic–inorganic hybrid materials collapses to lose the structural features of the original networks and/or frameworks when exposed to different stimuli such as pH, vapor, water, high temperature, and organic solvents. This hampers further studies focusing on practical applications. Although several review articles provide reasonable pathways for the preparation of stable metal–organic frameworks (MOFs) and coordination polymers (CPs), the synthesis and design of stable materials containing organic species remain challenging. In this frontier article, we discuss the development of crystalline MOF, CP, metallophosphate, and metallophosphite materials, and provide a feasible approach for the formation of stable organic–inorganic hybrid compounds that combine MOFs (or CPs) and phosphate (or phosphite) building elements. In addition to their interesting structures, the synthetic strategies and structural stabilities of such hybrid composites are also presented. [ABSTRACT FROM AUTHOR]

An exploratory study of the lead-tellurium-oxygen phase space led to two new compounds, Ba3PbTe6O16 (BPTO) and Na2Pb9(μ6-O)2(Te2O10)2 (NPTO), which were synthesized under hydrothermal conditions at 550 °C and 210 °C, respectively, and characterized by single-crystal X-ray diffraction, infrared and X-ray photoelectron spectroscopy. BPTO adopts a layer structure. The Te4+ cation in BPTO is bonded to four oxygen atoms at about 2.0 Å with two more oxygens at about 3.0 Å. The seesaw-shaped TeO4 units share corners to form 2D layers containing six-membered rings and the Ba2+ and Pb2+ cations are situated in the interlayer region. The structure of NPTO contains dimers of edge-sharing Te6+O6 octahedra, which are connected through five-coordinate Pb2+ cations. A unique six-coordinate O atom is at the center of the octahedron formed by five Pb2+ and one Na+ cations. BPTO is one of the few metal tellurites which were synthesized under supercritical hydrothermal reaction conditions. The Pb2+ cation in NPTO shows pronounced stereochemical effects of the lone electron pair. In contrast, BPTO shows no stereochemical evidence of the inert pair. [ABSTRACT FROM AUTHOR]

Three series of copper hydride clusters [Cu8H6L6]2+ (1), [Cu4HX2L4]+ where X− = Cl− (2a), Br− (2b), I− (2c), N3− (2d) and SCN− (2e), and [Cu4HX3L3] where X− = Br− (3b) and I− (3c) (L = 2-(diphenylphosphino)pyridine, dppy) were synthesized and characterized by single-crystal X-Ray crystallography and standard spectroscopic techniques. The metal core of 1, Cu8, can be described as a bicapped octahedron, while those of 2 and 3 series adopt tetrahedral structures. The hydride positions were deduced from difference electron density maps and corroborated by NMR and DFT calculations. For 1, there are two μ4-H−, one each in the two tetrahedral cavities of the two capping atoms and four μ3-H− on the six triangular faces around the waist of the octahedron. For [Cu4HX2L4]+ and [Cu4HX3L3] series, the single μ4-H− resides in the center of the Cu4 tetrahedron. It was found that these three series of copper clusters are intimately connected and can convert from one to another under specific reaction conditions. Their transformation pathways were investigated in detail. Spontaneous resolution to form optically pure enantiomeric single crystals was observed for [Cu4H(SCN)2L4]+ (2e) and [Cu4HBr3L3] (3b). Photoluminescence was observed for [Cu4HX2L4]+, as well as [Cu4HX3L3] with strong emissions from green to yellow regions. [ABSTRACT FROM AUTHOR]

Facile synthesis and postsynthetic modification of a rectangular 1,2,4-triazole-based NHC macrocycle have been developed. The silver complex [Ag2(1)2](BF4)2 is derived from the corresponding triazole salt H2-1(BF4)2 upon reaction with Ag2O. The structure of the metallocyclic Ag–NHC complex [Ag2(1)2](BF4)2 was determined by single-crystal X-ray diffraction analysis. The metal–carbene template undergoes photodimerisation of its terminal cinnamic esters (UV irradiation, λ = 365 nm) and generates a macrocyclic tetra (NHC) ligand. The desired tetra-1,2,4-triazole macrocycle was isolated in good yield by eliminating the metal ions from the photodimerisation product. All complexes were fully characterized by multinuclear NMR measurements (1H, 13C{1H}, COSY, HSQC and HMBC) and ESI mass spectroscopy. [ABSTRACT FROM AUTHOR]

A novel class of cyclometalated macrocycles [(Cp*Ir)2(R–NC–C6H2–CN–R)2]2(pyrazine)2·(OTf)4[R = Ph (4a), p-MeOC6H4(4b), p-MeC6H4(4c), p-ClC6H4(4d), Me (4e)]; [(Cp*Rh)2(R–NC–C6H2–CN–R)2]2(pyrazine)2·(OTf)4[R = Ph (4a′), p-MeOC6H4(4b′), p-MeC6H4(4c′)] and [(Cp*Ir)2(R–CN–C6H4–NC–R)2]2(pyrazine)2·(OTf)4[R = Ph (5a), p-MeOC6H4(5b)] was stepwise constructed through the double-site C–H activation of aromatic bis-imine substrates. The structures of binuclear complexes and tetranuclear macrocycles were confirmed by single-crystal X-ray diffraction. Isomers were found both in binuclear species and macrocyclic complexes. Flexible substrates led to the existence of isomers for binuclear species, yet gave no isomers after macrocyclic constructions; rigid ones, in contrast, led to isomers only for macrocyclic species. The isomers of tetranuclear macrocycles were thermodynamically stable to reversible transformation on a scale of days. Robust bonding and a certain degree of rigidity were invoked to explain the existence of isomers. This is the first example, to our knowledge, in which coordinated macrocycles containing half-sandwich Cp*M (M = Ir, Rh) fragments have been constructed, without a dynamic reversible process. [ABSTRACT FROM AUTHOR]

Reactions of half-sandwich iridium and rhodium complexes [Cp*MCl2]2(1a: M = Ir, 1b: M = Rh) and the half-sandwich ruthenium complex [(p-cymene)RuCl2]2(1c) with 4DPDS gave the corresponding binuclear complexes [{Cp*MCl2]2}(μ-4DPDS) (2a: M = Ir, 2b: M = Rh) and [{(p-cymene)RuCl2]2}(μ-4DPDS) (2c), which can be converted into binuclear metallamacrocycles. The metallamacrocycles [Cp*M(μ-4DPDS)Cl]22+(3a: M = Ir, 3b: M = Rh) and [(p-cymene)Ru(μ-4DPDS)Cl]22+(3c) are composed of two half-sandwich units and two 4DPDS ligands with the same chirality. The macrocycle 3cis chiral and changes its shape slightly depending on the guests accommodated above and below the cavities. [ABSTRACT FROM AUTHOR]

The first example of a thio-functionalized zincophosphite material (NTOU-2S) incorporating the 2,5-thiophenedicarboxylate (TPDC) ligands was synthesized using a hydro(solvo)thermal method and structurally characterized by single-crystal X-ray diffraction. Interestingly, the perspective view of the crystal structure for NTOU-2S is similar to our previous report of NTOU-2 but the carboxylate organic ligands (TPDC for NTOU-2S; 1,4-benzenedicarboxylate, BDC, for NTOU-2) in both compounds adopt different types of bis-monodentate coordination models (the unusual cis bonding versus a trans linkage) to bridge the metal atoms of inorganic tubes in the formation of large-channel zincophosphite frameworks, resulting in structural and functional diversities. The thiophene-based compound also displayed higher thermal stability and removal ability for the softer Hg2+ cations from water solutions than the performance of sulfur-free NTOU-2. In addition, the synthesis, structural characteristics, removal properties of heavy metal cations, and thermal and chemical stabilities for both compounds were also reported. [ABSTRACT FROM AUTHOR]

An iridium(iii)-catalyzed C–N-bond-forming direct synthesis of carborane azo derivatives was developed. The reaction of o-carborane monocarboxylate with aryldiazonium salt in the presence of a catalytic amount of [Cp*IrCl2]2 and NaOAc in CH3CN at 80 °C gave the corresponding carborane azo derivative in good yield. A series of cyclometalated iridium/rhodium complexes that contain Cp*M–B (M = Ir, Rh) bonds, and are stabilised by the intramolecular coordination of nitrogen donors, were successfully isolated and structurally characterised. [ABSTRACT FROM AUTHOR]

Photochemical reactions are vital synthetic means for the synthesis of natural products and highly strained molecules. However, it remains an immense challenge to control the chemo- and regioselectivity in the photoreactions of anthracene derivatives while maintaining high reactivity. Herein, we report the synthesis of two photoactive metallarectangles 1a and 1b by coordination-driven self-assembly of 2,6- and 2,7-bifunctionalized anthracenes with a half-sandwich rhodium template. By taking advantage of the rhodium template, the anthracene groups within the metallarectangles can be preorganized in a parallel fashion and exclusively undergo a photochemical [4 + 4] cycloaddition. As a result, the syn-photodimers were obtained in quantitative yields under irradiation at 365 nm. The photocycloaddition of metallarectangles 1a and 1b was found to be reversible via photo- and thermal cleavage reactions, even after repeating three times. Furthermore, pure organic photodimers 3a and 3b, which are difficult to synthesize by conventional organic methods, can be readily dissociated from the metalloassemblies in high yields. [ABSTRACT FROM AUTHOR]

A series of complexes of novel chelating thione-alkene S(η2-C=C)S tridentate ligands bound to late transition metals (Ir, Rh, Pd) were isolated and characterised. Counter-anions play an important role in the binding of the alkene moiety to the metals. Different solvents were observed to affect the stability of the rhodium complexes. [ABSTRACT FROM AUTHOR]

A dynamic guest-binding study of BODIPY-derivative 3 (3 = 1,3,5,7,8-pentamethyl-4,4-difluoro-4-bora-3a,4a-diaza-s-indacene) with two Cp*RhIII-based organometallic cages [Cp*6Rh6(μ-CA)3(tpt)2](OTf)61 (H2CA = chloranilic acid, tpt = 2,4,6-tripyridyl-1,3,5-triazine) and [Cp*6Rh6(μ-DHNA)3(tpt)2](OTf)62 (H2DHNA = 6,11-dihydroxynaphthacene-5,12-dione) have been demonstrated. While guest 3 displays a strong green fluorescence emission, the host–guest complexes 3⊂1 and 3⊂2 exhibit almost no emission. However, fluorescence emission can be again ‘turned on’ by adding coronene (4) or pyrene (5) into the solution of 3⊂1 and 3⊂2. Guests 4 and 5 show stronger binding affinities toward the organometallic cages 1 and 2 due to the strong electrostatic interactions between the electron-rich guest and electron-deficient tpt resulting in the displacement of 3 by 4 or 5, which eventually helps the fluorescence enhancement. Further guest-binding studies using a Job's plot experiment illustrate the formation of discrete 1 : 1 host–guest complexes which are also supported by 1H NMR spectroscopy and ESI mass spectrometry. The anion-exchange study with sodium chloride reveals that the chloride ion can effectively disassemble the host frameworks of 1 and 2 releasing the fluorescent guest 3 which can be again encapsulated into the cavity of reassembled cages promoted by the addition of silver triflate. [ABSTRACT FROM AUTHOR]