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Despite the ultra‐high photoluminescence quantum yield (PLQY) of 0D hybrid manganese halides as state‐of‐the‐art luminescent materials, intrinsic water stability remains an unsurpassable barrier due to the serious hygroscopicity of the hydrogen‐bonding structure. Herein, a synthetic strategy that realizes adjustable emission color and high water resistance in a 0D hybrid manganese chloride family based on the same cation of [H2TMDAP]2+ (TMDAP = N,N,N′,N′‐tetramethyl‐1,3‐diaminopropane) is reported. Specifically, direct solution or solid‐state reaction of precursor materials generates [H2TMDAP]3[MnCl4]2[Mn2Cl6], while additional Zn2+‐doping as a structural directing agent results in [H2TMDAP]Mn0.63Zn0.37Cl4. Functionally, the [Mn/ZnCl4]2− tetrahedron based [H2TMDAP]Mn0.63Zn0.37Cl4 displays green light emission at 521 nm with a PLQY of 63.9%. [H2TMDAP]3[MnCl4]2[Mn2Cl6] is composed of a [MnCl6]4− octahedron based [Mn2Cl6]2− chain and a discrete [MnCl4]2− tetrahedron, but it only exhibits single red emission at 628 nm with a PLQY of 48.1%. Compared with water‐instable [H2TMDAP]Mn0.63Zn0.37Cl4, [H2TMDAP]3[MnCl4]2[Mn2Cl6] represents extraordinary chemical stability in humid air and water over 1 month, manifested by an unchanged structural lattice and sufficient emission intensity. Significantly, the ultra‐high water proof performance of [H2TMDAP]3[MnCl4]2[Mn2Cl6] is nearly unmatchable among all previously reported manganese halides as far as is known. The combined merits of tunable emission wavelength, high PLQY, and stability highlight the potential applications of title materials in solid‐state lighting and display diodes. [ABSTRACT FROM AUTHOR]

In recent years, organic–inorganic hybrid metal halides have emerged as a highly promising class of semiconducting light emitting diodes (LEDs) due to their fascinating photoluminescence properties. Here, by specifically selecting different organic cations as templates, a series of new hybrid cuprous halides have been solvothermally prepared, namely [Me-Py]CuI2 (1), [(Me)2-DABCO]Cu2I4 (2), [Me-MePy]Cu2I3 (3), and [H2DABCO]Cu3X5 (X = I (4) and Br (5)). These hybrid cuprous halides feature one-dimensional (1D) [CuI2]−, [Cu2I3]− and [Cu3X5]2− (X = Br, I) chains surrounded and charge-balanced by organic cations. Under UV photoexcitation, these hybrid cuprous halides exhibit strong tunable photoluminescence from cyan (480 nm) to red (675 nm) emissions with large Stokes shifts (345 nm). The intrinsic nature of PL emissions is also investigated based on temperature-dependent PL emission, lifetime, photoluminescence quantum efficiencies, etc. [ABSTRACT FROM AUTHOR]

With transition metal (TM) complex cations as structure-directing agents (SDAs), one type of new organic-inorganic hybrid iodoargentates, namely, [TM(2,2-bipy) 3 ]Ag 5 I 7 (TM = Zn, Ni, Co), have been solvothermally synthesized and structurally characterized. All the title compounds contain one-dimensional (1D) [Ag 5 I 7 ] 2 − chains composed by [Ag 5 I 10 ] units based on [AgI 4 ] tetrahedra, which are interconnected by [TM(2,2-bipy) 3 ] 2 + via hydrogen bonds to form 3D supramolecular networks. The UV–vis diffuse-reflectance measurements reveal that the compounds possess semiconductor behaviors with band gaps of 1.94–2.58 eV tuned by different TM complex cations. The title hybrid materials feature stable photocatalytic degradation activities over organic pollutants under visible light irradiation mainly originating from the electron absorption abilities of TM complex cations. Based on radical-trapping experiments and electronic band structural calculation, the possible photocatalytic mechanism and photochemical stability is also proposed. [ABSTRACT FROM AUTHOR]

The incorporation of unsaturated [Mn(1,2-dap)] 2+ , [Mn(1,2-dap) 2 ] 2+ , [Mn(2,2-bipy)] 2+ (1,2-dap=1,2-diaminopropane) complex cations with thioarsenate anions of [As III S 3 ] 3− and [As V S 4 ] 3 − led to three new hybrid manganese thioarsenates, namely, [Mn(1,2-dap)] 2 MnAs 2 S 6 ( 1 ), [Mn(1,2-dap) 2 ]{[Mn(1,2-dap)] 2 As 2 S 8 } ( 2 ) and (NH 4 )[Mn(2,2-bipy) 2 ]AsS 4 ( 3 ). In compound 1 , the unsaturated [Mn(1,2-dap)] 2+ complexes, [MnS 4 ] 6− tetrahedra and [As III S 3 ] 3− trigonal-pyramids are condensed to form the 1D [Mn(1,2-dap)] 2 MnAs 2 S 6 chain, whereas compound 2 features 2D layer composed of [Mn(1,2-dap)] 2+ and [Mn(1,2-dap) 2 ] 2+ complexes as well as [As V S 4 ] 3− tetrahedral units. For compound 3 , two [As V S 4 ] 3− anions bridge two [Mn(2,2-bipy)] 2+ complex cations into a butterfly like {[Mn(2,2-bipy)] 2 As 2 S 8 } 2 − anionic unit. Magnetic measurements indicate the ferrimagnetic behavior for compound 1 and antiferromagnetic (AF) behaviors for compounds 2–3 . The UV–vis diffuse-reflectance measurements and electronic structural calculations based on density functional theory (DFT) revealed the title compounds belong to semiconductors with band gaps of 2.63, 2.21, and 1.97 eV, respectively. The narrow band-gap of compound 3 led to the efficient and stable photocatalytic degradation activity over organic pollutant than N-doped P25 under visible light irradiation. [ABSTRACT FROM AUTHOR]

With a [TM(phen)3]2+ (TM = transition metal, phen = 1,10-phenanthroline) complex and N-alkylated [(Me)2-2,2′-bipy]2+ (Me = methyl, 2,2′-bipy = 2,2′-bipyridine) as cations, a series of hybrid iodoargentates, namely [TM(phen)3]2Ag3I7 (TM = Mn (1), Fe (2)), [Mn(phen)3]Ag5I7 (3) and [(Me)2-2,2′-bipy]2Ag7I11 (4), have been solvothermally prepared and structurally characterized. Compounds 1 and 2 feature isolated windmill-shaped [Ag3I7]4− trimers based on [AgI3] triangles, whereas compound 3 contains two-dimensional (2D) microporous [Ag5I7]2− layers composed of [Ag3I7] and [Ag7I13] secondary building units (SBUs) based on [AgI4] tetrahedra. In compound 4, a 2D [Ag7I11]4− slab is formed by alternating interconnection of two different types of [Ag7I12] double chains via corner-sharing with one-dimensional (1D) large channels occupied by [(Me)2-2,2′-bipy]2+ cations. UV-vis diffuse-reflectance measurements reveal that the title compounds possess semiconducting behaviors with smaller band gaps of 1.85, 1.78, 1.89 and 2.03 eV, respectively. Sample 4 shows highly efficient photocatalytic degradation activity over organic pollutants than N-doped TiO2 (P25) under visible light irradiation. Moreover, a possible mechanism for the stable photocatalytic activity is proposed based on band structure calculation. Finally, the luminescence properties and thermal stabilities of the title compounds are also studied. [ABSTRACT FROM AUTHOR]

Withdifferent transition metal (TM) complexes as structure-directingagents or structure-building units, a series of new mercury thioantimonateswith abundant architectures ranging from one-dimensional (1D) ribbonsto two-dimensional (2D) layers have been solvothermally synthesizedand structurally characterized. Compounds [Co(en)3]Hg2Sb2S6(1) (en = ethylenediamine)and [Ni(1,2-dap)3]2HgSb3S7Cl (2, 1,2-dap = 1,2-diaminopropane) containa discrete 2D [Hg2Sb2S6]n2n–layer and1D [HgSb3S7]n3n–chain, respectively. Compounds[Ni(1,2-dap)3]HgSb2S5(3) and [Mn(dien)2]HgSb2S5(4, dien = diethylenetriamine) feature distinct 2D[HgSb2S5]n2n–layer and 1D [HgSb2S5]n2n–ribbon, respectively, whereas the 1D [HgSb2S5]n2n–chains are attached by [TM(tren)]2+complexes via TM–Sbonds to form 1D {[TM(tren)]HgSb2S5}nribbons in compounds [TM(tren)]HgSb2S5(TM = Mn (5), Fe (6), Co(7), tren = tris(2-aminoethyl)amine). Compounds [TM(dien)2]Hg3Sb4S10(TM = Mn (8), Co(9), Ni(10)) feature 2D [Hg3Sb4S10]n2n–anionic layers separated by[TM(dien)2]2+cations. The most interestingstructural feature of these compounds is the presence of three differenttypes of coordination environments of Hg centers including linear[HgS2] unit, [HgS3] triangle, and [HgS4] tetrahedron. The optical properties and thermal stabilities ofthe title compounds were studied by UV–vis spectra and thernogravimetricanalyses, respectively. The photocatalytic experiments indicated that 3, 4, and 10were able to degraderhodamine B (RhB) under visible irradiation. [ABSTRACT FROM AUTHOR]

The new two-dimensional coordination polymer, poly[(μ4-1-phenyl-1 H-1,2,3,4-tetrazole-5-thiolato)copper(I)], [Cu(C7H5N4S)] n, has been prepared under solvothermal conditions by reacting CuBr with 1-phenyl-1 H-1,2,3,4-tetrazole-5-thiol (Hptt) in an acetonitrile and acetone solution. In the crystal structure, each CuI ion is coordinated by two N atoms and two S atoms from four ptt− ligands, and each ptt− ligand links four CuI ions to form two-dimensional layers which lie parallel to the (100) plane. These layers stack along the [100] direction via van der Waals interactions. [ABSTRACT FROM AUTHOR]

One new manganese thiogermanate, [(dien)2Mn]Ge2S4 (dien=diethylenetriamine), was prepared under mild solvothermal conditions and structurally and spectroscopically characterized. The title compound crystallizes in the orthorhombic system, chiral space group P212121 (no. 19) with a=9.113(4) Å, b=12.475(5) Å, c=17.077(7) Å, V=1941.5(15) Å3 and Z=4. Its structure features a three-dimensional (3D) network composed of a one-dimensional (1D) [Ge2S4]2− anionic chain and a [(dien)2Mn]2+ complex interconnected via various hydrogen bonds. The most interesting structural feature of the compound is the presence of two different oxidation states of germanium centers in the 1D [Ge2S4]2− chain, which is also supported by the result of X-ray photoelectron spectroscopy measurement. The optical property of the title compound has also been studied by UV–vis spectra. [ABSTRACT FROM AUTHOR]

Details of the structures of two polymorphs of tris(ethylenediamine)cobalt(III) tetrathioantimonate(V), [Co(C2H8N2)3][SbS4], are reported. The first polymorph crystallizes in the orthorhombic space group Pna21, whereas the second polymorph belongs to the tetragonal space group P42 bc. Both structures contain octahedral [Co(en)3]3+ cations (en is ethylenediamine) and tetrahedral [SbS4]3− anions, which are interconnected via various N-H...S hydrogen bonds to form two different types of three-dimensional network. [ABSTRACT FROM AUTHOR]

A new ternary potassium cobalt stannide, K13CoSn17- x ( x = 0.1), was obtained by reacting the mixture of the corresponding pure elements at high temperature, and structurally characterized by single-crystal X-ray diffraction study. K13CoSn17- x ( x = 0.1) crystallizes in the orthorhombic space group Pbca (No. 61) with a = 26.2799(7) Å, b = 24.1541(6) Å, c = 29.8839(6) Å, V = 18969.3(8) Å3, and Z = 16. Its structure contains isolated [CoSn9] monocapped square antiprism and [Sn4] tetrahedron in the ratio 1:2, forming a hierarchical variant of Laves phase MgZn2. The structural relation between the title compound with MgZn2 as well as other binary stannides is also discussed. [ABSTRACT FROM AUTHOR]

Abstract: One new AgI complex, [Ag2(aip)(NH3)]n (H2aip = 5-aminoisophthalic acid), has been prepared and structurally and spectroscopically characterized. The title complex crystallizes in the monoclinic system P21/c (no. 14) with a =6.975(2) Å, b =8.756(3) Å, c =16.086(6) Å, β =97.318(4)°, V=974.4(6) Å3 and Z=4. Its structure features a three-dimensional (3D) network composed of two-dimensional (2D) flexuous layer interconnected via weak hydrogen bonds. In aqueous solution, the H2aip exhibits blue emission, while the title complex with tetranuclear silver(I) cores and weak Ag…Ag bonds shows visible intense purple luminescence. [Copyright &y& Elsevier]

Abstract: A dinuclear vanadium 24-membered macrocycle with double-ring, [V2O2L2(μ-CH3COO)]− (H2L=3,3′-(1,3,4-thiadiazole-2,5-diyl)bis(sulfane-diyl) bis(4-hydroxypent-3-en-2-one)), was prepared in high yield from the reaction of VO2(acac) with 2,5-dimercapto-1,3,4-thiadiazole dipotassium salt (K2SSS) and acetylacetone (Hacac) at room temperature. Its closure of 24-membered macrocycle has resulted from the formation of U-shape units via S–C bonding between original SSS2− and acac− ligands, while the bridging CH3COO− has created from an unexpected decomposition of Hacac. The obtained two products were characterized by single crystal X-ray diffraction, XRD, ESR, TGA and magnetism analyses. A possible mechanism for formation of the bimetal 24-membered macrocycle has been discussed. [Copyright &y& Elsevier]