Presented here is the solvothermal preparation of two luminescent coordination polymers (L-CPs) based on the same mixed ligands, namely [Cd₂(1,4-NDC)₂(dppe)] (1) and [Mn₃(OH)₂(1,4-NDC)₂(dppe)(H₂O)] (2) (1,4-NDCH₂=1,4-naphthalene dicarboxylic acid, dppe=1,3-di(4-pyridyl)propane). Both the title compounds feature a neutral three-dimensional (3D) network. Photoluminescence (PL) studies indicated that the compound 1 based on d¹⁰ Cd²⁺ exhibited dual emissions with tunable intensities that could result in direct white-light emission based on the intraligand charge transfer (LLCT); while the compound 2 showed a single band of yellow emission based on the charge transfer between the ligands and the metal ion (LMCT), due to the partially filled d-orbital of Mn²⁺ ion. The temperature-dependent powder X-ray diffraction patterns (PXRD) and PL spectra were further measured to identify their thermal stabilities. This work may provide a certain guiding significance for exploiting L-CPs based on different metal ions.

Presented are the ionothermal syntheses, characterizations, and properties of a series of two- and three-dimensional selenidostannate compounds synergistically directed by metal–amine complex (MAC) cations and ionic liquids (ILs) of [Bmmim]Cl (Bmmim=1-butyl-2,3-dimethylimidazolium). Four selenidostannates, namely, 2D-(Bmmim)₃[Ni(en)₃]₂[Sn₉Se₂₁]Cl (1, en=ethylenediamine), 2D-(Bmmim)₈[Ni₂(teta)₂(μ-teta)]Sn₁₈Se₄₂ (2, teta=triethylenetetramine), 2D-(Bmmim)₄[Ni(tepa)Cl]₂[Ni(tepa)Sn₁₂Se₂₈] (3, tepa=tetraethylenepentamine), and 3D-(Bmmim)₂[Ni(1,2-pda)₃]Sn₈Se₁₈ (4, 1,2-pda=1,2-diaminopropane), were obtained. Single-crystal X-ray diffraction analyses revealed that compounds 1 and 2 possess a lamellar anionic [Sn₃Se₇]_n²ⁿ⁻ structure comprising distinct eight-membered ring units, whereas 3 features a MAC-decorated anionic [Ni(tepa)Sn₁₂Se₂₈]_n⁶ⁿ⁻ layered structure. In contrast to 1–3, compound 4 exhibits a 3D open framework of anionic [Sn₄Se₉]_n²ⁿ⁻. The structural variation from 1 to 4 clearly indicates that on the basis of the synergistic structure-directing ability of the MACs and ILs, variation of the organic polyamine ligand has a significant impact on the formation of selenidostannates.

Presented herein are two luminescent magnesium coordination polymers (Mg-CPs), namely [Mg₂(H₂O)₂(2-NDC)₄(1,10-phen)₂] (1) and [Mg₂(H₂O)(1,4-NDC)₂(1,10-phen)] (2), in which 2-NDCH=2-naphthalenecarboxylic acid, 1,4-NDCH₂=1,4-naphthalene dicarboxylic acid, and 1,10-phen=1,10-phenanthroline. Based on the mixed ligands, the title compounds exhibit linker-based photoluminescence (PL) properties thanks to the unique configuration of the Mg²⁺ ions. The two compounds show interesting dual emission on excitation of the different luminophores of the mixed linkers. In particular, the emissions of compound 2 could be tuned from green to yellow simply by varying the excitation energies. Furthermore, 2 could be excited by using a commercial λ=450 nm blue LED chip to generate white-light emission, which allows the fabrication of a white-light-emitting diode (WLED) with 20 lm W⁻¹ luminous efficacy. This work may provide a new method for designing tunable PL CPs by using the low-cost and abundant magnesium ion.

Chalcogenidometalates exhibit rich and diverse structures and properties applicable to ion exchange, thermoelectrics, photocatalysis, nonlinear optics, and so on. This personal account summarizes our recent progress in constructing chalcogenidometalates by combining metal coordination tetrahedra and the asymmetric coordination geometries of Sb³⁺ in the presence of organic species (typically organic amines and metal-organic amine complexes), which has been demonstrated as an effective strategy for synthesizing chalcogenidometalates with diversified structures and interesting properties. The linkage modes of asymmetric SbQ_n (n = 3, 4) geometries and group 13 (or 14) metal coordination tetrahedra are analyzed, and the secondary building units (SBUs), with different compositions and architectures, are clarified. The crucial role and function of organic species in the formation of chalcogenidometalates are explored, with an emphasis on their powerful structure-directing features. In particular, some chalcogenidometalates in this family exhibit excellent ion-exchange properties for Cs⁺ and/or Sr²⁺ ions; the factors affecting ion-exchange properties are discussed to understand the underlying ion-exchange mechanism.

A 3D organic–inorganic hybrid compound, (2-MepyH)₃ [{Fe(1,10-phen)₃}₃][{Pr₄Sb₁₂O₁₈(OH) Cl_11.5}(TDC)_4.5({Pr₄Sb₁₂O₁₈(OH)Cl_9.5} Cl)]⋅3 (2-Mepy)⋅28 H₂O (1; 2-Mepy=2-methylpyridine, 1,10-phen=1,10-phenanthroline, H₂TDC=thiophene-2,5-dicarboxylic acid), was hydrothermally synthesized and structurally characterized. Unusually, two kinds of high-nuclearity clusters, namely [(Pr₄Sb₁₂O₁₈ (OH)Cl₁₁)(COO)₅]⁵⁻ and [(Pr₄Sb₁₂O₁₈ (OH)Cl₉)Cl(COO)₅]⁴⁻, coexist in the structure of compound 1; two of the latter clusters are doubly bridged by two μ₂-Cl⁻ moieties to form a new centrosymmetric dimeric cluster. An unprecedented spontaneous and reversible single-crystal-to-single-crystal transformation was observed, which simultaneously involved a notable organic-ligand movement between the metal ions and an alteration of the bridging ion in the dimeric cluster, induced by guest-release/re-adsorption, thereby giving rise to the interconversion between compound 1 and the compound (2-MepyH)₃[{Fe(1,10-phen)₃}₃][{Pr₄Sb₁₂O₁₈(OH)Cl_11.5}(TDC)₄({Pr₄Sb₁₂O₁₈Cl_10.5(TDC)_0.5(H₂O)_1.5}O_0.5)]⋅ 25 H₂O (1′). The mechanism of this transformation has also been discussed in great detail. Photocatalytic H₂-evolution activity was observed for compound 1′ under UV light with Pt as a co-catalyst and MeOH as a sacrificial electron donor.

A polar indium thioantimonate, namely [Ni(en)₃][InSbS₄] (1) (en = ethylenediamine), has been synthesized under solvothermal conditions. Its structure features a left-handed helical anionic chain of [InSbS₄]_n^2n– moieties built upon trinuclear heterometallic clusters of {In₂SbS₈} as secondary building units. The [Ni(en)₃]²⁺ cations, acting as structure directors and charge balancing agents, are located among the chains and form extensive N–H···S and C–H···S hydrogen bonds with the S atoms of the anionic chains. The thermal stability, optical and ferroelectric properties, as well as theoretical band structure and density of states (DOS) have been studied.

A series of novel organically templated germanium antimony sulfides have been solvothermally synthesized and structurally, thermally, and optically characterized. The compound [Me₂NH₂]₆[(Ge₂Sb₂S₇)(Ge₄S₁₀)] (1) features two distinct tetranuclear [Ge₂Sb₂S₇]²⁻ and [Ge₄S₁₀]⁴⁻ isolated clusters. The compound [(Me)₂NH₂][DabcoH]₂[Ge₂Sb₃S₁₀] (2) (Dabco=triethylenediamine) features a 1D-[Ge₂Sb₃S₁₀]_n³ⁿ⁻ ribbon constructed with two [GeSbS₅]_n³ⁿ⁻ chains bridged by Sb³⁺ ion in ψ-SbS₄ configuration. Compounds [M(en)₃][GeSb₂S₆] (M=Ni (3), Co (4) en=ethylenediamine) feature the unique 2D grid layer structures of [GeSb₂S₆]_n²ⁿ⁻. The compound [(Me)₂NH₂]₂[GeSb₂S₆] (5) previously reported by us features a 3D chiral microporous structure with the chiral channels. The optical absorption spectra indicate that all the compounds are wide bandgap semiconductors. Thermal stabilities of these compounds have been investigated by thermogravimetric analyses (TGA).