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A newly synthesized coordination polymer, [Cd(DMSO)(H2O)]3[Fe(CN)6]2 (CdHCF‐T), based on Cd2+ and Fe(CN)63− ions was prepared in a DMSO/H2O mixed solution and crystalized in the trigonal space group P‐31c. This novel 3D structure presented an interesting single‐crystal to single‐crystal transformation when the coordinated DMSO molecules were replaced by H2O, forming a well‐known Cd Prussian Blue analogue (Cd‐PBA). This occurrence is a rare phenomenon in transition metal hexacyanometallates and may provide a new strategy for obtaining new structures and overcoming the difficulty of growing single crystals of Prussian Blue analogues. Subsequent gas sorption and separation investigations based on the obtained Cd‐PBA were also carried out to evaluate its C2H2/CO2 separation capability. [ABSTRACT FROM AUTHOR]

We present here the syntheses and structural characterizations of inorganic polymeric cluster compounds, Cs[Mn(salen)]3[{Mo6Br6Se2}(CN)6] (1) and (H3O)(TBA)[Mn(salen)]2[{Mo6Br6Se2}(CN)6] (2) (TBA=tetrabutylammonium ((n‐C4H9)4N+)), built‐up from [{Mo6Br6Se2}(CN)6]4− molecular building blocks and Mn(salen)+ complexes (salen = salen = N,N′‐bis(salicylidene)ethylenediamine). The nature of additional counter cations (i. e. Cs+ or TBA+) enables to control the interactions between the [{Mo6Br6Se2}(CN)6]4− building blocks and the Mn(salen)+ groups. Thus, 1 was obtained by slow diffusion of a methanol solution of K2Cs2[{Mo6Br6Se2}(CN)6] cluster compound into a methanol solution of Mn(salen)ClO4. 2 was obtained in a similar way but after the addition of tetrabutylammonium bromide into the solution of Mn(salen)ClO4. 1 is a bimetallic 3D coordination compound (R3‾c ${R\bar{3}c}$) and 2 is a bimetallic 2D compound (P1‾ ${P\bar{1}}$). Structural correlations between 1 and 2 are discussed and compared with relevant examples found in the literature. [ABSTRACT FROM AUTHOR]

Ten homoleptic lanthanide containing 1D‐coordination polymers, three heterobimetallic lanthanide/alkaline earth complexes as well as two alkaline earth complexes of the formula 1∞[Ln(2‐PyPz)3], [Tb2AE(2‐PyPz)8], and [AE(2‐PyPz)2(2‐PyPzH)2], Ln=La−Nd, Sm−Ho, AE=Ca, Sr, Ba were obtained by reactions of the lanthanide (Ln) and/or the alkaline earth metals (AE) with the ligand 3‐(2‐pyridyl)pyrazole. Organic melt based and/or solvothermal synthesis results in a redox reaction. The investigated compounds exhibit fair thermal stability up to 400 °C. The Ce3+ compound exhibits a bright and red 5d‐based broad band emission with a maximum at around 640 nm under UV excitation marking an example of a strong reduction of the exited 5d states of Ce(III). The co‐doping of the Gd‐containing coordination polymers with Eu3+ and Tb3+ allows for a shift in the chromaticity from the ion specific 4 f‐based emission colors close to white light emission and thus for a versatile tuning of the chromaticity. The co‐doping of Eu3+ with Tb3+ and vice versa shows metal‐to‐metal energy transfer (MMET) between 4 f‐levels of Tb3+ and Eu3+, which influences the tuning of the emission colour. [ABSTRACT FROM AUTHOR]

[Li{C5(CN)5}(H2O)] was prepared by salt metathesis between LiCl and [Ag{C5(CN)5}], followed by recrystallization from methanol. The compound crystallizes in the orthorhombic space group Pnma and forms a coordination polymer. Three cyano substituents in 1,2,3 position coordinate to three different lithium ions forming a ribbon structure with adjacent 14‐membered rings, while the remaining two cyano groups act as hydrogen bond acceptors towards two water hydrogen atoms of a neighboring ribbon. As a consequence, a wavy sheet structure results. [ABSTRACT FROM AUTHOR]

A new Cd(II) coordination polymer of [Cd(H2L)(4,4'‐bipy)(H2O)]n (1, H4L=4‐[(3,4‐dicarboxyphenyl)disulfanyl]benzene‐1,2‐dicarboxylic acid, 4,4'‐bipy=4,4'‐bipyridine) was hydrothermally synthesized. The H4L ligand was in situ generated via the formation of disulfide bond between two 4‐sulfanylbenzene‐1,2‐dicarboxylic acid molecular. The in situ generated H4L ligand deprotonated two protons into H2L2−, which acts as a bidentate ligand to connected Cd(II) ions into a 2D layered structure with the assistance of 4,4'‐bipy ligands. The solids of 1 emits strong blue luminescence, and can be used as a luminescence probe for the detection of Co2+ ions. The limit of detection (LOD) of Co(II) ions by 1 was calculated to be 5.4 μM. [ABSTRACT FROM AUTHOR]

By assembling Cd2+ ions with two reported squaramide‐based ligands in solvothermal reaction condition, two new MOFs with the formulas Cd2(L1)(DMF)3 (sq‐Cd‐MOF‐1) (H4L1=5,5'‐((3,4‐dioxocylcobut‐1‐ene‐1,2‐diyl)bis(azanediyl) diisophthalic acid) and Cd(L2)(dpe) (sq‐Cd‐MOF‐2) (H2L2=3,3'‐((3,4‐dioxocyclobut‐1‐ene‐1,2‐diyl)bis(azanediyl)) dibenzoic acid, dpe=1,2‐di(pyridine‐4‐yl)ethane) are obtained. The MOFs are characterized by elemental analysis, IR, TGA, single‐crystal X‐ray diffraction, and PXRD. X‐ray data analysis reveals that sq‐Cd‐MOF‐1 possesses a new three‐dimensional framework with one dimension narrow apertures, while the structure of sq‐Cd‐MOF‐2 contains a novel ring‐ring connecting chain‐based double layer, as a two‐dimensional MOF. sq‐Cd‐MOF‐2 maintains high porosity via the packing of these layers. More importantly, reversible crystal to crystal transformation between sq‐Cd‐MOF‐2 and its activated state (sq‐Cd‐MOF‐2ac) is observed, triggered by the solvent in the pores. Michael addition reaction of the derivatives of β‐nitrostyrene and acetylacetone demonstrates that sq‐Cd‐MOF‐2 as a heterogeneous catalyst exhibits excellent catalytic capacity and stability. These results are useful for developing research on 2D soft MOFs and their potential application. [ABSTRACT FROM AUTHOR]

Two Co(II) coordination polymers, {[Co(ca)(bpe)(H2O)] ⋅ H2O}n (1) and [Co(ca)(bibp)]n (2) (H2ca=citraconic acid, bpe=1,2‐di(4‐pyridyl)ethylene, bibp=4,4′‐bis(imidazolyl)biphenyl) were prepared by hydrothermal reactions, and characterized by single‐crystal X‐ray diffractions, elemental analysis, FT‐IR, PXRD and TGA. Compound 1 shows a 2D grid layer containing Co‐carboxylate chains. Compound 2 exhibits a three‐dimensional metal‐organic framework with the dia topology type and 66 topology symbol. Both compounds have high thermal stabilities and good phase purity. The photocatalytic reactions of two compounds were investigated under UV irradiation in the presence of H2O2, and the results show that both compounds are highly efficient photocatalysts for MB and RhB degradation, which may be used as potential materials for wastewater treatment. [ABSTRACT FROM AUTHOR]

A new binuclear complex {[Cd(phen)2(H2O)] ⋅ (TMA)2−}2 has been synthesized through the reaction of o‐phenanthroline (phen), 3‐thiophenemalonic acid (H2TMA), and cadmium acetate in a 1 : 2 (v/v) EtOH‐H2O mixture at room temperature. This complex can undergo single‐crystal‐to‐single‐crystal (SCSC) transformation to a new mononuclear complex [Cd(phen)3] ⋅ 2(HTMA)− ⋅ H2TMA} by a simple in‐situ solvent evaporation method at room temperature without changing the reaction system. In the whole SCSC process, with the solvent water molecules decreasing and the concentration of ligands increasing, the phen ligands replace the coordination water and coordinate with cadmium ions, finally resulting in the crystal structure transformation in the solid state. [ABSTRACT FROM AUTHOR]

Two new MOFs with a Zn4 SBU, namely {[Zn2(teaH)] ⋅ 2(μ‐bdc)0.5}2 (I) and {[Zn2(MedeaH)] ⋅ 3(μ‐bdc)0.5}2 ⋅ (H2O) (II), have been prepared through altering polyalcohol amines. Single‐crystal X‐ray analysis reveals that their topological controllability mainly arise from the SBU connection being dependent on ethanolic arms of polyalcohol amines. Topological evolution is used to improve our understanding for the feasibility to tune their topology toward SBU connection. Compound I shows a 44 network in which the Zn4 rings act as planar four‐connected node, whereas II features a 3D pcu network based on the non‐planar six‐connected Zn4 SUBs. The luminescent properties of the two compounds have also been investigated. [ABSTRACT FROM AUTHOR]

We report the synthesis, crystal structures, and properties of three lanthanide(III) coordination complexes based on 2‐thiopheneacrylic acid (Htpa) of the formula [Ln(tpa)3(H2O)3] ⋅ 3(Htpa) (Ln=Tb (1), Dy (2), Er (3)). The complexes were characterized by single crystal X‐ray diffraction, powder X‐ray diffraction, elemental analysis, IR, TGA, and photoluminescence spectroscopy. Structural analysis indicates that all three complexes are isostructural and crystallize in the trigonal space group R3. The structures of these complexes consist of a discrete neutral mononuclear species [Ln(tpa)3(H2O)3] and the Htpa molecule. In the crystal, the complex species are self‐assembled into a one‐dimensional (1D) supramolecular chain through classical O−H⋅⋅⋅O hydrogen bonds existing between water molecules and carboxylate oxygen atoms. The adjacent chains are further joined together by C−H⋅⋅⋅π hydrogen bonds involving the thiophene moieties, resulting in the formation of a 3D supramolecular framework. The frameworks feature 1D channels with a dimeter of ca. 1.5 nm that can accommodate Htpa molecules to allow the formation of cocrystals via strong hydrogen bonds. In addition, the solid‐state luminescence and thermal properties of these complexes were also investigated. [ABSTRACT FROM AUTHOR]

A new [Ca(H2O)6]2+ cations‐templated coordination polymer, namely {[Ca(H2O)6][Cu4(btec)2(μ3‐OH)2]}n (1, H4btec=1,2,4,5‐benzenetetracarboxylic acid), has been prepared via the solvothermal reactions of CuCl2 ⋅ 2H2O, CaCl2, and H4btec. X‐ray structural analysis revealed that it features a tetranuclear [Cu4(COO)6(μ3‐OH)2] cluster‐based 3D anionic framework with (4,8)‐connected scu topology that was further balanced by the isolated [Ca(H2O)6]2+ cations. The framework of 1 shows high thermostability under air atmosphere. Moreover, such compound shows high photocatalytic activity for the degradation of methyl blue (MB) with the degradation efficiency of 94.5 %, and the possible photocatalytic mechanism was also clarified. [ABSTRACT FROM AUTHOR]

Two new coordination polymers [Cu(L)(phen)]n (1) and {[Mn2(L)2(phen)2]⋅H2O}n (2, H2L is 4,4′‐(azanediylbis(methylene))dibenzoic acid, phen is o‐phenanthroline) were synthesized using hydrothermally method. Complexes 1 and 2 were characterized by powder XRD, FT‐IR, elemental analysis, thermogravimetry, and X‐ray single‐crystal diffraction. Complex 1 belongs to monoclinic system with space group P21/n while complex 2 belongs to triclinic system with space group Pī. Complex 1 is 1D coordination polymers while complex 2 is 2D coordination polymers. Hirshfeld surface analysis of 1 and 2 were investigated and discussed in detail. Moreover, Magnetic studies reveal that complex 2 displays dominant antiferromagnetic interactions between MnII ions through syn‐syn‐carboxyl bridges. [ABSTRACT FROM AUTHOR]

Two noncentrosymmetric d10 metal centered coordination polymers with formula [Zn(PTA)Cl2] ⋅ H2O (1) and [Hg3(PTA)3Cl6] (2) have been successfully prepared by the reaction of rigid non‐centrosymmetric ligand 3,5‐dimethyl‐N‐(pyridin‐4‐ylmethylene)‐4H‐1,2,4‐triazole‐4‐amine (PTA) and corresponding metal salts ZnCl2 and HgCl2. Both 1 and 2 feature acentric 1D zigzag chain arrangements, in which each chain is composed of linear 2‐connected PTA ligands and V‐shaped 2‐connected metal nodes Zn(II) or Hg(II). Complex 1 possesses C2 symmetric eqitlateral 1D zigzag chain structure and corresponding crisscross array. In contrast with 1, 2 displays dissymmetric ineqitlateral 1D zigzag chain structure and common parallel arrangement. Being their acentric essence as well as colorless and transparent merits, the preliminary powder NLO properties of 1 and 2 were invesigated in solid‐state. The results indicated that the SHG intensities of 1 and 2 are about 1 and o.5 times that of commercial KDP. [ABSTRACT FROM AUTHOR]

Reactions of Ni(NCS)2 and 3‐cyanopyridine in different solvents lead to the formation of Ni(NCS)2(3‐cyanopyridine)4 (1) already reported in the literature, Ni(NCS)2(3‐cyanopyridine)2(H2O)2 (2), Ni(NCS)2(3‐cyanopyridine)2(CH3OH)2 (3), Ni(NCS)2(3‐cyanopyridine)2(CH3CN)2 (4) and Ni(NCS)2(3‐cyanopyridine)2 (5). The crystal structures of 1–4 consist of discrete octahedral complexes, in which the thiocyanate anions, as well as the 3‐cyanopyridine coligands, are only terminally N‐bonded. In compound 5 the Ni cations are octahedrally coordinated and linked by pairs of thiocyanate anions into dinuclear units that are further connected into layers by single μ‐1,3‐bridging anionic ligands. TG‐DTA measurements of the discrete complex 1 reveal that in the first step half of the coligands are emitted leading to the formation of compound 5. In contrast, compounds 2 and 3 transform into a new crystalline phase of the same composition (6) upon heating that should also contain μ‐1,3‐bridging anionic ligands, but the outcome of this reaction strongly depends on the reaction conditions. The acetonitrile complex 4 is unstable at room temperature and decomposes into a mixture of different phases including the aqua complex 2. Magnetic measurements of compound 5 prove a ferromagnetic transition at Tc=6.0 K. This result is compared to those obtained for other thiocyanate compounds exhibiting a similar layer topology. [ABSTRACT FROM AUTHOR]

The new compounds with the sum formulae [Cs([18]crown‐6)]2[Zn(C2H)4] ⋅ 8NH3, Rb3[Rb([18]crown‐6)(NH3)][Cd(C2H)4]2 ⋅ {[18]crown‐6 ⋅ 2NH3} ⋅ NH3 and [Cs([2.2.2]crypt)][In(C6H5)3(C2H)] were synthesized in liquid ammonia. The anionic units show tetrahedrally coordinated central atoms with four hydrogenacetylide ligands or one C2H− and three C6H5− ligands. Solid state starting materials for these ligands were either AC2H (A=Rb, Cs) or Cs2C2. The fact that the indium compound contains a hydrogenacetylide ligand, which was formed from Cs2C2, confirms again the equilibrium of the species C2H2, C2H− and C22− in liquid ammonia and again proves that acetylides slowly dissolve in this medium. [ABSTRACT FROM AUTHOR]