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A novel Cd( (II)-organic framework [Cd(Hcbic)] n (H 3 cbic = 1-(4-carboxybenz-yl)−1H-benzoim-idazole-5, 6-dicarboxylic acid) was assembled and characterized by X-ray single crystal analysis. The Cd-MOF features one-dimensional left and right-handed double helical chains with screw-pitch of about 4.727 Å and the 4-methyl benzoic acid groups of Hcbic 2− ligands in MOF-1 play many ribbons distributing in the two sides of the 2D networks. It is found that MOF-1 shows high selectivity ( K SV = 1.8 × 10 5 L / mol) for Fe 3+ ions in water solution with luminescent quenching because of the existence of uncoordinated carboxyl groups within open frameworks, which indicates that MOF-1 is a simple and reliable detection sensing reagent for Fe 3+ in practical applications. [ABSTRACT FROM AUTHOR]

Bifunctional organic ligands are very popular for the design of coordination polymers because they allow the formation of a great diversity of structures. In the title coordination polymer, the new bifunctional inversion‐symmetric ligand 2,5‐bis(1H‐1,2,4‐triazol‐1‐yl)terephthalic acid (abbreviated as H2bttpa) links CdII cations, giving rise to the three‐dimensional CdII coordination polymer catena‐poly[diaqua[μ4‐2,5‐bis(1H‐1,2,4‐triazol‐1‐yl)terephthalato‐κ4O1:O4:N4:N4′]cadmium(II)], [Cd(C12H6N6O4)(H2O)2]n or [Cd(bttpa)(H2O)2]n. The asymmetric unit consists of half a CdII cation, half a bttpa2− ligand and one coordinated water molecule. The CdII cation is located on a twofold axis and is hexacoordinated in a distorted octahedral environment of four O and two N atoms. Four different bttpa2− ligands contribute to this coordination, with two carboxylate O atoms in trans positions and two triazole N atoms in cis positions. Two aqua ligands in cis positions complete the coordination sphere. The fully deprotonated bttpa2− ligand sits about a crystallographic centre of inversion and links two CdII cations to form a chain in a μ2‐terephthalato‐κ2O1:O4 bridge. This chain extends in the other two directions via the triazole heterocycles, producing a three‐dimensional framework. O—H…O hydrogen bonds and weak C—H…N interactions stabilize the three‐dimensional crystal structure. The FT–IR spectrum, X‐ray powder pattern, thermogravimetric behaviour and solid‐state photoluminescence of the title polymer have been investigated. The photoluminescence is enhanced and red‐shifted with respect to the uncoordinated ligand. [ABSTRACT FROM AUTHOR]

The hydroxo-bridged dinuclear copper (II)/phen complex [Cu2(phen)2(OH)2(H2O)2][Cu2(phen)2(OH)2Cl2]Cl2.6H2O (phen=1,10-phenanthroline) has been prepared and characterized by single crystal X-ray diffraction. The coordinated area of the complex shows two distorted [CuN2O2Ow] and [CuN2O2Cl] square-pyramidal and one strictly planar configuration CuO2Cu involving two O atoms of hydroxo-bridged, Cu2+ cations, N atoms of two phen ligands and disorder solvate water and chlorine anions. In the presence of H2O2, the complex of mono(1,10-phenanthroline)copper exhibits higher activity as a nuclease than bis(1,10-phenanthroline)copper. [Copyright &y& Elsevier]

A new coordination polymer (CP), namely, poly[[diaquatris[μ2‐1,4‐bis(1H‐imidazol‐1‐yl)benzene]bis[μ6‐4‐(2,4‐dicarboxylatophenoxy)phthalato]tetracobalt(II)] hexahydrate], {[Co4(C16H6O9)2(C12H10N4)3(H2O)2]·6H2O}n, has been synthesized by solvothermal reaction. The CP was fully characterized by IR spectroscopy, elemental analysis, thermogravimetric analysis, and powder and single‐crystal X‐ray diffraction. It presents a three‐dimensional (3D) structure based on tetranuclear CoII secondary building units (SBUs) with a tfz‐d net and point symbol (43)2(46·618·84). The 4‐(2,4‐dicarboxyphenoxy)phthalic acid (H4dcppa) ligands are completely deprotonated and link {Co4(COO)4}4− SBUs into two‐dimensional (2D) layers. Furthermore, adjacent layers are connected by 1,4‐bis(1H‐imidazol‐1‐yl)benzene (bib) ligands, giving rise to a 3D supramolecular architecture. Interestingly, there are numerous elliptical cavities in the CP where isolated unique discrete hexameric water clusters have been observed. The results of thermogravimetric and magnetic analyses are described in detail. [ABSTRACT FROM AUTHOR]

Two two-dimensional Ni(II) or Zn(II)-based coordination polymers, namely [[Ni3(μ4-cpboda)2(μ2-H2O)2(DMF)2(H2O)2]·3DMF·2HCOOH·2H2O]n (1) and [[Zn3(μ4-cpboda)2(μ2-H2O)2(DMF)2(H2O)2]·3DMF·3HCOOH·3H2O]n (2), a three-dimensional Ni(II)-based coordination polymer, namely [[Ni3(μ3-cpboda)2(1,4-bib)5(H2O)2]·DMF]n (3), and a dinuclear Zn(II) complex, namely [Zn (μ2-Hcpboda)(2,2-bipy)(H2O)]2 (4) (H3cpboda = 3,3′-((5-carboxy-1,3-phenylene)bis(oxy))dibenzoic acid, 2,2-bipy = 2,2-bipyridine, 1,4-bib = 1,4-di(1H-imidazol-1-yl)benzene), were successfully synthesized under solvothermal conditions and characterized via single-crystal X-ray and powder diffraction analyses, elemental analyses (EA), FT-IR spectroscopy, and thermogravimetric analysis (TGA). Complexes 1 and 2 show isomorphism and (3,4,6)-connected 2D sheet structures with the (32·4)2(32·83·9)2(34·4·282·94·103) topology. Complex 3 is a 4,4,7-connected 3D structure with the (42·52·62)2(46·5·614)2(54·6·8) topology. Complex 4 is only a simple dinuclear structure. Magnetization measurements disclose the weak ferromagnetic behavior between Ni(II) ions in the complexes 1 and 3. Fluorescence measurements indicate that 2 and 4 exhibit fast, sensitive, and selective luminescence quenching responses towards Cr2O72−/CrO42− in an aqueous solution. The limit of detection for Cr2O72−/CrO42− ions were estimated to be 0.51 and 0.60 ppm for 2 (0.89 and 1.03 ppm for 4), respectively, which are comparable to those reported for the CP-based fluorescent probes that can simultaneously detect Cr2O72−/CrO42− in aqueous environments. Moreover, 2 and 4 can be easily regenerated after the detection experiments, which is indicative of the excellent recyclability. All these results suggest that complexes 2 and 4 are highly selective and recyclable luminescence sensing materials for the quantitative detection of Cr2O72−/CrO42− anions in aqueous solutions. [ABSTRACT FROM AUTHOR]

Six two‐dimensional (2D) coordination polymers (CPs), namely, poly[{μ5‐3,3‐[(5‐carboxylato‐1,3‐phenylene)bis(oxy)]dibenzoato‐κ6O1:O1′:O3,O3′:O5:O5′}bis(N,N‐dimethylformamide‐κO)lanthanide(III)], [Ln(C21H11O8)(C3H7NO)2]n, with lanthanide/Ln = cerium/Ce for CP1, praseodymium/Pr for CP2, neodymium/Nd for CP3, samarium/Sm for CP4, europium/Eu for CP5 and gadolinium/Gd for CP6, have been prepared by solvothermal methods using the ligand 3,3′‐[(5‐carboxy‐1,3‐phenylene)bis(oxy)]dibenzoic acid (H3cpboda) in the presence of Ln(NO3)3. The complexes were characterized by single‐crystal X‐ray and powder diffraction, IR spectroscopy, elemental analysis and thermogravimetric analysis (TGA). All the structures of this family of lanthanide CPs are isomorphous with the triclinic space group P and reveal that they have the same 2D network based on binuclear LnIII units, which are further extended via interlayer C—H...π interactions into a three‐dimensional supramolecular structure. The carboxylate groups of the cpboda3− ligands link adjacent LnIII ions and form binuclear [Ln2(RCOO)4] secondary building units (SBUs), in which each binuclear LnIII SBU contains four carboxylate groups from different cpboda3− ligands. Moreover, with the increase of the rare‐earth Ln atomic radius, the dihedral angles between the aromatic rings gradually increase. Magnetically, CP6 shows weak antiferromagnetic coupling between the GdIII ions. The solid‐state luminescence properties of CP2, CP5 and CP6 were examined at ambient temperature and CP5 exhibits characteristic red emission bands derived from the Eu3+ ion (CIE 0.53, 0.31), with luminescence quantum yields of 22%. Therefore, CP5 should be regarded as a potential optical material. [ABSTRACT FROM AUTHOR]

Two cadmium(II) complexes based on 2-(3-(pyridin-2-yl)-1H-pyrazol-1-yl)benzoate with chemical formulas of [Cd2(ppb)4(H2O)2]·8H2O (1) and [Cd(Hppb)I2]n (2) (Hppb = 2-(3-(pyridin-2-yl)-1H-pyrazol-1-yl)benzoic acid), have been synthesized. Both complexes are well characterized by IR, TGA and X-ray single-crystal as well as powder diffraction. Structural analyses reveal that 1 is a binuclear complex and 2 has one-dimensional polymers, respectively, in which they are expanded to three-dimensional supramolecular structures by hydrogen bonds. The Cd(II) coordinated environments in 1 are slightly distorted octahedral geometries, but central atoms in 2 display distorted square pyramidal geometries. There are obvious differences in ligation modes of the ppb− or Hppb ligands for both complexes. In 1, four ppb− ligands are divided into two groups, displaying µ1-kN, N′ and µ2-kN, N′: kO coordination modes. Two ppb− ligands act as two µ1,6-bridges linking the binuclear Cd(II) cations with a distance of 6.282(2) Å. In 2 the neutral Hppb ligands exhibit a µ2-kN, N′: kO coordination mode, and connecting Cd(II) ions by µ1,6-bridges and forming an infinite 1D chain along b axis. Hirshfeld surfaces and fingerprint plots analyses indicate that weak interactions of C–H···π, π···π, O–H···O or O–H···I play important roles in crystal packings of 1 and 2. Luminescent measurements in solid-state show their different intensities in the luminescences of 1 and 2. A binuclear complex [Cd2(ppb)4(H2O)2]·8H2O (1) and a one-dimensional complex [Cd(Hppb)I2]n (2) were synthesized and characterized by X-ray crystal diffraction. Investigation of solid-state luminescence properties indicates the blue shifts of the emission λmax of complexes. [ABSTRACT FROM AUTHOR]

Three novel coordination polymers (CPs), namely poly[[di‐μ‐aqua‐bis{μ4‐3,3′‐[(5‐carboxylato‐1,3‐phenylene)bis(oxy)]dibenzoato‐κ5O1:O1′,O3:O5:O5′}bis(1,10‐phenanthroline‐κ2N,N′)trinickel(II)] dimethylformamide 1.5‐solvate trihydrate], {[Ni3(C21H11O8)2(C12H8N2)2(H2O)2]·1.5C3H7NO·3H2O}n, (I), poly[[di‐μ‐aqua‐bis{μ4‐3,3′‐[(5‐carboxylato‐1,3‐phenylene)bis(oxy)]dibenzoato‐κ5O1:O1′,O3:O5:O5′}bis(1,10‐phenanthroline‐κ2N,N′)tricobalt(II)] diethylamine disolvate tetrahydrate], {[Co3(C21H11O8)2(C12H8N2)2(H2O)2]·2C2H7N·4H2O}n, (II), and catena‐poly[[aqua(1,10‐phenanthroline‐κ2N,N′)zinc(II)]‐μ‐5‐(3‐carboxyphenoxy)‐3,3′‐oxydibenzoato‐κ2O1:O3], [Zn(C21H12O8)(C12H8N2)(H2O)]n, (III), have been synthesized by the reaction of different metal ions (Ni2+, Co2+ and Zn2+), 3,3′‐[(5‐carboxy‐1,3‐phenylbis(oxy)]dibenzoic acid (H3cpboda) and 1,10‐phenanthroline (phen) under solvothermal conditions. All the CPs were characterized by elemental analysis, single‐crystal and powder X‐ray diffraction, FT–IR spectroscopy and thermogravimetric analysis. Complexes (I) and (II) have isomorphous structures, featuring similar linear trinuclear structural units, in which the central NiII/CoII atom is located on an inversion centre with a slightly distorted octahedral [NiO6]/[CoO6] geometry. This comprises four carboxylate O‐atom donors from two cpboda3− ligands and two O‐atom donors from bridging water molecules. The terminal NiII/CoII groups are each connected to the central NiII/CoII cation through two μ1,3‐carboxylate groups from two cpboda3− ligands and one water bridge, giving rise to linear trinuclear [M3(μ2‐H2O)2(RCOO)4] (M = Ni2+/Co2+) secondary building units (SBUs) and the SBUs develop two‐dimensional‐networks parallel to the (100) plane via cpboda3− ligands with new (32·4)2(32·83·9)2(34·42.82·94·103) topological structures. Zinc complex (III) displays one‐dimensional coordination chains and the five‐coordinated Zn atom forms a distorted square‐pyramidal [ZnO3N2] geometry, which is completed by two carboxylate O‐atom donors from two distinct Hcpboda2− ligands, one O atom from H2O and two N atoms from a chelating phen ligand. Magnetically, CP (I) shows weak ferromagnetic interactions involving the carboxylate groups, and bridging water molecules between the nickel(II) ions, and CP (II) shows antiferromagnetic interactions between the Co2+ ions. The solid‐state luminescence properties of CP (III) were examined at ambient temperature and the luminescence sensing of Cr2O72−/CrO42− anions in aqueous solution for (III) has also been investigated. [ABSTRACT FROM AUTHOR]

Five novel coordination polymers (CPs), formulated as {[Co3(μ4-cpboda)2(μ1,1-OH2)2(2,2-bipy)2]·1.5DMF·2H2O}n (1), {[Co3(μ3-cpboda)2(4,4′-bpy)3(H2O)2]·4H2O}n (2), {[Co(μ2-H2cpboda)2(1,4-bib)3(H2O)2]·H2O·DMF·1.5HCOOH}n (3), [Cd(μ3-Hcpboda)(1,4-bib)]n (4), and {[Cd3(μ4-cpboda)2(μ1,1-OH2)2(phen)2]·2DMF·1.5H2O}n (5) (H3cpboda = 3,3′-((5-carboxy-1,3-phenylene)bis(oxy))dibenzoic acid, 2,2-bipy = 2,2-bipyridine, 4,4′-bpy = 4,4′-bipyridine, 1,4-bib = 1,4-di(1H-imidazol-1-yl)benzene, phen = 1,10-phenanthroline) have been synthesized under solvothermal conditions and characterized by elemental analyses (EAs), single-crystal X-ray diffraction analyses, X-ray powder diffraction analyses (PXRD), FT-IR spectra, and thermogravimetric analyses (TGAs). The structural analyses reveal that these complexes have four 2D coordinate polymers and one 3D framework, in which metal ions are in octahedral coordination geometries in 1–3 and 5, but seven-coordinated disordered pentagonal bipyramids in 4. Complexes 1 and 5 represent linear trinuclear [M3(μ1,1-OH2)2(μ1,3-COO)4] SBUs in 1 (M = Co(ii)) and in 5 (M = Cd(ii)) based on a 3,4,6-connected net with a point symbol (32·4)2(32·83·9)2(34·42·82·94·103) net, complex 2 exhibiting a (3-c)2(4-c)(4-c)2 3D structure with the (52·6·82·9)2(52·62·92)(52·6)2 topology and complexes 3 and 4 having a novel 2D framework with the point symbol of (44·62). Magnetization analyses disclose the antiferromagnetic (AF) behaviors between Co(ii) ions in complexes 1 & 3 and S = 3/2 (Co2+) spin Heisenberg chains with alternating magnetic sequences (F/F/AF)n in 2. Fluorescence measurements indicate that 4 and 5 are promising luminescence sensors for the detection of CrO42− and Cr2O72− anions in aqueous solution. [ABSTRACT FROM AUTHOR]

A new cobalt(II) coordination polymer (CP), poly[[bis[μ6‐4‐(4‐carboxylatophenoxy)benzene‐1,3‐dicarboxylato‐κ6O1:O1:O3:O3′:O4:O4′]bis(1,10‐phenanthroline‐κ2N,N′)tricobalt(II)] 0.72‐hydrate], {[Co3(C15H7O7)2(C12H8N2)2]·0.72H2O}n, (I), is constructed from CoII ions and 4‐(4‐carboxyphenoxy)isophthalate (cpoia3−) and 1,10‐phenanthroline (phen) ligands. Based on centrosymmetric trinuclear [Co3(phen)2(COO)6] secondary building units (SBUs), the structure of (I) is a three‐dimensional CP with a (3,6)‐connected net and point symbol (42.6)2(44.62.87.102). The positions of four [Co3(phen)2(COO)6] SBUs and four cpoia3− ligands reproduce a Chinese‐knot‐shaped arrangement along the ab plane. (I) has been characterized by single‐crystal X‐ray diffraction, IR spectroscopy, powder X‐ray diffraction (PXRD) and thermostability analysis. It shows a good thermal stability from room temperature to 673 K. In addition, the temperature dependence of the magnetic properties was measured. [ABSTRACT FROM AUTHOR]

Four manganese (II) compounds are obtained by the reaction of manganese salts, triazole-derivatives and auxiliary reagents in aqueous solution or mix-solvents by routine or hydrothermal reactions. X-ray crystal structure analyses reveal that a neutral 0D compound [Mn(Hmctrz) 2 (H 2 O) 2 ] ( 1 ) (H 2 mctrz = 1 H -1,2,4-triazole-3-carboxylic acid) displays a centro-symmetric mononuclear octahedral entity with two Hmctrz − anions and two water molecules; two neutral 2D clusters [Mn(Hdctrz)(H 2 O) 2 ] n ( 2 ) (H 3 dctrz = 1 H -1,2,4-triazole-3,5-dicarboxylic acid) and [Mn 2 (pbtrz)(btca)] n ·4nH 2 O ( 3 ) (pbtrz = 1,3-bis(1,2,4-triazol-1-yl)-propane&H 4 btca = benzene-1,2,4,5-tetracarboxylic acid) possess layer structures with Hdctrz 2 − linkers ( 2 ) and Mn(II)-pbtrz-Mn(II) building blocks periodically extended by μ -btca 4 − connectors ( 3 ); [Mn(pbtrz)] n ·nOAc·nOH ( 4 ) shows a 3D diamond-shaped cationic framework with the anion void volume of 49.2%. Nitrogenous bases are used as the auxiliary ligand in compound 3 and the temple ligand in compounds 1 , 2 , and 4 . Compounds 1 – 4 show antiferromagnetic coupling that has been fitted by different models with the molecular field approximate with D = − 0.129(1) cm −1 for 1 , J = − 0.354(4) cm −1 for 2 and J = − 0.696(6) cm −1 for 3 , respectively. The magnetic differences can be related to different superexchange interactions transmitted by the crystal lattice and/or the zero field splitting (ZFS) of the 6 A 1g single-ion states of 1 and the syn-anti -COO − of 2 as well as the mixed magnetic bridges of μ 1 -O and μ -pbtrz- μ -COO − of 3 . [ABSTRACT FROM AUTHOR]

The design and synthesis of coordination polymers (CPs) have attracted much interest due to the intriguing diversity of their architectures and topologies. The functional solid catena‐poly[μ2‐aqua‐triaqua{μ4‐5‐[4‐carboxyphenoxy)methyl]benzene‐1,3‐dicarboxylato}{μ3‐5‐[4‐carboxyphenoxy)methyl]benzene‐1,3‐dicarboxylato}dicobalt(II)], [Co2(C16H10O7)2(H2O)4]n or [Co2(HL)2(μ2‐H2O)(H2O)3]n, was synthesized successfully by self‐assembly of CoII ions with 5‐[(4‐carboxyphenoxy)methyl]isophthalic acid (H3L). The title compound was obtained under hydrothermal conditions and exhibits a twofold interpenetrated three‐dimensional skeleton with hms 3,5‐conn topology according to the cluster representation for valence‐bonded metal–organic frameworks (MOFs). It has been characterized by single‐crystal X‐ray diffraction, IR spectroscopy, powder X‐ray diffraction (PXRD), thermogravimetric analysis and susceptibility measurements. The antiferromagnetic coupling between adjacent CoII centres occurs via superexchange through the ligands. [ABSTRACT FROM AUTHOR]

Based on a bifunctional 2-(pyridine-2-yl)-1H-4,5-imidazole-dicarboxylic acid ligand, a novel family of lanthanide coordination polymers with formulas [Ln(HPIDC)(C2O4)0.5(H2O)]n (Ln = La, 1; Ce, 2) and [Ln2(HPIDC)(C2O4)2(H2O)3]n·2nH2O (Ln = Pr, 3; Nd, 4; Sm, 5; Eu, 6; Gd, 7; Tb, 8; Dy, 9; Ho, 10; Er, 11), (H3PIDC = 2-(pyridine-2-yl)-1H-imidazole-4,5-dicarboxylic acid & H2C2O4 = oxalic acid) has been prepared under hydro-solvothermal conditions and characterized by single crystal X-ray diffraction, elemental analysis, IR spectroscopy, and thermogravimetric analysis. Notably, the ligands adopt the same μ3-kN,O:kO′,O′′:kO′′′ conformation in all compounds, which brings about two types of isostructural lanthanide coordination polymers. Namely, 1 and 2 crystallize in the monoclinic space group P21/n and are composed of [Ln2(COO)2] dinuclear subunits with networks having the symbol (63·82·10)2(63)2(8). Meanwhile, 3–11 crystallize in the monoclinic space group P21/c and are constructed with tetranuclear [Ln4(COO)4] subunits with networks having the symbol (103)2(104·122)(10)2. The photoluminescence measurement indicates that Eu(iii) and Tb(iii) coordination polymers show very strong reddish-orange and green emission bands with CIE chromaticity coordinates (0.612, 0.325) and (0.284, 0.523) and quantum yields of 54.3% & 34.7%, respectively. The magnetic properties of 3 and 7–11 are investigated, and the results indicate a ferromagnetic interaction between Gd(iii) magnetic centers in complex 7 and antiferromagnetic interactions in other complexes. [ABSTRACT FROM AUTHOR]

Three new Ni(ii)-clusters based on a Y-shaped ligand (biphenyl-3,4′,5-tricarboxylate, H3BPT), [Ni5(HBPT)4(OH)2(H2O)12]n (1), [Ni4(BPT)2(OH)2(H2O)6]n·4nH2O (2), and [Ni7(BPT)2(1,4-bib)2(OH)6(HCO2)2]n·3nH2O (3) (1,4-bib = 1,4-bi(1H-imidazol-1-yl)benzene), have been synthesized under solvothermal conditions. They were studied by infrared spectroscopy (IR), single crystal X-ray diffraction, thermogravimetric analysis (TGA), and magnetochemistry. The complexes contain low nuclear Ni-clusters as building units (BUs). Structurally, in 1, the cluster BUs of [Ni5(μ3-OH)2]8+ can be viewed as two reverse triangles sharing a common vertex, which are connected by the partially deprotonated μ2–η1:η1-HBPT2− forming 1D chains. The BUs of [Ni4(μ3-OH)2]6+ clusters in 2 can be considered as two reverse triangles sharing a common edge and extended by deprotonated μ6–η1:η1:η1:η1:η2-BPT3− constructing a 2D framework. The 3D framework of complex 3 consists of a [Ni7(μ3-OH)4(R-COO)7(HCO2)3] cluster BUs with fully deprotonated μ5–η1:η1:η1:η1:η1:η1-BPT3− and 1,4-bib ligands. In addition, TGA reveals that the complexes are stable in the range of 293–548 K. Magnetostructural analyses indicate ferromagnetic coupling of J1 = 1.85(3) and J2 = 2.25(4) cm−1 in 1 and J = 5.76(6) cm−1 in 2, whereas magnetic parameters J1 = −2.64(3), J2 = −23.22(19) and J3 = 12.02(5) cm−1 indicate an alternating magnetic chain (AF/F) in 3. [ABSTRACT FROM AUTHOR]

Coordination polymers (CPs) built by coordination bonds between metal ions/clusters and multidentate organic ligands exhibit fascinating structural topologies and potential applications as functional solid materials. The title coordination polymer, poly[diaquabis(μ4-biphenyl-3,4′,5-tricarboxylato-κ4 O3: O3′: O4′: O5)tris[μ2-1,4-bis(1 H-imidazol-1-yl)benzene-κ2 N3: N3′]dicopper(II)dicopper(I)], [CuII2CuI2(C15H7O6)2(C12H10N4)3(H2O)2] n, was crystallized from a mixture of biphenyl-3,4′,5-tricarboxylic acid (H3bpt), 1,4-bis(1 H-imidazol-1-yl)benzene (1,4-bib) and copper(II) chloride in a water-CH3CN mixture under solvothermal reaction conditions. The asymmetric unit consists of two crystallographically independent Cu atoms, one of which is CuII, while the other has been reduced to the CuI ion. The CuII centre is pentacoordinated by three O atoms from three bpt3− ligands, one N atom from a 1,4-bib ligand and one O atom from a coordinated water molecule, and the coordination geometry can be described as distorted trigonal bipyramidal. The CuI atom exhibits a T-shaped geometry (CuN2O) coordinated by one O atom from a bpt3− ligand and two N atoms from two 1,4-bib ligands. The CuII atoms are extended by bpt3− and 1,4-bib linkers to generate a two-dimensional network, while the CuI atoms are linked by 1,4-bib ligands, forming one-dimensional chains along the [20] direction. In addition, the completely deprotonated μ4-η1:η1:η1:η1 bpt3− ligands bridge one CuI and three CuII cations along the a (or [100]) direction to form a three-dimensional framework with a (103)2(10)2(42.6.102.12)2(42.6.82.10)2(8) topology via a 2,2,3,4,4-connected net. An investigation of the magnetic properties indicated a very weak ferromagnetic behaviour. [ABSTRACT FROM AUTHOR]

A new type of 2D light-emitting coordination polymer [Cd(H 2 L)(H 2 O) 2 ] n (CP1) (H 4 L=3,5-bis(3,4-dicarboxyphenyl)pyridine) was successfully constructed, which shows stability in a wide range of pH solution. More importantly, this material is a multifunctional luminescence sensing material which can become a good candidate for La3+/Eu3+/Tb3+/Dy3+ ions selective sensing with lower detection limits. A multifunctional light-emitting sensing material, which can selectively detect La3+/Eu3+/Tb3+/Dy3+ ion. [Display omitted] • A 2D undulating coordination polymer Cd-CP was successfully synthesized. • Cd-CP can sensitize rare earth ions. • Cd-CP was used as a fluorescent sensing material for detecting La3+/Eu3+/Tb3+/Dy3+ ions. [ABSTRACT FROM AUTHOR]

Self-assembly of CuCl2, NdCl3, 5-bromosalicylaldehyde and glycylglycine yields the ion-pair copper(II)-neodymium(III) complex, poly[[decaaquabis[μ3-2-({2-[(5-bromo-2-oxidobenzylidene)amino]acetyl}azanidyl)acetato]bis[μ2-2-({2-[(5-bromo-2-oxidobenzylidene)amino]acetyl}azanidyl)acetato]tetracopper(II)dineodymium(III)] bis{[2-({2-[(5-bromo-2-oxidobenzylidene)amino]acetyl}azanidyl)acetato]cuprate(II)} tetradecahydrate], {[Cu4Nd2(C11H8BrN2O4)4(H2O)10][Cu(C11H8BrN2O4)]2·14H2O} n. The anion is planar and mononuclear, showing an approximately square-planar coordination of the metal atom, while the cation is a hexanuclear centrosymmetric transition metal-lanthanide (Cu-Nd) heterometallic complex, with the independent copper cations in square-planar and square-pyramidal coordinations. The asymmetric unit comprises one half of this cation, one anion and seven solvent water molecules. The positions of the six metal centres in the cation reproduce a Chinese knot arrangement. The dipeptidic Schiff base releases three H atoms and can act as a tetradentate, a pentadentate or a hexadentate ligand. Longer interactions between the pentadentate ligands and the Jahn-Teller CuII cation link the hexanuclear aggregates into cationic chains in the [010] direction in which 14- and 22-membered subloops occur. Extensive hydrogen bonding in three dimensions involves both the coordinated and the solvent water molecules. [ABSTRACT FROM AUTHOR]

A new Gd3+ coordination polymer (CP), namely, poly[diaqua[μ4‐1′‐carboxy‐3,3′‐(diazene‐1,2‐diyl)dibenzene‐1,2,2′‐tricarboxylato]gadolinium(III)], [Gd(C16H7N2O8)(H2O)2]n, (I), has been synthesized hydrothermally from Gd(NO3)3·6H2O and azobenzene‐2,2′,3,3′‐tetracarboxylic acid (H4abtc). The target solid has been characterized by single‐crystal and powder X‐ray diffraction, elemental analysis, IR spectroscopy and susceptibility measurements. CP (I) crystallizes in the monoclinic space group C2/c. The structure features a 4‐connected topology in which Gd3+ ions are connected by carboxylate groups into a linear chain along the monoclinic symmetry direction. Adjacent one‐dimensional aggregates are bridged by Habtc3− ligands to form a two‐dimensional CP in the (10) plane. A very short hydrogen bond [O...O = 2.4393 (4) Å] links neighbouring layers into a three‐dimensional network. A magnetic study revealed antiferromagnetic Gd...Gd coupling within the chain direction. CP (I) displays a significant magnetocaloric effect (MCE), with a maximum −ΔSm of 27.26 J kg−1 K−1 for ΔH = 7 T at 3.0 K. As the MCE in (I) exceeds that of the commercial magnetic refrigerant GGG (Gd3Ga5O12, −ΔSm = 24 J kg−1 K−1, ΔH = 30 kG), CP (I) can be regarded as a potential cryogenic material for low‐temperature magnetic refrigeration. [ABSTRACT FROM AUTHOR]

A novel cadmium coordination polymer, namely, {[Cd(Htcpb)(DMF)(H2O)2]·1.5H2O}n(1) has been hydrothermally synthesized from Cd(NO3)2·4H2O and a flexible triangle ligand of 1,3,5-tris(4-carboxyphenoxy)benzene (H3tcpb). The structure has been determined by single-crystal X-ray diffraction analysis, elemental analysis, IR spectrum, powder X-ray diffraction, and thermanalysis. The structural analysis displays that complex 1 obtained at 120 °C features a 1D chain containing mononuclear cadmium centers. The fluorescence property of complex 1 was examined in the solid-state at room temperature, and upon excitation at 290 nm, it exhibits distinct fluorescence with the maximum emission at 389 nm. [ABSTRACT FROM AUTHOR]

A new chiral one-dimensional gadolinium coordination polymer [Gd(HDTTA)3(CH3OH)3]n (1) (D-H2DTTA = (+)-Di-p-toluoyl-D-tartaric acid) was synthesized at room temperature, and fully structurally characterized by Infrared (IR), elemental analysis (EA), single-crystal and powder X-ray diffraction (PXRD). The structure analysis shows that complex 1 belongs to the trigonal system with R3 space group and displays an infinite chain structure along the c axis. In 1, each Gd3+ cation is in the tri-capped trigonal prism geometry, and neighboring Gd3+ cations are connected by three partly deprotonated HDTTA− ligands with the Gd···Gd distance of 7.686(1) Å. The circular dichroism (CD) spectrum demonstrates the chirality of the complex. Magnetic studies reveal that complex 1 displays weak antiferromagnetic interactions between Gd3+ cations and it exhibits a small magnetic entropy change (−ΔSm = 7.26 J kg−1 K−1 with ΔH = 7 T and T = 2.5 K) because of long Gd···Gd distance and relatively low magnetic density. [ABSTRACT FROM AUTHOR]

• A novel Tb coordination polymer with formula [Tb(cpboda) (DMF) 1.863 (HCOOH) 0.137 ] n , has been prepared using a solvothermal method. • The Tb-CP is a high-efficiency luminescent CP sensor for detecting PO 4 3− ions at a very low concentration with a detection limit to down 4.53 × 10−8 M (0.0096 ppm). • A simple filter paper can detect quickly and easily PO 4 3− ions. Phosphate usually plays an important role not only in biological processes but also in environmental pollution, and therefore there is an urgent need for a simple, quick and efficient method to detect phosphate ions. For this design, a new terbium coordination polymer (Tb-CP) has been prepared under hydro-solvothermal conditions using 3,3′-((5-carboxy-1,3-phenylene)bis(oxy))dibenzoic acid (H 3 cpboda) in the existence of Tb(NO 3) 3 ‧6H 2 O. It was studied by infrared spectroscopy (IR), single crystal X-ray diffraction, thermogravimetric analysis (TGA), and fluorescence method. Structurally, the Tb-CP gives a 2D network based on binuclear Tb(III) units. Optically, the Tb-CP is prepared as a colloidal nanoparticle suspension for detecting phosphate in water solution. Namely, the suspensions show intense green emissions gradually disappear with the addition of PO 4 3− ions, indicating that the Tb-CP can rapidly, sensitively and reversibly detect phosphate ions in aqueous solutions. This can be applied in pollutant monitoring with a limit of detection down to 4.53 × 10−8 M (0.0096 ppm). Furthermore, a convenient method is successfully set to observe PO 4 3− ions in applications. [ABSTRACT FROM AUTHOR]

In the structure of the title compound, heptaaqua- 1K³O,2κ²O,3κ²O-(μ3-2,6-bis{[bis(carboxylatomethyl)amino]methyl}-4-chlorophenolato-1κO;2κ4O,O',N,O¹;3κ4 O¹ N', O",-O'")dinickel(II)sodium(I) pentahydrate, [NaNi2(C16H14ClN2O9)(H2O)7]·5H2O or [Ni2(Cl-HXTA)(H2O)4{Na(H2O)3}]·-5H2O, the trinuclear complex unit consists of two distorted NiNO5 octahedra bridged by a phenolate O atom and an NaO4 tetrahedron bridged to one of the Ni octahedra by a carboxylate O atom. There are four intramolecular hydrogen bonds forming four six-membered rings in the complex and the complex molecules are connected to each other by a very complicated hydrogen-bond network. [ABSTRACT FROM AUTHOR]

A new mononuclear europium complex incorporating the (+)‐di‐p‐toluoyl‐d‐tartaric acid (d‐H2DTTA) ligand, namely, catena‐poly[tris{μ2‐3‐carboxy‐2,3‐bis[(4‐methylphenyl)carbonyloxy]propanoato}tris(methanol)europium(III)], [Eu(C20H17O8)3(CH3OH)3]n, (I), has been synthesized and characterized by IR spectroscopy, elemental analysis, powder X‐ray diffraction and single‐crystal X‐ray diffraction analysis. The structure analysis indicates that complex (I) crystallizes in the trigonal space group R3 and exhibits an infinite one‐dimensional chain structure, in which the Eu3+ ion is surrounded by six O atoms from six d‐HDTTA− ligands and three O atoms from three coordinated methanol molecules, thus forming a tricapped trigonal prism geometry. The d‐H2DTTA ligand is partially deprotonated and adopts a μ1,6‐coordination mode via two carboxylate groups to link adjacent Eu3+ ions, affording an infinite one‐dimensional propeller‐shaped coordination polymer chain along the c axis, with an Eu...Eu distance of 7.622 (1) Å. Moreover, C—H...π interactions lead to the formation of helical chains running along the c axis and the whole structure displays a snowflake pattern in the ab plane. The circular dichroism spectrum confirms the chirality of complex (I). The solid‐state photoluminescence properties were also investigated at room temperature and (I) exhibits characteristic red emission bands derived from the Eu3+ ion (CIE 0.63, 0.32), with a reasonably long lifetime of 0.394 ms, indicating effective energy transfer from the ligand to the metal centre. In addition, a magnetic investigation reveals single‐ion magnetic behaviour. The spin‐orbit coupling parameter (λ) between the ground and excited states is fitted to be 360 (2) cm−1 through Zeeman perturbation. Therefore, complex (I) may be regarded as a chiral optical‐magneto bifunctional material. [ABSTRACT FROM AUTHOR]

Abstract In this work, we demonstrate a solvent-assisted structural transformation between two 3D metal-organic frameworks (MOFs) ([Zn 4 ( α -bptc) 2 (H 2 O) 3 ] n ( 1 ) → {[Zn 2 ( α -bptc)(H 2 O) 4 ]·(pra)} n ( 2 )) ( α -H 4 bptc = 2,3,3′,4′-biphenyl tetra-carboxylic acid and pra = pyridin-2-amine) at room temperature by immersing complex 1 in a mother solution. The structural transformation involves not only solvent exchange but also the cleavage and formation of coordination bonds, which is confirmed by infrared spectroscopy, single-crystal X-ray diffraction analysis, powder X-ray diffraction patterns, and thermogravimetric analysis. Structural analyses revealed that significant modifications occurred during the transformation including the changes in lattice parameters, unit cell volume, space group, coordination number, secondary building units, and topological type. In the case of drastic structural transitions, significant changes in properties were also observed. Complex 2 displayed the interesting uptake and release of iodine with the changes in visible color, UV and fluorescence spectra, and fully reversible I2 uptake of 8.5 mg g−1, which further suggested about its future application as iodine absorbing material. Graphical Abstract Irreversible solvent-assisted structural transformation between two 3D Zn(II)-MOFs. Unlabelled Image Highlights • A Zn(II) compound 2 based on α -H 4 bptc is synthesized and fully characterized. • Irreversible solvent-assisted structural transformation between two 3D Zn(II)-MOFs. • The transformation is accomplished by coordination bond cleavage and formation. • Complex 2 displays reversible I 2 uptake with visible color change. [ABSTRACT FROM AUTHOR]

A series of novel similar lanthanide metal–organic frameworks, namely, [Ln2L12L2(4−x−y)L3xL4y]·nH2O (LnMOF-1–13) (LnMOF-1: Ln = La, x = 0.7, y = 1.3, n = 4.7; LnMOF-2: Ln = Ce, x = 0.7, y = 1.3, n = 4.7; LnMOF-3: Ln = Pr, x = 1, y = 1, n = 5; LnMOF-4: Ln = Sm, x = 1, y = 1, n = 2.5; LnMOF-5: Ln = Eu, x = 1, y = 1, n = 3; LnMOF-6: Ln = Tb, x = 0, y = 2, n = 2; LnMOF-7: Ln = Dy, x = 1, y = 1, n = 3; LnMOF-8: Ln = Er, x = 0, y = 1, n = 3; LnMOF-9: Ln = Nd, x = 1.4, y = 1.4, n = 3.6; LnMOF-10: Ln = Gd, x = 1, y = 1, n = 3; LnMOF-11: Ln = Ho, x = 1.6, y = 0, n = 3; LnMOF-12: Ln = La0.44Eu0.10Tb0.46, x = 1, y = 1, n = 7; LnMOF-13: Ln = La0.66Eu0.11Tb0.23, x = 1, y = 1, n = 7; L1 = 5-((4-formylphenoxy)methyl)isophthalic acid anion, L2 = C3H7ON, L3 = H2O, L4 = HCOOH), have been prepared using a solvothermal method and characterized by single crystal and powder X-ray diffraction, IR spectroscopy, elemental analysis and thermogravimetric analysis. All structures are similar and possess a 3D binodal (3,6)-connected net with the point symbol (42·6)2(44·62·87·102). Furthermore, the luminescence measurements indicate that compounds LnMOF-5 and LnMOF-6 display intense characteristic red and yellowish-green emission with quantum yields of 23.30% & 28.25%, respectively. And the three-component La:Eu,Tb-doped compounds exhibit white emission under UV irradiation, especially the compound LnMOF-12 which exhibits the Commission International de l'Eclairage (CIE) chromaticity coordinate (0.332, 0.333) with pure white light emission (Φ = 11.22% at 345 nm). Additionally, the magnetic properties of LnMOF-10 are also investigated. [ABSTRACT FROM AUTHOR]

Four new manganese(ii) metal–organic frameworks based on H4bpta (H4bpta = 3,3′,5,5′-biphenyltetracarboxylic acid) and N-donor ligands, namely [Mn2(4,4′-bipy)(bpta)]n (1), [Mn2(1,4-bib)2(bpta)]n·2n(H2O·DMF) (2), [Mn2(1,3-bimb)2(bpta)]n·2nH2O (3), and [Mn2(1,4-bimb)2(bpta)]n·2nH2O (4) (4,4′-bipy = 4,4′-bipyridine, 1,4-bib = 1,4-bis(imidazol-1-yl)benzene, 1,3-bimb = 1,3-bis((1H-imidazol-1-yl)methyl)benzene, and 1,4-bimb = 1,4-bis((1H-imidazol-1-yl)methyl)benzene), have been obtained under solvothermal conditions. In these complexes, the fully deprotonated bpta4− ligands link binuclear SBUs to construct 2D layers with (4,4)-connected topologies. Complex 1 is a 3D network with 1D zigzag chains built up from 4-connected bpta4− ligands that contain carboxylate groups bridging Mn2+ ions in a rather rare syn–syn geometry. Complex 2 exhibits a 3D porous network with syn–anti bridging dimeric subunits. Complex 3 is a (3,4)-connected 2D novel network with double helix chains formed by cis-1,3-bimb linkers. The structure of complex 4 is similar to that of 2, but it consists of tiny pores due to trans-1,4-bimb linkers. Magnetic studies reveal that 1 is perfectly fitted by the modified Fisher model to yield an effective intrachain antiferromagnetic coupling (J = −2.21(1) cm−1). Complexes 2–4 show antiferromagnetic interactions (J = −1.57(2) cm−1 for 2, and J = −0.68(2) cm−1 for 3) in dimeric units of Mn2(μ-COO)22+ related to double syn–anti and syn–syn carboxylate bridges. An important repetitive feature of all these complexes with syn–anti or syn–syn carboxylate bridges is that the antiferromagnetic coupling is very small. In addition, the gas sorption exploration of 2 exhibits relatively high sorption of CO2 but very low sorption of N2, making it a promising material for CO2/N2 separation. [ABSTRACT FROM AUTHOR]

Careful investigation of the effects of metal ions and pH value resulted in five multi-dimensional metal−organic complexes, [Co 5 ( μ 3 -OH) 2 ( α -bptc) 2 (H 2 O) 6 ] n ( 1 ), {(H 3 O) 2 [Co 4 ( μ 3 -O)( α -bptc) 2 (H 2 O)]·4H 2 O} n ( 2 ), {K 2 [Zn 4 ( μ 3 -OH) 2 ( α -bptc) 2 (H 2 O) 3 ]} n ( 3 ), [Zn 4 ( α -bptc) 2 (H 2 O) 3 ] n ( 4 ), and {[Cd 4 ( α -bptc) 2 (H 2 O) 7 ]·2H 2 O} n ( 5 ) ( α - H 4 bptc = 2,3,3 ' ,4 ' - biphenyl tetracarboxylic acid). The complexes consisted of different highly connected secondary building units (SBUs) assembled via hydrothermal in situ routes. The pH value as well as the kinds of metal ions influenced the coordination modes of α -H 4 bptc and also introduced the hydroxyl ligand at high pH value, resulting in the diversity of SBUs and dimensionality. Variable temperature magnetic measurements indicated the antiferromagnetic behavior in the Co 5 core in 1 , and the intra - chain ferrimagnetic behavior in complex 2 . Moreover, the luminescent properties of the complexes 3 − 5 indicated the existence of intra - ligand charge transfer. [ABSTRACT FROM AUTHOR]

• A novel 1D Cd-coordination polymer is synthesized by solvothermal method. • The CP1 is an excellent luminescence sensor with good water stability, thermal stability and wide pH stability. • The CP1 has strong selectivity for Tb3+, the low detection limit (11.4 nM) and the limit of quantification (37.9 nM). • The CP1 could monitor Tb3+ with the test strips by the naked eyes under the 254 nm UV light. A novel chiral Cd-coordination polymer (CP1) was synthesized by solvothermal reaction with chiral ligand 1,4-bis((L‑serine)methyl)benzene (L-H 2 bsmb) and cadmium oxide, and the structure of CP1 was characterized by single-crystal X-ray diffraction, fourier transform infrared spectoscopy (FT-IR), powder X-ray diffraction (PXRD), thermogravimetric analysis (TGA), elemental analysis (EAs), solid circular dichroism (CD) and fluorescence spectroscopy. One dimensional chain for CP1 was constructed to a chiral 3D structure by intermolecular hydrogen bonds between carboxyl group and coordination water molecules and weak interaction of C‒H•••π. In aqueous system, the fluorescence of CP1 shows excellent stability. Through the detection experiments towards 32 different ions, it was found that CP1 has specific selection for Tb(Ⅲ) ions with the fast response time (within 1 min), low detection limit (11.4 nM), strong anti-interference ability and good recyclability. Fluorescent test strips based on CP1 allow to sense Tb(Ⅲ) ion quickly and easily by naked eyes, which provides an excellent method for monitoring Tb(Ⅲ) in human body and water systems. A novel luminescent CP 1 sensor can distinguish Tb3+ quickly and easily by the naked eye. [Display omitted] [ABSTRACT FROM AUTHOR]

Abstract: One hetero-bimetallic Cu(II)/Cd(II) compound, [CdII(H2O)2][CuII(mal)2(H2O)2] n (1) (H2mal=malonic acid) has been synthesized and characterized using single crystal X-ray crystallography, thermogravimetric (TG) studies and X-ray powder diffraction (XRPD) measurements. The compound crystallizes in orthorhombic Pbcn space group having cell dimensions a =6.6260(12)Å, b =13.958(2)Å and c =13.052(2)Å. The solid state structure of compound 1 demonstrates a 3D pillared layered coordination network generated through the simultaneous bridging as well as chelating mode of malonate towards the Cd(II) and Cu(II), respectively. TG analysis reveals relatively high thermal stability for the compound (decomposition temperature ∼320°C). The thermal study also reveals that the coordinated waters attached to both the metal centers (Cd(II) and Cu(II)) are reversibly lost and gained and this behavior is also corroborated by XRPD studies. [Copyright &y& Elsevier]

One mononuclear penta-coordinated Cu(II) complex, [CuLCl2] · H2O (1), where L is a tridentate ligand H2N–(CH2)2–NC(NH2)–NH–C(NH2)NH [=1-(2-aminoethyl)biguanide], has been synthesized and characterized crystallographically. In an attempt to prepare bis(ethylenediamine)bis(biguanide)Cu(II), it resulted in a different product, [CuLCl2] · H2O (1), where Cu(II) was found to occupy the base of a square pyramid formed by N3Cl2 coordination. The ligand L is believed to be generated in situ in presence of Cu(II), since neither L can be prepared independently nor it can be removed from complex 1. Similar attempts with Ni(II) Co(II), Zn(II), Fe(II) or Fe(III) salts failed, and we conclude that Cu(II) acted as a template for the formation of 1. The solid-state structure of 1 is interesting because one monomeric unit, i.e. [CuLCl2] self-recognizes other monomeric unit centrosymmetrically to form a supramolecular dimer through N–H···Cl hydrogen bonding. The single lattice water molecule played an important role in the formation of 2D supramolecular sheets involving these dimers and become an integral part of such self-assembled structure. The EPR spectrum of complex 1 in the frozen state is consistent with a typical monomeric tetragonal Cu(II) environment. Electrochemical study of 1 in aqueous medium showed an irreversible reductive response at –0.65 V versus SCE, which can be assigned to CuII/CuI redox couple. [Copyright &y& Elsevier]

In the title compound, [MnCl2(C10H8N2)2]·SC(NH2)2, the MnII atom is coordinated by four N atoms from two 2,2′-bipyridyl ligands and two Cl− anions, resulting in a distorted cis-MnCl2N4 octa­hedral geometry. The complexes and thio­urea mol­ecules are connected by N—H⋯Cl and N—H⋯S hydrogen bonds, leading to one-dimensional tapes which are further organized into a three-dimensional structure through π–π, C—H⋯π and C—H⋯Cl inter­actions. [ABSTRACT FROM AUTHOR]