Inorganic Chemistry Communications (v.22, #C)

Contents List (iii-xiv).

Metal-directed assembly of metal(II) benzoates (M = Mn, Ni, Co, Cu, Zn, and Cd) with 1,2-bis(4-pyridyl)ethene: Light- and photo-induced [2 + 2] cycloaddition by Jin Hoon Kim; Jeong Mi Bae; Hong Gyu Lee; Nack Joo Kim; Kwang-Deog Jung; Cheal Kim; Sung-Jin Kim; Youngmee Kim (1-5).
We showed a systematic investigation on the coordination polymers assembled from metal(II) benzoates and bpe ligands. 1-Mn and 5-Zn show ladder-type double chains, 2-Co does a simple linear chain, 3-Ni does a two-dimensional sheet, 4-Cu does a chain containing paddle-wheel dinuclear units, 6-Cd does a thick one-dimensional structure containing newly generated [2 + 2] addition product 4pycb ligands. In addition, light-induced [2 + 2] addition reaction occurs for CdII ions, and C = C double bonds that were aligned for photo-induced [2 + 2] cycloaddition in ZnII ion undergo the photo-induced cycloaddition by UV lamp. Luminescences of compounds 3 and 4 showed strong emissions, while relatively weak luminescences were observed for 1 and 2. Moreover, 4-Cu and 1-Mn have shown efficient catalytic reactivities, while 2-Co, 3-Ni and 6-Cd have displayed a very slow conversion. The reactivities of the compounds used in this study are in the order of 5-Zn > 4-Cu > 1-Mn > 2-Co ≫ 3-Ni > 6-Cd.Four novel MII coordination polymers (M = Mn, Ni, Cu, and Cd) were synthesized, and their structures (including known Co and Zn compounds) were systematically investigated. Moreover, light and photo-induced [2 + 2] cycloaddition is discussed.Display Omitted►The coordination polymers were synthesized from metal(II) benzoates and bpe ligands. ►The light-induced [2 + 2] addition reaction occurs for CdII ions. ►The C=C double bonds in ZnII and MnII compounds were aligned for photo-induced [2 + 2] cycloaddition.
Keywords: 1,2-bis(4-pyridyl)ethene; [2+2] cycloaddition; Coordination polymers; Transesterification;

Two new mixed ligand CoII coordination polymers, [Co(TP)(bpp)(H2O)] n (1) and {[Co43-OH)2(BTC)2(bpp)2(H2O)2]·bpp} n (2) (TP = terephthalate, BTC = 1,2,3-benzenetricarboxylate, bpp = 1,3-bis(4-pyridyl)propane), have been synthesized by hydrothermal reactions of Co(NO3)2·6H2O with bpp and TP2− or BTC3− ligands. They were characterized by single-crystal X-ray diffraction, Thermogravimetric Analysis (TGA), Elemental Analysis (EA) and IR. Single-crystal X-ray diffractions reveal that two complexes feature various metal-carboxylate subunits extended further by bpp ligands to form one-dimensional (1D) to 3D polycatenation or 3D network, respectively. 1 contains a type of 1D zigzag ladders which are further interlocked with the other two vertically identical ones, resulting in a 3D entangled architecture. 2 exhibits a 3D porous and magnetic framework containing the chair-like tetranuclear clusters, and the framework of 2 can be simplified as in 412·63 topology with 6-connected [Co43–OH)2]6+ cluster as node. TGA for 1 and 2, magnetic properties for 2 are also discussed.The hydrothermal reaction of Co(II) nitrate, flexible 1,3-bis(4-pyridyl)propane with terephthalate resulted in a 1D ladder → 3D polycatenated coordination polymer. The self-assembly of Co(II) nitrate, 1,3-bis(4-pyridyl)propane with 1, 2, 3-benzenetricarboxylate resulted in a 3D porous and magnetic framework in 412·63 topology with the chair-like [Co43–OH)2]6+ cluster as node.Display Omitted► Two novel CoII coordination polymers were prepared. ► A 3D polycatenation containing interlocked 1D ladder. ► A porous and magnetic polymer with tetranuclear clusters in 412·63 topology.
Keywords: Coordination polymer; Polycatenation network; Tetranuclear cluster;

Two chiral complexes, [Cu(L1)(L2)H2O]·3H2O (1) and [Ni(L1)(SCN)(H2O)2]·2H2O (2) (HL1 = L-histidine, HL2 = L-alanine), have been synthesized through slow evaporation of solvent and characterized by single-crystal X-ray diffraction, IR, powder X-ray diffraction, element analysis and circular dichroism measurements. Complexes 1 and 2 crystallize in the monoclinic system with chiral space group P21, respectively. Interestingly, magnetic and ferroelectric studies reveal that complexes 1 and 2 demonstrate ferromagnetic and ferroelectric properties.Two chiral complexes constructed from mixed L-histidine and L-alanine or thiocyanate ligands have been synthesized through slow evaporation of solvent. Magnetic and ferroelectric studies reveal that complexes 1 and 2 demonstrate ferromagnetic and ferroelectric double functions in aspect of multiferroic complexes.Display Omitted► Two chiral complexes have been synthesized through slow evaporation of solvent. ► The two complexes crystallize in the monoclinic system with chiral space group P21, respectively. ► Both ferromagnetic and ferroelectric behaviors were observed.
Keywords: Chiral complexes; Circular dichroism; Ferromagnetic property; Ferroelectric property;

A copper(II) compound ([LCu(μ-OH)CuL(H2O)]ClO4)n (1) [where HL  =  2-[(2-dimethylamino-ethylimino)-methyl]-4-nitro-phenol, is a well known Schiff base], has been synthesized and characterized by elemental analysis, IR and UV–Vis spectroscopy and single-crystal X-ray diffraction studies. The compound features a copper(II) polymeric coordination network composed of binuclear species [LCu(μ-OH)CuL(H2O)]+ as building blocks. It crystallizes in monoclinic space group P2 1 /c with cell dimensions a = 22.1453(9), b = 7.8314(3), c = 18.5626(8) and β=108.509(3). The potentially tridentate Schiff base shows a tetra-dentate bonding mode for the 1st time.A copper(II) compound, ([LCu(μ-OH)CuL(H2O)]ClO4)n (1) [where HL  =  2-[(2-dimethylamino-ethylimino)-methyl]-4-nitro-phenol, has been synthesized and its molecular structure has been elucidated on the basis of X-ray crystallography. The compound features a copper(II) polymeric coordination network composed of binuclear species [LCu(μ-OH)CuL(H2O)]+ as building blocks. This dinclear species undergoes polymerization utilizing the nitro functionality of the Schiff base.Display Omitted►A copper(II) polymer containing peripheral nitro oxygen bridge and μ-OH core ►Structural elucidation on the basis of X-ray crystallography ►A potential tridentate Schiff base in a tetra-dentate binding mode
Keywords: Copper(II); Polymer; Schiff base; μ-OH; Crystal structure;

Synthesis, magnetism and quantum Monte Carlo studies of two Cu(II)-based ferromagnetic coordination polymers by Gui-lin Zhuang; Wen-xian Chen; Jun Zheng; Wu-lin Chen; Jian-guo Wang (18-21).
Two Cu(II)-based coordination polymers, {Cu(CMBA)(H2O)}n (1) and {Cu(CMBA)(4, 4′-bpy)0.5(H2O)}n (2) (H2CMBA = 2-(Carboxymethyl-amino)-3-methyl-butyric acid, 4, 4′-bpy = 4, 4′-bipyridine), were obtained under microwave irradiation. Magnetic property measurements indicate that both of them feature ferromagnetic characteristic. Furthermore, quantum Monte Carlo studies respectively reveal that the coupling parameters between the adjacent Cu(II) ions are 8.20 cm− 1 for 1 and 3.60 cm− 1 for 2, respectively. Moreover, it is found that 4, 4′-bpy ligand serves as a weak antiferromagnetic propagation pathway with − 0.36 cm− 1 between two adjacent Cu(II) chains in 2, resulting in the differences of magnetization between 1 and 2.Two Cu(II)-based coordination polymers prepared under microwave irradiation reveal ferromagnetic propagation of 8.20 cm− 1 for 1 and 3.60 cm− 1 for 2 by quantum Monte Carlo method.Display Omitted► Two Cu(II) based coordination polymers of H2CMBA ligand were obtained. ► Magnetic measure exhibits that they feature ferromagnetic properties. ► Quantum Monte Carlo studies reveal the coupling parameters of two Cu(II) ions. ► 4, 4′-bpy ligand exhibits weak antiferromagnetic interaction with − 0.36 cm− 1.
Keywords: Coordination polymer; Magnetism; Quantum Monte Carlo;

A three-dimensional heterometallic MnIICuII azide-bridged coordination polymer: Synthesis, structure, and magnetic properties by Zhi-Guo Gu; Wen Zhou; Fei-Fei Bao; Chun-Yan Pang; Xin-Xin Xu; Zaijun Li (22-25).
A new three-dimensional heterometallic MnIICuII azide-bridged coordination polymer, [Mn2Cu(N3)6(en)2] n (1), was synthesized by assembling MnII, CuII, azide, and ethylenediamine in solution condition. The 3D structure of 1 can be described as end-on (EO) azide-bridged Mn2Cu trinuclear units linked by end-to-end (EE) azide bridges. Magnetic analysis of 1 indicates that the EO- and EE-azide bridges mediate the ferromagnetic and antiferromagnetic exchange interactions, respectively, with the antiferromagnetic coupling dominating the magnetic properties.A new three-dimensional heterometallic MnIICuII azide-bridged coordination polymer, [Mn2Cu(N3)6(en)2] n (1) has been synthesized and structurally characterized. Magnetic measurements indicate antiferromagnetic coupling dominating the magnetic properties of 1.Display Omitted► Three-dimensional heterometallic MnIICuII azide-bridged coordination polymer. ► Mn2Cu trinuclear units linked by end-to-end azide bridges. ► Antiferromagnetic coupling dominating the magnetic properties.
Keywords: Heterometallic; Azide-bridged; Three-dimensional; Magnetic properties;

A rare homochiral lanthanium(III)-camphorate coordination polymer with 4-connected sql topology by Zhi-Qiang Jiang; Gui-Yuan Jiang; Zhen Zhao; Duan-Chuan Hou; Min Zou; Yao Kang (26-28).
A rare two-dimensional (2D) La(III) chiral hybrid organic–inorganic coordination polymer [La2(D-cam)2(CH3COO)2(DMA)4] (1 D-H2cam = D-camphoric acid; DMA = N,N-dimethylacetamide) based on paddle-wheel subunit has been solvothermally prepared and structurally characterized by single-crystal X-ray diffraction. Compound 1 exhibits a rare low-connected layered structure with sql topology, and further stacking of layers leads to a 3D supramolecular framework. The thermogravimetric behavior and chiral nature of 1 have been also investigated. The solid-state circular dichroism(CD) measurements with the Cotton effects at λmax  = 280 nm apparently show that the bulk sample of 1 is homochiral.Presented here is a novel two-dimensional (2D) La(III) coordination polymer constructed from paddle-wheel subunits, which exhibits a rare layered structure with sql topology and homochiral environment.Display Omitted► A novel two-dimensional (2D) La(III) coordination polymer constructed from paddle-wheel subunits ► A rare layered structure with 4-connected sql topology ► The bulk sample of 1 possessing homochiral environment
Keywords: Lanthanium; Solvothermal synthesis; Coordination polymer; Chirality; Cotton effect;

The first hybrid Bi(III) supramolecular compound based on organic ammonium and 18-crown-6, [(4-FBNH3)3·(18-crown-6)3·(Bi2Cl9)] (1), has been synthesized and characterized by single crystal X-ray diffraction, elemental analysis, IR, XRPD and 1H NMR (4-FBNH3  = 4-fluorobenzenaminium). The Bi(III) centers were chelated through three μ 2-Cl donors to form a macro-anion (Bi2Cl9)3− unit. And the rotator-stator assembly, [(4-FBNH3)·(18-crown-6)]+, was formed by the 4-FBNH3 + cation inserting into the crown ether through strong N―H…O H-bonding interactions. The large anions and rotator-stator cations were alternately stacked together to build the supramolecular functional compound. In addition, the thermal analysis and luminescent properties were investigated.The first hybrid Bi(III) supramolecular compound based on macrocycle has been synthesized and characterized by single crystal X-ray diffraction, elemental analysis, IR, XRD, 1H NMR, DSC and fluorescence properties. The Bi(III) centers were chelated through three μ 2-Cl donors to form a macro-anion (Bi2Cl9)3− unit. And the rotator-stator assembly, [(4-FBNH3)•(18-crown-6)]+, was formed by the cations inserting into the crown ether through strong N―H…O H-bonding interactions. The large anions and rotator-stator cations were alternately stacked together.Display Omitted► The first hybrid Bi(III) supramolecular compound based on macrocyclic rotator-stator assembly. ► The rotator-stator assemblies were formed by the cations inserting into the crown ether. ► The Bi(III) centers were chelated through three μ 2-Cl donors to form a macro-anion (Bi2Cl9)3− unit.
Keywords: Bi(III) complex; Crystal structure; Fluorescence; Rotator-stator assembly; Macrocycle;

Synthesis, structure and catalytic activity of dicarbene dipalladium complexes with different substituents by Long Yang; Jianfeng Zhao; Yunfei Li; Kaiqi Ge; Yongzhong Zhuang; Changsheng Cao; Yanhui Shi (33-36).
A series of ethylene bridged di-NHC dipalladium complexes (15) with different substituents on N of imidazolydene were prepared. The influence of the different substituents on the structure and catalytic reactivity of the complexes were studied. The molecular structures of 3 and 4 were determined by X-ray diffraction studies. The structures of complexes consist of two perpendicular pseudo-square-planar subunits in a cis configuration. The catalytic activity of the new binuclear palladium complexes was successfully tested in the Mizoroki–Heck reaction. The complexes with aryl substituent have better activity than that with alkyl substituent, meanwhile, the different substituents on phenyl group have a little effect on both regioselectivity and the yield of the product as well.Novel di-NHC dipalladium complexes with different N-substituted imidazolylidenes have been synthesized. Two molecular structures have been determined. The complexes with aryl substituents on N of NHC showed good catalytic activity for the arylation of olefinsDisplay Omitted► Novel di-NHC dipalladium complexes with different N-substituted imidazolylidenes have been synthesized. ► Two molecular structures have been determined. ► The two palladium subunits are in cis configuration. ► π–π Stacking plays an important role in the configuration of the palladium subunits. ► The complexes with aryl substituents on N of NHC showed good catalytic activity for the arylation of olefins.
Keywords: Dipalladium; N-heterocyclic carbene; Ethylene bridge; Different substituent; Mizoroki–Heck reaction;

A new heptanuclear compound [{Cu(TPA)CN}6W(CN)2][ClO4]8·14H2O (1) (TPA = tris(2-pyridylmethyl)amine) was synthesized by the reaction of [Cu(TPA)]2 + unit and K4W(CN)8. The cyanometalate core is encapsulated by mononuclear copper moieties via cyano bridges. 1 crystallizes in monoclinic space group P21/c with a = 22.01(2) Å, b = 26.87(3) Å, c = 31.64(2) Å, β  = 128.87(2)°, and Z  = 4. Variable temperature magnetic measurements have demonstrated that very weak ferromagnetic interaction between the nearest paramagnetic CuII centers is exhibited. Thus weak ferromagnetic coupling might be transferred by ―NC―W―CN― bridging units.A new heptanuclear compound with octacyanometalates was synthesized. Variable temperature magnetic measurements have demonstrated that very weak ferromagnetic interaction between the nearest paramagnetic CuII centers is exhibited.Display Omitted► One new hepta-bimetallic complex containing octacyanotungstate(IV) has been synthesized. ► Very weak intercluster ferromagnetic coupling between the nearest paramagnetic Cu(II) ions is exhibited. ► Thus weak coupling might be mediated through the ―NC―W―CN― bridging units.
Keywords: Heptanuclear compound; Cyanide; Ferromagnetic interaction; Octacyanotungstate;

A new hetero-tetranuclear complex [MnIII 2NiII 2(HL)2L2(OAc)2(CH3OH)2]CH3OH (1) has been synthesized and fully characterized, where H2L is N-(2-hydroxy-5-fluro-methylphenyl)-3-imine-2-propanol. The X-ray diffraction analysis of 1 shows that four metal ions as well as coordinated O atoms in one molecular unit exhibit a dicubane-like core with two missing vertexes. The extension of the magnetic exchange in 1 has been evaluated by means of a spin Hamiltonian, yielding the parameters of J1  = − 11.85 cm− 1, J2  = − 6.44 cm− 1 and J3  = 0.34 cm− 1, D = 2.26 cm− 1 and g = 2.12, assumed under same anisotropy D and g. And the DNA cleavage ability of 1 was also investigated.The hetero-tetranuclear Mn2 IIINi2 II complex has an overall antiferromagnetic behavior as well as effective DNA cleavage activity even in low concentration.The Mn2 IIINi2 II complex has an overall antiferromagnetic behavior.Display Omitted► A new MnIII 2NiII 2 core complex has been characterized. ► Magnetic measurements reveal antiferromagnetic interactions among the metal ions. ► The complex has effective DNA cleavage activity.
Keywords: Hetero-tetranuclear complex; Magnetic property; Crystal structure; DNA cleavage;

A two-fold interpenetrating metal-organic framework based on tetranuclear zinc-carboxylate clusters by Xiu Zhang; Guangchao Ma; Fanzhen Kong; Zhangyu Yu; Ruihu Wang (44-47).
A novel two-fold interpenetrating 3D framework consisting of unprecedented tetranuclear Zn(II)-carboxylate units has been synthesized. The tripodal semi-rigid tricarboxylate ligand and 4,4-bipy link the tetranuclear units into a 3,8-connected tfz-d topological network.A two-fold interpenetrating 3,8-connected tfz-d topological network consisting of novel tetranuclear Zn(II)-carboxylate units has been synthesized using the tripodal semi-rigid tricarboxylate ligand and 4,4-bipy.Display Omitted► The tripodal semi-rigid tricarboxylate ligand is used for the construction of MOFs. ► The coordination polymer consists of unprecedented tetranuclear Zn(II)-carboxylate units. ► A 3,8-connected tfz-d topology is exhibited.
Keywords: Coordination polymer; Crystal structure; Fluorescence; Zn(II);

Core protonation of a series of meso-tetraarylporphyrins (aryl = phenyl, 4-chlorophenyl and 4-methoxyphenyl) with weak and strong carboxylic acids was studied by cyclic voltammetry and UV–vis absorption spectroscopy. Positive shifts of the first and second oxidation and reduction potentials, observed upon protonation of the porphyrins are in close agreement to the observed red shifts of the Q(0,0) bands in the UV–vis spectra and give evidence for the stabilization of the eg (LUMO) and a2u (HOMO) orbitals. Significantly larger positive shifts of the reduction potentials (0.622–0.892 V and 0.527–0.913 V for ΔE1 and ΔE2, respectively) compared to the oxidation ones (0.06–0.397 V and 0.085–0.166 V for ΔE1 and ΔE2, respectively) indicate much greater stabilization of the LUMOs compared to the HOMOs upon diprotonation of the porphyrins. Also, larger red shifts of the Soret bands relative to the Q(0,0) bands (ΔνSoret/ΔνQ(0,0)  = 1.61–6.32) for the used porphyrins are more in accordance with destabilization of the a1u orbital upon the reaction.Diprotonation of meso-tetraarylporphyrin with protic acids is associated with positive shifts of the reduction and oxidation potentials which in combination with the red shifts of the Soret and Q(0,0) bands give convincing evidence for the stabilization of the a2u and eg orbitals and destabilization of the a1u ones.Display Omitted► Effects of core protonation on the oxidation and reduction potentials of porphyrins. ► Significantly larger shifts of the reduction potentials compared to the oxidation ones. ► Close correlation between the electrochemical and spectrophotometric shifts.
Keywords: Porphyrin protonation; Absorption bands shift; Cyclic voltammetry; Oxidation potentials; Reduction potentials;

Exploring the mechanism of in situ formation of oxalic acid for producing mixed fumarato-oxalato lanthanide (Eu, Tb and Gd) frameworks by Cristiane K. Oliveira; Juliano R. de Menezes Vicenti; Robert A. Burrow; Severino Alves; Ricardo L. Longo; Ivani Malvestiti (54-59).
Mixed fumarato-oxalato ligands lanthanide metal-organic frameworks (MOFs) [Ln2(fum)2(ox)(H2O)4]⋅4H2O (Ln = Eu, Gd, and Tb) were obtained from hydrothermal treatment of aqueous acid solutions of trivalent lanthanide ions and fumaric acid with nitrate or sodium hypochlorite as oxidants. The crystal structure for [Gd2(fum)2(ox)(H2O)4]⋅4H2O was determined. Other oxidants (H2O2 and NaSO4) or conditions (NaOCl at room temperature and atmospheric pressure) yielded other MOFs or products. Oxalic acid was formed in situ and mechanisms based on the hydration of fumaric acid mediated by Ln3+ followed by oxidation and decarboxylation steps were proposed. The mechanisms were able explain the dual role of Ln3+ ions and the nature of the oxidant in forming the frameworks.Hydrothermal synthesis of mixed ligands [Ln2(fum)2(ox)(H2O)4]⋅4H2O (Ln = Eu, Gd, and Tb) MOFs. The in situ mechanisms for oxalic acid formation are proposed and show the dual roles of Ln3+ and relevance of choosing adequate oxidant.Display Omitted► First mechanistic study of in situ oxalate formation from fumaric acid. ► Formation of mixed ligand fumarato-oxalato lanthanide MOFs. ► Hydrothermal synthesis of lanthanide based coordination polymers.
Keywords: In situ reaction; Hydrothermal treatment; Lanthanide; MOF; Reaction mechanism;

Squarato-metal(II) complexes: Part 5 † For part 4 see reference 2a. . Polynuclear copper(II) complexes bridged by squarate and croconate dianions by Febee R. Louka; Alivia D. Stewart; Eric Regel; Franz A. Mautner; Serhiy Demeshko; Franc Meyer; Salah S. Massoud (60-64).
Two polynuclear Cu(II) complexes namely 1-D polymeric {[Cu(DPA)(μ1,2-C4O4)(H2O)]∙2H2O}n (1) and the tetranuclear {[Cu2(DPA)2(μ-1,1,2,3-C5O5)(H2O)](ClO4)2∙ H2O}2 (2) where DPA = bis(2-pyridylmethyl)amine, C4O4 2−  = squarate dianion, and C5O5 2−  = croconate dianion were synthesized and structurally characterized by X-ray crystallography. The C4O4 2− and C5O5 2− dianions are bridging the Cu2+ centers via a μ-1,2-bis(monodentate) and μ-1,2,3-bis(bidentate)-μ-1-(monodentate) bonding modes in complexes 1 and 2, respectively. A new coordination bonding mode is reported for the bridged croconate in the later complex. Hydrogen bonds stabilize the supramolecular 2D and 3D systems in the complexes. Magnetic susceptibility measurements for the 1D-polymeric complex 1 reveal insignificant coupling between the Cu(II) ions, whereas the tetranuclear croconato complex 2 exhibits moderate antiferromagnetic coupling between the central Cu(II) ions (J  = − 9.4 cm–1) and weak antiferromagnetic coupling between the terminal Cu(II) ions (J  = − 5.1 cm–1).Two bridged squarato- and croconato-Cu(II) complexes 1-D polymeric {[Cu(DPA)(μ1,2-C4O4)(H2O)]∙2H2O}n and the tetranuclear {[Cu2(DPA)2(μ1,1,2,3-C5O5)(H2O)](ClO4)2∙ H2O}2 were synthesized. The croconato complex adopts a new binding mode. The two compounds were structurally and magnetic characterized.Display Omitted► Structural characterization of 1-D polymeric {[Cu(DPA)(μ1,2-C4O4)(H2O)]∙2H2O}n. ► Structural characterization of tetranuclear {[Cu2(DPA)2(μ1,1,2,3-C5O5)(H2O)](ClO4)2∙ H2O}2. ► New coordination bonding mode for the bridged croconate ligand. ► Magnetic properties of bridging squarato- and croconato-copper(II) complexes.
Keywords: Copper; Polynuclear complexes; Bridged squarate; Bridged croconate; Crystal structure; Magnetic properties;

Biologically inspired phosphino platinum complexes by Avijita Jain; Monte L. Helm; John C. Linehan; Daniel L. DuBois; Wendy J. Shaw (65-67).
Platinum complexes containing phosphino amino acid and amino acid ester ligands, built upon the PPhNR′ 2 platform, have been synthesized and characterized (PPhNR′ 2 = [1,3-diaza]-5-phenyl phosphacyclohexane), R' = Gly (glycine) or Gly-ester (glycine ethyl ester). These complexes were characterized by 31P, 13C, 1H, 195Pt NMR spectroscopy, and mass spectrometry. The X-ray crystal structure of one of the complexes, [PtCl2(PPhNGly-ester 2)2], is reported, confirming cis-square planar geometry about the platinum. These complexes provide a foundation upon which larger peptides can be attached, to allow the introduction of enzyme-like features onto small molecular catalysts.A series of biologically inspired Pt amino acid complexes have been prepared and characterized by 1H, 13P, 195Pt and 13C NMR spectroscopy and X-ray crystallography. These complexes have potential applications in water soluble and chiral chemistry, as well as providing a foundation for attaching enzyme-like features onto small molecule catalysts.Display Omitted► Four amino acid containing platinum phosphine complexes were synthesized. ► Complex characterization includes 31P, 195Pt, 1H and 13C NMR and mass spec. ► The X-ray crystal structure of cis-[PtCl2(PPhNGly-ester 2)2] is reported.
Keywords: Amino acid complexes; Bioinspired complexes; Bioinorganic ligands;

Syntheses, crystal structures and anticancer activities of three novel transition metal complexes with Schiff base derived from 2-acetylpyridine and l-tryptophan by Nan Zhang; Yu-hua Fan; Zhen Zhang; Jian Zuo; Peng-fei Zhang; Qiang Wang; Shan-bin Liu; Cai-feng Bi (68-72).
Three novel transition metal coordination complexes, Cu(C18H16N3O2)2·2CH3OH (1), Zn(C18H16N3O2)2·2CH3CH2OH (2) and Cd(C18H16N3O2)2·2CH3OH (3) (C18H16N3O2: 2-acetylpyridine-L-tryptophan) have been synthesized and characterized by IR, UV, elemental analysis, 1H NMR and X-ray diffraction single crystal analysis. The three crystals crystallize in the tetragonal crystal system, space group P43212. They are all six-coordinated by two nitrogen atoms from C=N, two nitrogen atoms from pyridine rings and two carboxylic oxygen atoms in different ligands, forming a distorted octahedron geometry. Each ligand serves as a bridging ligand to link metal ions through carboxylic oxygen atoms, leading to a three-dimensional coordination polymer. The anticancer activities of these three complexes on MDA-MB-231 breast cancer cells were also investigated. The results indicate that all of the three complexes can inhibit the cellular proliferation. Furthermore, Cd(C18H16N3O2)2·2CH3OH (3) has the highest anti-proliferative activity among the three complexes. In addition, Cd(C18H16N3O2)2·2CH3OH (3) can inhibit proteasomal chymotrypsin-like activity and also can induce apoptosis on human breast cancer MDA-MB-231 cells.Cellular morphological changes of MDA-MB-231 cells treated with Cd(C18H16N3O2)2·2CH3OH (3) for 24 h.Display Omitted►Cu(II), Zn(II) and Cd(II) coordination polymers with Schiff bases were synthesized. ►The crystal structures of the three coordination polymers were determined. ►The anticancer activity of the Cd(II) coordination polymer was studied.
Keywords: l-tryptophan; 2-acetylpyridine; Schiff base; Crystal structure; Anticancer activity;

A complex of composition [CuI 4CuII(mtpo)4(H2O)2Cl2]n (1) was synthesized from reaction of Hmtpo (Hmtpo = 5-methyl-[l,2,4]-triazolo-[l,5-a]-pyrimidin-7-o1) with one equivalent of CuCl2·2H2O in water at 100 °C under autogenous pressure. Complex 1 was fully characterized by X-ray single crystal diffraction, elemental analysis and IR spectroscopy. X-ray analysis reveals that complex 1 is a mixed-valence coordination polymer and displays 1-D chain structure. Compound 1 was able to heterogeneously catalyze the ketalization reaction of 2-butanone and ethylene glycol to afford 2-ethyl-2-methyl-[1,3]-dioxolane in excellent yield under mild conditions.A mixed-valence 1-D polymeric chain complex [CuI 4CuII(mtpo)4(H2O)2Cl2]n (1) was synthesized and characterized. Compound 1 was able to catalyze the ketalization reaction of 2-butanone and ethylene glycol.Display Omitted► A mixed-valence 1-D polymeric chain complex was prepared. ► The structure of the complex was determined by X-ray analysis. ► The complex was able to catalyze the ketalization reaction.
Keywords: Mixed-valence complex; 1-D chain; Solvothermal synthesis; Catalytic activity;

To investigate the effect of positional isomerism of ligands on the construction of coordination polymers, three Cd(II) complexes with tripyridyltriazole tectons and thiocyanate anions have been prepared and characterized, namely, [Cd(L 4 )(μ-SCN)(SCN)] n (1), [Cd(L 5 )(SCN)2] n (2), and [Cd(L 6 )(μ-SCN)2] n (3) (L 4  = 3,4-bis(2-pyridyl)-5-(3-pyridyl)-1,2,4-triazole, L 5  = 3-(2-pyridyl)-4,5-bis(3-pyridyl)-1,2,4-triazole, and L 6  = 3-(2-pyridyl)-4-(4-pyridyl)-5-(3-pyridyl)-1,2,4-triazole. Crystal structure analysis indicates that the isomeric effect of ligands plays a crucial role in regulating the distinct 1D coordination patterns for 13, with the aid of the versatility of thiocyanate anion. The solid-state properties such as thermal stability and fluorescence of 13 have also been studied.This work presents the syntheses, crystal structures, and thermal and fluorescent properties of three distinct 1D Cd(II) coordination polymers based on a series of isomeric tripyridyltriazole tectons and thiocyanate anions.Display Omitted► Three Cd(II) thiocyanate coordination polymers have been synthesized and characterized. ► The isomeric tripyridyltriazole ligands therein show different binding modes. ► The distinct 1D coordination assemblies are determined by positional isomerism of the ligands.
Keywords: Cd(II) complexes; 1D Coordination polymers; Tripyridyltriazole tectons; Positional isomerism of ligands; Thiocyanate anion;

By hydrothermal reactions of Zn(II) nitrate with N-(4-carboxyl)benzyl-l-alanine acid (H2L), a novel Zn(II) complex, namely, [Zn(HL)2(H2O)2] (1), have been obtained. Single crystal X-ray diffraction analysis reveals that complex 1 crystallizes in the C2 space group and displays a 0D dimensional structure. The Zn(II) ions are four-coordinated and each Zn(II) ion coordinated with two HL anions forming a [Zn(HL)2(H2O)2] unit. The stacking of such units by hydrogen bonds results in its supramolecular structure. Complex 1 shows a second harmonic generation response that is ~ 1.5 times that of KDP (KH2PO4).By hydrothermal reactions, a novel Zn(II) complex, namely, [Zn(HL)2(H2O)2] (H2L = N-(4-carboxyl)benzyl-L-alanine acid), have been obtained. Single crystal X-ray diffraction analysis reveals that it crystallizes in the C2 space group and displays a 0D dimensional structure. It shows a second harmonic generation response that is ~ 1.5 times that of KDP.Display Omitted► A novel Zn(II) complex base on the reduced Schiff-base ligand have been obtained. ► It crystallizes in the noncentrosymmetric C2 space group. ► It shows a second harmonic generation response that is ~ 1.5 times that of KDP. ► It would be candidates for potential photoactive materials.
Keywords: Hydrothermal synthesis; Reduced Schiff base; Second harmonic generation; Crystal structure;

Synthesis, crystal structures and competitive binding property of a family of functionalized calix[4]arene ionophores by Vallu Ramakrishna; Subrata Patra; E. Suresh; Anjani K. Bhatt; Pragnya A. Bhatt; Amjad Hussain; Parimal Paul (85-89).
A family of calix-crown hybrid molecules incorporating crown-4, crown-5 and crown-6 moieties as ionophore has been synthesized to evaluate their competitive complexing and extracting ability towards different alkali and alkaline earth metal ions. Selectivity of these ionophores towards Li+, Na+, K+, Ca2+, Mg2+ and Sr2+ has been evaluated with aqueous solution containing equimolar mixture of these ions. The concentration of metal ion in the extract (organic phase) has been estimated by ion chromatographic assay. Two of the ionophores show strong complexation with Na+ and K+, whereas the third ionophore exhibits no complexation with any metal ions used in this study. Association constants (K a) for the binding of Na+ and K+ with two of these ionophores have been determined spectrophotometrically. Molecular structures of the Na+ and K+ complexes of these ionophores have been established by single crystal X-ray study. 1H NMR study of the ionophores and their complexes has also been carried out to investigate conformational behavior of the ionophores and their metal complexes in solution. Results have been discussed in light of various factors contribute to determine ion-selectivity.Competitive complexing ability of a number of calix-crown hybrid molecules has been studied using a series of alkali and alkaline earth metal ions in aqueous media; selectivity and binding constants have evaluated and the molecular structures of the complexes formed have been determined by single crystal X-ray study.Display Omitted► A family of calix-crown hybrid molecules as chemo sensor has been synthesized. ► Competitive complexing ability of these ionophores has been evaluated. ► Selectivity has been determined by estimation of metal ions in the extract. ► X-ray structures of the complexes formed have been determined. ► It reveals that the size-matching factor plays predominant role in ion-selectivity.
Keywords: Calixarenes; Ion-selectivity; Crystal structure; Binding constant; Two-phase extraction;

[Ru(tpy)(H4bbdip)]2+ as an anion-selective colorimetric sensor by Ling-Min Pei; Qi-Tian Lin; Hui Chao; Liang-Nian Ji (90-92).
A new ruthenium(II) polypyridyl complex [Ru(tpy)(H4bbdip)]2+ (1) (tpy = terpyridine, H4bbdip = 2,6-bis(benzo[1,2-d:4,5-d′]diimidazole-2′-yl)pyridine) was developed as an optical sensor with selective colorimetric responses toward F and OAc over other tested anions (Cl, Br, I, NO3 , HSO4 , H2PO4 ).A new ruthenium(II) polypyridyl complex [Ru(tpy)(H4bbdip)]2+ (1) was developed as an optical sensor with selective colorimetric responses toward F and OAc over other tested anions (Cl, Br, I, NO3 , HSO4 , H2PO4 ).Display Omitted► Synthesis of a new ruthenium(II) polypyridyl complexes [Ru(tpy)(H4bbdip)]2+. ► [Ru(tpy)(H4bbdip)]2+ was developed as a colorimetric sensor for F and OAc. ► UV-vis and 1H NMR titrations were performed to investigate the interaction between anions and Ru(II) complex.
Keywords: Ruthenium(II) polypyridyl complex; Colorimetric; Sensor; Anion;

Assembly of two new Mn(II) coordination polymers based on 5-aminoisophthalate: Structural diversity and properties by Xia Yin; Tian-Tian Xiao; Jun Fan; Sheng-Run Zheng; Ning Wang; Song-Liang Cai; Jing-Bo Tan; Wei-Guang Zhang (93-97).
Two new Mn(II) coordination polymers, namely, [Mn(Haip)2(H2O)2] (1), and [Mn2(aip)2(bpy)]·3H2O (2) were obtained under hydrothermal conditions (aip = 5-aminoisophthalate; bpy = 2, 2′-bipyridine). Compound 1 features a 1D loop-like chain structure, and complex 2 possesses an interesting (3, 5)-connected 2-nodal 3D architecture with the Schläfli symbol of (4.62)(4.67.82), which is constructed from helical chains. Coordination modes of H2aip molecules and coligands have significant effect on the structures of the resulting complexes. Moreover, variable-temperature magnetic susceptibility measurement of complex 2 exhibits antiferromagnetic interactions between nearest Mn(II) ions with J  = − 0.88(5) cm− 1 and g = 2.04(3).Two complexes possess a 1D chain and a (3, 5)-connected 2-nodal 3D architecture, respectively. Variable-temperature magnetic susceptibility measurement of compound 2 shows antiferromagnetic interactions between nearest Mn(II) ions.Display Omitted► Two complexes with different topologies are obtained via hydrothermal reactions. ► Complex 2 was constructed by connection of dinuclear Mn(II) building blocks. ► Coligand and coordination modes of aip affected on structures of two complexes. ► Complex 2 exhibits antiferromagnetic interactions between nearest Mn(II) ions.
Keywords: 5-aminoisophthalate; Mn(II) coordination networks; Synthesis; Crystal structure; Magnetism property;

Hydrolytically stable Schiff base as highly sensitive aluminium sensor by Soham Samanta; Bhaskar Nath; Jubaraj B. Baruah (98-100).
A highly fluorescence sensitive sensor for selective detection of aluminium (III) and also to differentiate isomeric acids or two isomers of receptors are presented.Highly sensitive aluminium ion sensing by specific Schiff bases are observed. The fluorescence emissions at neutral condition with less interference with essential elements are advantageous over existing ones.Display Omitted► Hydrolytically stable Schiff base for sensor for aluminium detection is presented. ► Sensor is effective in presence of other ions like Fe3+, Zn2+ and Cu2+. ► The use of these sensors to distinguish fumeric acid from maleic acid is shown.
Keywords: Schiff base; Aluminium sensor; Hydrolysis;

A novel coordination polymer [H2N(CH3)2]2[Cd2(L)2(SO4)]∙DMF (1) (L  = 6-mercapto-3-pyridinecarboxylate) has been prepared by the solvothermal reaction of CdSO4 and 6,6′-dithiodinicotinic acid in DMF, in which 6,6′-dithiodinicotinic acid was in situ reduced to L. Single crystal X-ray diffraction reveals that 1 displays a 3D porous framework with [H2N(CH3)2]+ cations derived from the hydrolyzed DMF molecules. Further topological analysis reveals an unusual (3,4)-connected (4.82)2(42.82.102)(8.102) net of 1, which is the first metal–organic replica of sqc1121 network.A novel coordination polymer [H2N(CH3)2]2[Cd2(L)2(SO4)]∙DMF (1) (L  = 6-mercapto-3-pyridinecarboxylate) has been prepared by in situ synthesis from the S―S cleavage of 6,6′-dithiodinicotinic acid. Significantly, complex 1 is the first MOF paradigm of sqc1121 net with (4 ⋅ 82)2(42  ⋅ 82  ⋅ 102)(8 ⋅ 102) topology.Display Omitted► An unusual MOF replica of sqc1121 net with (4 ⋅ 82)2(42  ⋅ 82  ⋅ 102)(8 ⋅ 102) topology ► An in situ ligand synthesis paradigm of S―S bond cleavage ► Offering effective means for constructing unique coordination networks
Keywords: In situ ligand synthesis; Crystal/topology structure; Properties;

Slow magnetic relaxation in one dimensional nitronyl nitroxide-Dy(III) chain suggesting single-chain magnet behavior by Ruina Liu; Chuanxi Xiong; Sanping Zhao; Jing Wu; Qiong Li; Dong Fang (104-107).
Two new nitronyl nitroxide bridged one-dimensional lanthanide complexes [Dy(hfac)3(NIT-2thien)]n (1); [Dy(hfac)3(NIT-3Brthien)]n (2) (hfac = hexafluoroacetylacetonate; NIT-2thien = 2-(2′-thienyl)-4,4,5,5-tetramethyl-imidazoline-1-oxyl-3-oxide; NIT-3Brthien = 2-(3′-bromo-2′-thienyl)-4,4,5,5- tetramethyl-imidazoline-1-oxyl-3-oxide) have been successfully prepared. Single crystal X-ray crystallographic analysis reveals that both complexes consist of linear chains built up by Dy(hfac)3 units bridged by nitronyl nitroxide radicals through their NO groups. AC measurements indicate that two complexes are out-of-phase frequency-dependent suggesting single-chain magnet behavior.Two new nitronyl nitroxide bridged one-dimensional lanthanide complexes [Dy(hfac)3(NIT-2thien)]n (1); [Dy(hfac)3(NIT-3Brthien)]n (2) have been successfully prepared. Both complexes consist of linear chains built up by Dy(hfac)3 units bridged by nitronyl nitroxide radicals through their NO groups. AC measurements indicate that two complexes are out-of-phase frequency-dependent suggesting single-chain magnet behavior.Display Omitted► Two new lanthanide-radical complexes were successfully prepared. ► Both complexes are 1D chains bridged by radicals through their NO groups. ► They are out-of-phase frequency-dependent suggesting SCM behavior.
Keywords: Lanthanide; Nitronyl nitroxide; Frequency-dependent; Single-chain magnet behavior;

Valence-directed assembly and magnetic properties of two polynuclear pyrazine-2-amidoxime Fe complexes by Lan An; Li-juan Zhong; Jun Feng; Shi-zhen Du; Xiao-ming Lu (108-112).
The reaction of FeCl3·6H2O/FeCl2·4H2O, pyrazine-2-amidoxime (H2pzaox) and triethylamine (1:1:2 mol ratio) in MeOH/H2O (v/v = 1:1) affords undecanuclear and trinuclear complexes [Fe114-O)72-O)3(Hpzaox)9(H2O)6Cl]Cl3·5CH3OH·5H2O (1) and [Fe3(Hpzaox)6]Cl2·10H2O (2), respectively. The compounds were characterized by IR, X-ray crystallography and temperature-/field-magnetic susceptibility measurements. Complexes 1 contains the [FeIII 11(O)10]13 + core comprising eleven FeIII ions in a two floors ‘Tower’ disposition which was linked by nine oxime “N―O” groups of the H2pzaox ligands.In complex 1, Hpzaox- anion shows μ 2:η 1 η 1 η 1 and μ 3:η 1 η 1 η 2 two coordination modes. Trinuclear complex 2 is a mix valence with Fe(III)–Fe(II)–Fe(III) coordinated compound in which the ligands are only coordinated through μ 2:η 1 η 1 η 1 mode. Three oxime groups “N―O” bridge the adjacent metal centers with Fe⋯Fe separation of 3.5255(8) Å. Magnetic measurements of undecanuclear and trinuclear compounds in the 2–300 K temperature range reveal anti-ferromagnetic interactions between the Fe ions.The “metallic skeleton” of the Fe11 cluster (green). Hydrogen atoms and solvent molecules are omitted for clarity.Display Omitted► A new undecanuclear Fe complexe has been synthesized. ► A mix-valence trinuclear Fe complex with the μ 2:η 1 η 1 η 1 coordination mode. ► Anti-ferromagnetic interactions between the Fe ions of the two compounds.
Keywords: Polynuclear iron complex; Self-assemble; Magnetic properties; Pyrazine-2-amidoxime;

Ag(I)-N-heterocyclic carbene complexes of N-allyl substituted imidazol-2-ylidenes with ortho-, meta- and para-xylyl spacers: Synthesis, crystal structures and in vitro anticancer studies by Rosenani A. Haque; Mohammed Z. Ghdhayeb; Abbas Washeel Salman; Srinivasa Budagumpi; Mohamed B. Khadeer Ahamed; Amin M.S. Abdul Majid (113-119).
A series of N-allyl substituted xylyl-linked imidazolium salts (710) and their respective Ag(I)-N-heterocyclic carbene (NHC) complexes (1114) have been synthesized and characterized by a number of spectral and analytical techniques. Molecular structure of complexes 13 and 14 were established by single‐crystal X-ray diffraction method. The in vitro anticancer activity of all imidazolium salts and their Ag(I)-carbene complexes were investigated using human colorectal (HCT 116) cancer cell lines. Imidazolium salts displayed no activity for HCT 116 cell lines, except for 9; yielding IC50 value of 15.9 μM. Ag(I)-carbene complexes 1214 showed exceptionally good activity (0.9–1.3 μM) against tested cancer cell lines. Furthermore, complex 11 displayed relatively good anticancer activity with IC50 value of 5.2 μM, which is almost equal to standard used.A series of new N-allyl substituted xylyl-linked imidazolium salts and their respective Ag(I)-N-heterocyclic carbene (NHC) complexes were synthesized and evaluated for anticancer potential using human colorectal (HCT 116) cancer cell lines.Display Omitted► A series of imidazolium salts and Ag(I)-NHC complexes were synthesized. ► Compounds were characterized by elemental, NMR and X-ray diffraction techniques. ► The in vitro anticancer activity of all compounds was investigated. ► Ag-complexes showed exceptionally good anticancer activity (0.9–5.2 μM).
Keywords: Anticancer activity; Ag(I)-N-heterocyclic carbene complex; Human colorectal cell line; Xylyl-spacer; X-ray diffraction;

Two isostructural lanthanide complexes, [Ln2(INO)4(NO3)2]n·2nDMF [Ln = Eu (1), Tb (2)] (INO = isonicotinate-N-oxide; DMF =  N,N-dimethylformamide), have been synthesized under the solvothermal condition and characterized by single-crystal X-ray diffraction, X-ray powder diffraction (XRD), thermogravimetric analysis (TGA) and elemental analysis (EA). In these two complexes, each dinuclear Ln(III) unit is connected with six neighboring dinuclear units, which finally constructs a three-dimensional (3D) framework. Along the crystallographic [0 0 1] direction, there are one-dimensional (1D) tunnels, in which free DMF molecules reside as guests. Additionally, the photoluminescent properties of 1 and 2 are also discussed.Two isostructural lanthanide(III) complexes both exhibit 3D microporous pcu structures containing di-nuclear lanthanide(III) units, in which free DMF molecules reside as guests. To further investigate the properties of the above complexes, the photoluminescent properties of 1 and 2 are also discussed.Display Omitted► Two microporous lanthanide(III) complexes both exhibit 3D pcu structures. ► Free DMF molecules reside in 1D tunnels as guests. ► The title complexes emit intensely in the visible region.
Keywords: Solvothermal; Lanthanide; Crystal structure; Luminescence;

Syntheses and photophysical properties of cyclometallated iridium (III) acetylide complexes by Jun-Zhi Fu; Xu Zhang; Jin-Yun Wang; Li-Yi Zhang; Zhong-Ning Chen (123-125).
A series of cyclometallated iridium(III) acetylide complexes Ir(ppy)2(PPh3)(CCR) (R = C6H5 3, C6H4But-4 4, C6F5 5, C6H4COMe-4 6, SiMe3 7) were synthesized by substitution of coordination chloride in precursor Ir(ppy)2(PPh3)Cl (2, ppy = 2-phenylpyridine) with an acetylide ligand. These complexes are brightly luminescent in fluid dichloromethane at ambient temperature, originating from 3MLCT/3LLCT/3IL states as supported by TD-DFT studies. It is demonstrated that substitution of coordination chloride in precursor 2 (λ em  = 456 and 485 nm, Φ em  = 1.6%) with an acetylide ligand results in obvious red-shift of the emission as well as significant enhancement of the luminescence efficiency in 37 (λ em  = 480–510 nm, Φ em  = 9.5%–19%) since the energy level of non-emissive d–d transition is highly raised and thus d–d state deactivation is significantly suppressed.Substitution of coordination chloride in precursor Ir(ppy)2(PPh3)Cl with a strong-field acetylide ligand causes an obvious red-shift of the emission as well as significant enhancement of luminescent quantum yields in complexes Ir(ppy)2(PPh3)(CCR) (R = C6H5, C6H4But-4, C6F5, C6H4COMe-4, SiMe3).Display Omitted► Substituting Cl with an acetylide ligand in Ir(ppy)2(PPh3)Cl gave stable acetylide complexes. ► They exhibit bright solution luminescence at 298 K due to 3MLCT/3LLCT states. ► The luminescence is much improved upon substituting Cl with an acetylide ligand.
Keywords: Acetylide; Iridium; Luminescence; 2-phenylpyridine;

Hetero-binuclear near-infrared (NIR) luminescent ZnLn (Ln = Nd, Yb or Er) complexes self-assembled from the benzimidazole-based ligand by Guo-Xiang Shi; Wei-Xu Feng; Dan Zou; Xing-Qiang Lü; Zhao Zhang; Yao Zhang; Dai-Di Fan; Shun-Sheng Zhao; Wai-Kwok Wong; Richard A. Jones (126-130).
With the [Zn(HL) 2 (Py)] compound from the benzimidazole-based ligand H 2 L (H 2 L: 2-(1H-benzo[d]imidazol-2-yl)-6-methoxyohenol) as the precursor, the series of four hetero-binuclear ZnLn arrayed complexes [ZnLn(HL) 2 (Py)(NO 3 ) 3 ] (Ln = Nd, 1; Ln = Yb, 2; Ln = Er, 3; Ln = Gd, 4) have been obtained by the further reaction with Ln(NO 3 ) 3 ·6H2O, respectively. The result of their photophysical properties shows that the strong and characteristic NIR luminescence of Nd3 + or Yb3 + ion with emissive lifetimes in microsecond range, has been sensitized from the excited state (1LC and 3LC) of the benzimidazole-based ligand.Display Omitted► Hetero-binuclear Zn–Ln arrayed complexes assembled from the benzimidazole-based ligand ► Arrangement of energy donors around the Ln3 + ion ► Enhancement of near-infrared luminescent properties
Keywords: ZnLn arrayed benzimidazole-based complexes; NIR luminescence; Sensitization and energy transfer;

A unique lanthanide coordination polymer, formulated as {[Pr3(Heimda)2(μ 2-HCOO) (μ 2-C2O4)2·5H2O]}n (H3eimda = 2-ethyl-1H‐imidazole‐4,5‐dicarboxylic acid, H2C2O4  = oxalic acid) (1), has been hydrothermally synthesized by using lanthanide(III) nitrate, H3eimda acid at the presence of two kinds of carboxylate as coligands. The polymer was characterized by elements analysis, IR spectroscopy, thermogravimetry, variable-temperature magnetic susceptibility and single‐crystal X-ray diffraction study. Polymer 1 possesses three-dimensional (3-D) framework with Pcu topology, containing the original 1D zig-zag chain composed of [Pr-HCOO]2+ moieties. Variable temperature magnetic susceptibility measurements indicate that depopulation of the Stark levels or possible antiferromagnetic interactions within polymer 1 leads to the continuous decrease of χ M T when the samples are cooled from 300 to 2 K, and the photoluminescence properties of polymer 1 were also investigated.A unique lanthanide coordination polymer, formulated as {[Pr3(Heimda)2(μ 2-HCOO) (μ 2-C2O4)2·5H2O]}n has been hydrothermally synthesized and characterized. The depopulation of the Stark levels or possible antiferromagnetic interactions within the polymer lead to a continuous decrease of χ M T when the samples are cooled from 300 to 2 K, and the photoluminescent properties of polymer 1 were investigated.Display Omitted► To the best of our knowledge, this is the first (3, 4)-connected porous coordination framework containing nine-coordinated lanthanide ion. ► It displays possible weak antiferromagnetic coupling between the neighboring Pr(III) ions. ► The luminescent properties of polymer 1 were also investigated.
Keywords: Lanthanide coordination polymer; Substituted dicarboxylic ligand; Luminescence property; Antimagnetic properties;

A hexa-{MnIII–Schiff-base}-decorated cyclic polyoxovanadate as photocatalyst for dye degradation by Qiong Wu; Xiuli Hao; Xiaojia Feng; Yonghui Wang; Yangguang Li; Enbo Wang; Xiangqing Zhu; Xinghua Pan (137-140).
A new organic–inorganic hybrid compound (NH4)2[{Mn(salen)(H2O)}6V6O18](NO3)2·30H2O (salen2−  =  N,N′-(ethylene)bis(salicylideneiminate)) (1) was synthesized by the reaction between NH4VO3 and [Mn(salen)(H2O)2]ClO4 in a methanol–water solution with pH = 5.0 adjusted by nitric acid. Compound 1 was characterized by elemental analyses, TG, IR, UV–vis, XPS and the single-crystal X-ray diffraction. Compound 1 possesses a discrete cyclic hexanuclear vanadates, which is unprecedentedly grafted by six [Mn(salen)(H2O)2] units. Such a new hybrid compound displays good UV photocatalytic activity for RhB degradation.A new cyclic polyoxovanadate decorated by six {MnIII–Schiff-base} units was synthesized, exhibiting good UV photocatalytic activity for RhB degradation.Display Omitted► A new hybrid compound 1 based on polyoxovanadate and MnIII–Schiff-base units is synthesized. ► The discrete hexanuclear vanadate is unprecedentedly decorated by six MnIII–Schiff-base units. ► Compound 1 shows good UV photocatalytic activity for RhB degradation.
Keywords: Polyoxovanadate; Schiff-base; Hybrid; Photocatalytic activity;

Two dinuclear pyrophosphate-bridged copper(II) complexes displaying unusually strong O―H―O interactions by Mireille Perec; Rosana P. Sartoris; Rafael Calvo; Ricardo Baggio (141-145).
The crystal and molecular structures of two copper(II) dinuclear complexes bridged by the inorganic pyrophosphate tetraanion, namely, [Cu(bipy)(cis-H2P2O7)]2·3H2O 1 and [Cu2(terpy)2(HP2O7)]·2H2O(OH) 2, are reported (bipy = 2,2′-pyridine; terpy = 2,2′:6′,2″-terpyridine). Both compounds are characterized by two very strong O―H―O interactions which play a fundamental role in their crystal structure building. Compound 1 is identical to the recently reported compound 1a (Marino et al. Inorg. Chem. 50 (2011) 378–389), except for the supramolecular interaction which is revised in the present communication. Analysis of our data for 1 reveals the existence of a strong double well O―H⋯O′ ↔ O⋯(H―O)′ interaction around an inversion center (O―O: 2.433(2) Å), which binds dinuclear units together into [100] polymeric chains. Dinuclear compound 2 is monoclinic, halved by a twofold axis bisecting it through the central O atom of the bridge. The extreme disorder found in the solvates in 2 prevented an accurate description of the solvato content, and a detailed analysis of the H-bonding scheme. However, the extremely short O⋯O = 2.473(2) Å intermolecular distance points to a (quasi) symmetrical O―H―O interaction.The crystal and molecular structures of two copper(II) dinuclear complexes bridged by the inorganic pyrophosphate tetraanion, [Cu(bipy)(cis-H2P2O7)]2·3H2O 1 and [Cu2(terpy)2(HP2O7)]·2H2O(OH) 2, are reported (bipy = 2,2′-pyridine; terpy=2,2′:6′,2″-terpyridine). Both compounds are characterized by two very strong O―H―O interactions which play a fundamental role in their crystal structure building. The EPR spectra of powder samples do not show fine structure indicating that a zero-field splitting parameter is D = 0.Display Omitted► Dinuclear pyrophosphate-bridged Cu(II) complexes ► H-bonding and π⋯π interactions in supramolecular building ► Unusually strong H―O―H interactions in Cu(II) pyrophosphates ► EPR powder spectra
Keywords: Crystal structure; Pyrophosphate-bridge; Binuclear copper(II) complex; H-bonds; π–π bonds; EPR;

Ruthenium carbonyl compounds containing polypyridine ligands as catalysts in the reaction of N-benzylideneaniline hydrogenation by S.A. Moya; M. Vidal; K. Brown; C. Negrete-Vergara; G. Abarca; P. Aguirre (146-148).
The synthesis and characterization of ruthenium complexes containing polypyridine ligands: Ru(dppz)(PPh3)2Cl2, Ru(bpy)(PPh3)2Cl2, Ru(phen)(PPh3)2Cl2, Ru(dppz-Cl)(PPh3)2Cl2, Ru(phen)(CO)2Cl2, Ru(bpy)(CO)2Cl2 and Ru(dppz)(CO)2Cl2 (where dppz: dipyrido[3,2-a:2′,3′-c]phenazine, dppz-Cl: 10-chlororodypirido[3,2-a:2′,3′-c]phenazine, phen: 1,10-phenanthroline and bipy: 2,2′-bipyridine) are reported. The ruthenium complexes show high activity as catalysts in the hydrogenation reaction of N-benzylideneaniline and the hydrogen transfer reaction. The products of the catalysis were obtained with conversions between 21 and 91% after 2 h of reaction. The Ru(phen)(CO)2Cl2 complex was the catalyst that showed the highest conversion (91%) for the hydrogenation of N-benzylideneaniline. The complexes Ru(dppz)(PPh3)2Cl2, Ru(bpy)(PPh3)2Cl2 and Ru(dppz)(CO)2Cl2 showed 99% conversion in the hydrogen transfer reaction.We found a high catalytic activity in hydrogenation of N-benzylideneaniline using ruthenium carbonyl complex. The studied compound reported conversion of 91% with high selectivity in a short time of reaction.Display Omitted► Successful N-benzylideneaniline hydrogenation using ruthenium polypyridine complexes. ► Ruthenium carbonyl complex performs well in N-benzylideneaniline hydrogenation. ► The Ru-polypiridine complexes reduce the reaction time in hydrogenation of N-benzylideneaniline. ► Polypiridine ligands favoring the formation of hydride ruthenium complexes. ► The ruthenium hydride complexes in situ as a catalyst in hydrogenation of imine.
Keywords: Ruthenium hydrogenation; Imine hydrogenation; Homogeneous catalysis;

Luminescent, second-order NLO and magnetic properties of the hydrogen-bond based network derived from 2,2′-bipyridine-6,6′-dicarboxylate by Xiaochen Shan; A.O. Ibrahim; Youfu Zhou; Huabin Zhang; Jie Ma; Feilong Jiang; Maochun Hong (149-153).
Complexes [Zn(bpdc)(H2O)2] (1) and [Mn(bpdc)(H2O)3]∙2.5H2O (2) were assembled by 2,2′-bipyridine-6,6′-dicarboxylate (H2bpdc) with Zn2+ or Mn2+ under hydro/solvo-thermal conditions. Complexes 1 and 2 are extended from mononuclear to 1D, 2D and 3D supramolecular network step by step with the help of intramolecular weak interactions. The luminescent properties of 1 had been investigated in details, which show intense blue emission with relatively good quantum yield. The 2 displays nonlinear optical (NLO) activity comparable with that of KDP, and exhibits weak antiferromagnetic coupling between the Mn (II) ions by the hydrogen bonds.Compound 1 display intense blue luminescence and 2 revealed NLO response and antiferromagnetic coupling. Both of them extend from mononuclear to 3D supramolecular network by the intermolecular interactions.Display Omitted► The two mononuclear complexes are assembled by 2,2′-bipyridine-6,6′-dicarboxylate. ► The intense blue fluorescence of 1 originates from MLCT. ► 2 crystallizes in acentric space group and shows NLO activity. ► The antiferromagnetic coupling of 2 caused by hydrogen bonds.
Keywords: Fluorescence; Nonlinear optics; Magnetic properties; 2,2′-bipyridine-6,6′-dicarboxylate;

The bisfacial cobalt(II) complex [(HC(3-Phpz)2(5-Phpz))2Co][BF4]2 (1) was prepared by reaction of the tris(pyrazolyl)methane HC(3-Phpz)3 with Co(BF4)2·6H2O. A remarkable ligand rearrangement reaction occurs resulting in incorporation of the new ligand HC(3-Phpz)2(5-Phpz). Complex 1 was characterised by X-ray crystallography, mass spectrometry, IR spectroscopy and elemental analysis. DFT studies on both ligands as well as on complex 1 complement the experimental investigation.The bisfacial cobalt(II) complex [(HC(3-Phpz)2(5-Phpz))2Co][BF4]2 was prepared by reaction of the tris(pyrazolyl)methane HC(3-Phpz)3 with Co(BF4)2·6H2O. A remarkable ligand rearrangement reaction occurs resulting in incorporation of the new ligand HC(3-Phpz)2(5-Phpz).Display Omitted► Novel bisfacial cobalt(II) complex [(HC(3-Phpz)2(5-Phpz))2Co][BF4]2 was prepared and structurally characterised. ► Ligand HC(3-Phpz)3 undergoes rearrangement reaction resulting in formation of the new ligand HC(3-Phpz)2(5-Phpz). ► First rearrangement was observed for tris(pyrazolyl)methanes. ► DFT study shows stability of rearranged ligand in the cobalt(II) complex.
Keywords: Cobalt; Tris(pyrazolyl)methane; Rearrangement; X-ray diffraction; Density functional theory;

Reaction of the chiral aliphatic N-substituted diketiminate ligand, N,N′-Di(R-phenylethyl)-2-amino-4-iminopent-2-ene (R,R-nacnac CH(Me)PhH), with AlMe3 affords the monomeric dimethylaluminum complex R,R-nacnac CH(Me)PhAlMe2 (R,R-1). Complex S,S-nacnac CH(i-Pr)PhAlMe2 (S,S-2) is prepared by S,S-nacnac CH(i-Pr)PhH and AlMe3. Complexes R,R-1 and S,S-2 are the first examples of chiral β-diketiminate ligands with main group metals. All these two complexes exhibit activity for the ring-opening polymerization of ε-caprolactone in the absence of alcohol, and complex R,R-1 shows a higher activity with a narrow molecular weight distribution (PDI = 1.17) in toluene.The first example R,R-nacnac CH(Me)PhAlMe2 (R,R-1) of chiral β-diketiminate ligands with main group metals is prepared. Complex R,R-1 shows a high activity for the ring-opening polymerization of ε-caprolactone in the absence of alcohol, and has a good control over the polymerization reaction.Display Omitted► Dimethylaluminum complexes bearing a chiral diketiminate ligand are synthesized. ► Complex R,R-1 initiates the ε-caprolactone polymerization in the absence of alcohol. ► Complex R,R-1 initiates the ε-caprolactone polymerization in a “controlled” fashion.
Keywords: Aluminum complexes; Chiral β-diketiminate ligand; ε-Caprolactone; Initiator; Ring-opening polymerization;

Chiral mononuclear copper(II) complexes, [Cu(L R,R )(ClO4)2] (1) and [Cu(L S,S )(ClO4)2] (2) and chiral polymeric compound, [Cu(L S,S )(CrO4)]·6H2O (3) have been synthesized (L R,R/S,S  = 1,8-di((R/S)-α-methylbenzyl)-1,3,6,8,10,13-hexaazacyclotetradecane). These compounds were characterized by X-ray crystallography, circular dichroism, and molecular magnetism. The copper(II) ions in 1–3 have a distorted octahedral geometry by coordinating four nitrogens of a macrocyclic ligand in a square planar conformation and two oxygens in the axial positions. 3 exhibits weak antiferromagnetic coupling via the chromate ions within the 1D chain. The circular dichroism (CD) spectrum of 1 has shown a negative and positive peak at 474 and 562 nm, and that of 2 has displayed an enantiomeric pattern. The CD spectrum of 3 appears positive signal above 610 nm.Chiral mononuclear copper(II) complexes (1, 2) and chiral polymeric compound 3 have been synthesized. All copper(II) ions have a distorted octahedral geometry by coordinating four nitrogens and two oxygens. 3 exhibits weak antiferromagnetic coupling via the chromate ions. The CD spectra of 1 and 2 are shown an enantiomeric pattern.Display Omitted►Chiral mononuclear copper(II) complexes 1 and 2 and chiral polymeric compound 3 have been synthesized and characterized. ►The X-ray single-crystal structures of 1–3 are obtained and analyzed in detail. ►The magnetic properties of 3 are measured and analyzed in detail. ►The circular dichroism spectra of 1–3 are measured and analyzed in detail.
Keywords: Copper(II) complex; Coordination polymer; Chiral ligand; Crystal structure; Magnetic properties; Circular dichroism;

A new three-dimensional (3D) anionic interrupted open-framework aluminophosphate [(C4N2H12)3·H2O][(Al2P3O12)2] (denoted AlPO-JU88) with an Al/P ratio of 2/3 was hydrothermally synthesized by using piperazine as a structure directing agent. The structure was determined by single-crystal X-ray diffraction structural analysis and was further characterized by X-ray powder diffraction, elemental (CHN), thermogravimetric (TG), and NMR analyses. The strict alternation of Al-centered tetrahedra (AlO4) and P-centered tetrahedra (PO2(=O)2 and PO3(=O)) via bridging oxygen atoms resulted in a 3D open-framework featuring a new type of super-cage of 46128. Six racemic helical (31 or 32) chains were linked together to form a twelve-ring (12R) channel along the [0 0 1] direction, forming a multi-directional intersecting 12R channel system together with the 12R channels run along [2 4 1], [2 –2 1], and [− 4 − 2 1] directions. The negative charge of the framework was balanced by doubly protonated piperazine molecules. Ion exchange experiment suggested that 22 mol% of the protonated piperazine can be exchanged by Na cations, showing a better ion exchange property for the 3D interrupted open-framework aluminophosphates.The synthesis, characterization, and ion exchange study of a new 3D anionic interrupted aluminophosphate [(C4N2H12)3·H2O][(Al2P3O12)2] (denoted AlPO-JU88) with multi-directional intersecting 12R channel system, helical chains, and a new type of super-cage was reported.Display Omitted► A new 3D anionic interrupted aluminophosphate was hydrothermally synthesized. ► The compound contains a multi-directional intersecting 12R channel system. ► The structure features helical chains and a new type of super-cage. ► The compound shows a good ion exchange property.
Keywords: Zeolite; Aluminophosphate; Helical chain; Ion-exchange; Super-cage;

Two new complexes, namely, Co(IDC)(phen) (1) and [Co(PrIDC)(phen)]n⋅nH2O (2) (H3IDC = 4,5-imidazoledicarboxylic acid, H3PrIDC = 2-propyl-1H-imidazole-4,5-dicarboxylic acid, and phen = 1,10-phenanthroline) have been hydrothermally synthesized and structurally characterized. Complex 1 crystallizes in a tetranuclear fashion with a square ring-like structure. Complex 2 shows an infinite one-dimensional chain structure, in which the six-coordinated Co3+ exhibits distorted octahedral geometry. It is particularly worth noting that the existence of the substitute group of 2-position in the 4,5-imidazoledicarboxylate ligand plays a critical role in the formation of the resulting diverse topological structures. The fluorescence properties of complexes 1 and 2 in the solid state have also been investigated.Two cobalt-imidazole-based dicarboxylate complexes have been prepared. The substitute group plays a critical role in the formation of the resulting structures. The fluorescence properties of both compounds are investigated.Display Omitted► Two cobalt-imidazole-based dicarboxylate complexes have been prepared. ► Compound 1 adopts square ring-like structure. ► Compound 2 adopts a one-dimensional chain structure. ► The substitute group plays a critical role in the formation of the resulting structures.
Keywords: Coordination polymers; Cobalt; Structure; Fluorescence property;

A hybrid compound based on porous metal–organic frameworks and polyoxometalates: NO adsorption and decomposition by Feng-Ji Ma; Shu-Xia Liu; Guo-Jian Ren; Da-Dong Liang; Sha Sha (174-177).
A new hybrid compound based on porous metal–organic frameworks and polyoxometalates H4[(Cu4Cl)3(BTC)8]2[SiW12O40]·(C4H12N)6·3H2O (NENU-15, BTC = 1, 3, 5-benzenetricarboxylate) has been hydrothermally synthesized and its crystal structure, stability and porosity have been characterized. The experimental results showed that the introduction of polyoxometalates improved the integral stability of the compound. In addition, NENU-15 was employed in NO removal for the first time. By virtue of the synergistic effect between host frameworks and guest polyoxometalates, it not only displayed good adsorption behavior for NO, but also exhibited superior activity in NO decomposition.By virtue of the synergistic effect between host frameworks and guest polyoxometalates, the hybrid compound not only displayed good adsorption behavior for NO, but also exhibited superior activity in NO decomposition.Display Omitted► A new hybrid compound based on porous MOFs and POMs was synthesized under hydrothermal condition. ► POMs guests enhanced the thermal stability while maintaining the permanently porosity of host frameworks. ► There existed synergetic effect between Keggin type POMs and Cu-containing MOFs. ► The hybrid compound displayed good adsorption behavior for NO. ► The hybrid compound exhibited superior activity in NO decomposition.
Keywords: Metal–organic frameworks; Polyoxometalates; Porous materials; Adsorption; Decomposition;

A highly selective and ratiometric sensor for Hg2+ based on a phosphorescent iridium (III) complex by Fang Yan; Qunbo Mei; Lianhui Wang; Bihai Tong; Zhijie Xu; Jiena Weng; Lingxia Wang; Wei Huang (178-181).
A new neutral iridium (III) complex Ir(TBT)2(acac) based on 2-thiophen-2-yl-benzothiazole (TBTH) ligands has been synthesized and characterized. Ir(TBT)2(acac) exhibited color change from red to orange without and with Hg2+, at the same time has a blue shift about 23 nm in fluorescent emission spectra. So it can serve as a highly selective chemodosimeter for Hg2+ with ratiometric and naked-eye detection. The sensor allowed determination of Hg2+ in the working range of 3 μM–10 μM with a detection limit of 2.14 μM. The phosphorescent chemosensor exhibited excellent selectivity and sensitivity for Hg2+ detection.A excellent selective and sensitive chemosensory based on neutral iridium (III) complex Ir(TBT)2(acac) has been synthesized and characterized. It can serve as a chemodosimeter for Hg2+ with ratiometric and naked-eye detection.Display Omitted► A new neutral iridium (III) complex Ir(TBT)2(acac) has been synthesized and characterized. ► It can serve as a chemodosimeter for Hg2+ with ratiometric and naked-eye detection. ► The probe exhibited excellent selective and sensitive luminescent chemodosimeter.
Keywords: Iridium (III) complex; 2-thiophen-2-yl-benzothiazole; Hg2+; Phosphorescent chemosensor;

Two kinds of discrete water clusters, acyclic water tetramer and larger (H2O)28 cluster with a novel topknot-shaped (H2O)24 core formed from lattice water molecules, are captured in the voids of a Ag(I) polymeric solid [Ag4(bpda)2(bpp)4·18H2O]n (1) (where bpp = 1,3-bis(4-pyridyl)propane and H2bpda = 1,1′-biphenyl-2,2′-dicarboxylate acid). The centrosymmetric (H2O)24 cluster is basically an assembly of two (H2O)12 subunits and each subunit (H2O)12 has the shape of cage-like water monodecamer hydrogen bonded to one water monomer. The lattice of a crystal host provides two different sizes of hydrophilic environments for stabilizing these clusters. Moreover, the thermogravimetric curve and photoluminescence spectra of 1 were discussed. 1 exhibits strong photoluminescence maximized at 495 nm upon 390 nm excitation at ambient temperature, of which the CIE chromaticity ordinate (x = 0.23, y = 0.42) is close to that of the green component.Acyclic tetrameric and (H2O)28 cluster with a topknot-shaped (H2O)24 core are captured in a Ag(I) polymeric solid. The (H2O)24 cluster is an assembly of two (H2O)12 subunits related by a center of symmetry and each subunit (H2O)12 has the shape of cage-like water mono-decamer hydrogen bonded to one water monomer.Display Omitted► Acyclic tetrameric and (H2O)28 cluster are captured in the voids of a Ag(I) complex. ► (H2O)28 cluster can be viewed as one topknot-shaped (H2O)24 unit and four dangling water molecules. ► The complex emits luminescence at 495 nm as excited by 390 nm wavelength. ► CIE chromaticity ordinate of the emission is close to that of edge of green component.
Keywords: (H2O)28 cluster; (H2O)24 cluster; Water tetramer; Photoluminescence; CIE-1931;

Water-soluble heterometallic copper(II)-sodium complex comprising arylhydrazone of barbituric acid as a ligand by Kamran T. Mahmudov; M. Fátima C. Guedes da Silva; Marco Glucini; Marco Renzi; Kátia C.P. Gabriel; Maximilian N. Kopylovich; Manas Sutradhar; Fabio Marchetti; Claudio Pettinari; Silvia Zamponi; Armando J.L. Pombeiro (187-189).
A new aqua-soluble CuII-Na coordination polymer, {[Cu(H2O)Na(H2O)(η 9-L)]·2H2O}n, was easily generated by self-assembly from copper(II) nitrate, sodium hydroxide and 2-hydroxy-5-nitro-3-(2-(2,4,6-trioxotetrahydropyrimidin-5(2H)-ylidene)hydrazinyl)benzene sulfonic acid (H3L) a new hydrosoluble arylhydrazone of barbituric acid. The complex was characterized by IR spectroscopy, elemental and single‐crystal X-ray diffraction analyses, which disclosed 1D metal-organic chains driven by the intricate nona-chelation of the fully deprotonated L3− derivative to five metal cations (three NaI and two CuII). These chains have intercalated crystallization water molecules enabling the expansion of the structure to 3D by means of extensive hydrogen bond interactions.A new aqua-soluble CuII-Na 1D coordination polymer with intercalated crystallization water molecules has been synthesized by using arylhydrazone of barbituric acid as a nonadentate versatile ligand.Display Omitted► A new type of aqua-soluble copper(II)-sodium heterometallic coordination polymer has been prepared and fully characterized. ► Previously unknown arylhydrazone of barbituric acid was used for the first time as a nonadentate versatile ligand. ► Intercalated water clusters support the overall 3D supramolecular arrangement.
Keywords: Arylhydrazone of barbituric acid; Copper(II)-sodium complexes; Crystal structure; Heterometallic polymer;

A new 3D Cu(I) coordination polymer with 4-connected umv topological network by Jie Shang; Xiao-Yuan Wu; Fei Wang; Wen-Bin Yang; Rong-Min Yu; Can-Zhong Lu (190-192).
Here we synthesize a novel 3D luminescent CuI-coordination polymer. X-ray structure analysis revealed that 1 is constructed from both left- and right-handed copper–sulfur helical chains combined by pyt-ligands into a 3D 4-connected framework with the (42  · 63  · 8) umv topology. Upon photo excitation, 1 exhibits strong green light-emission in solid state at room temperature.The new graphical abstract text is: A novel 3D luminescent CuI compound constructed by both left- and right-handed copper-sulfur helical chains shows the (42  · 63  · 8) umv topology.Display Omitted► A novel CuI-coordination polymer constructed from both left- and right-handed copper-sulfur helical chains. ► Compound 1 exhibits novel 4-connected net with the point symbol of (42  · 63  · 8). ► Compound 1 exhibits strong green light in solid state at room temperature.
Keywords: Copper; Hydrothermal synthesis; Topology; Luminescence; MOFs;