Four Complexes of Mn(Ⅱ), Co(Ⅱ), Ni(Ⅱ) and Cu(Ⅱ) Based on 2-Morpholine-4-yl-4,6-di-pyrazol-1-yl-1,3,5-triazine

Three azide bridged complexes, namely, [Mn_2L_2(N_3)_4(H_2O)_2](1), [Co_2L_2(N_3)_4]·(H_2O)_3(2) and [Ni_2L_2(N_3)_3(H_2O)]N_3·(H_2O)_4(3)(L = 2-morpholine-4-yl-4,6-di-pyrazol-1-yl-1,3,5-triazine), were synthesized by the reaction of L ligand, sodium azide with Mn(Ⅱ), Co(Ⅱ) and Ni(Ⅱ) chlorides. The copper(Ⅱ) chloride combined with thiocyanate and L ligand to form a mononuclear complex [CuL(CH_3OH)(SCN)(NCS)](4). Complexes 1~4 were characterized by IR, elemental analysis and X-ray crystallographic analysis. It was worth noting that two Mn(Ⅱ) atoms were connected by the end-to-end mode in 1, while Co(Ⅱ) and Ni(Ⅱ) atoms were connected by the end-on mode in 2 and 3. In complex 4, the central copper atom was coordinated with a sulfur atom and a nitrogen atom of the two thiocyanate ligands, respectively. Hydrogen bonds, π-π stacking interactions, thermogravimetric analysis and fluorescence properties of 1~4 were studied.     

One Novel Mn(Ⅱ) Complex with 1-Substituted-1H-1,2,3-triazole-4-carboxylic Acid:Crystal Structure,Fluorescence and Hirshfeld Surface Analysis

The crystal structure of one novel Mn(II) complex, [Mn(pmta)_3]_2[Mn(H_2O)_6]·4H_2O(1), is reported(Hpmta = 5-methyl-1-phenyl-1H-1,2,3-triazole-4-carboxylic acid). In the title compound, the asymmetric unit consists of a [Mn(pmta_)3]ˉ anion, half [Mn(H_2O)_6]~(2+) counter cation and two lattice H_2O molecules, and the intra- and intermolecular hydrogen bonds connect the complex into a supramolecular structure. The liquid-state fluorescence spectra of complex 1 have been determined. Hirshfeld surface analysis was also studied. The main intermolecular interactions in the complex are O···H and H···H contacts.     

A Novel Three-dimensional Mn(Ⅱ) Coordination Polymer Constructed from Biphenyl-3,3?,5,5?-tetracarboxylic Acid and Water

The title Mn(Ⅱ) coordination polymer,poly{[heptaaqua-(μ4-bi-phenyl-3,3?,5,5?-tetracarboxylate)-bimanganese(Ⅱ)] pentahydrate},[Mn_2(bpta)(H_2O)_7]_n·5n H_2O(I),is crystallized from a mixture of biphenyl-3,3?,5,5?-tetracarboxylic acid(H_4bpta) and MnCl_2·4H_2O in waterethanol under room temperature. Its asymmetric unit consists of one and two halves of crystallographically independent Mn(Ⅱ) cations,one fully deprotonated H4 bpta ligand,seven coordinated water molecules and five solvent water as guest molecules. In I,each Mn(Ⅱ) atom is octahedrally coordinated by six oxygen atoms from bpta~(4-) anions and coordinated water molecules. In the Mn(Ⅱ) cations,one half Mn(Ⅱ) ion of them located at a 2-fold axis generating a trinuclear [Mn_3(H_2O)_2(RCOO)_2] linker by μ1,1-O(water) and μ1,3-O,O?(carboxylate) bridges and another half Mn(Ⅱ) ion with an inversion is a mononuclear linker. These neighbouring trinuclear and mononuclear Mn(Ⅱ) cations are linked together by biphenyl-3,3?,5,5?-tetracarboxylates to form a three-dimensional framework with a(42.84) topology of a(4,4)-connected net,in which the positions of the trinuclear [Mn_3(H_2O)_2(R-COO)_2] linker as a 4-connector linking four bpta~(4-) ligands in I reproduce an eagle-shaped arrangement. The polymeric structure exhibits a water channel with an accessible void of 797.1 ?~3,amounting to 15.7% of the total unit-cell volume. Each of the cavities in the network is occupied by solvent water molecules.     

Preparations and characterizations of two MOFs constructed with hydroxylphenyl imidazole dicarboxylate

Using the hydrothermal reactions of Mn(Ⅱ) and Ba(Ⅱ) salts with 2-(3-hydroxylphenyl)-1H-imidazole-4,5-dicarboxylic acid(m-OHPhH_3IDC),two novel metal-organic frameworks,namely,{[Mn(mOHPhHIDC)(H_2O)]2H_2O}_n(1) and {[Ba(m-OHPhH_2IDC)_2(H_2O)_3]-2H_2O)_n,(2) have been synthesized and structurally characterized by single-crystal X-ray crystallography,elemental analyses,and IR spectroscopy.Complex 1 features a novel non-interpenetrated three-dimensional(3,4)-connected network with one-dimensional open channels.Complex 2 exhibits a two-dimensional layered structure with rhombic grids.The role of the central metals in the formation of final architectures has been discussed.Furthermore,luminescent and thermal properties of the two complexes have been studied.     

Two Novel Complexes Based on N-N Bridged Ligand:Syntheses,Crystal Structures,Fluorescence and Magnetic Property

Two novel coordination compounds,1[Zn_4(L_1)_4(NO_3)_2(H_2O)_2](NO_3)_2·2H_2O and 2[Mn_2(L_2)_2(DMF)(H_2O)_3](ClO_4)_2·DMF(HL_1 = N'-[(1E)-pyridine-2-ylmethylidene]pyrazine-2-carbohydrazide,H_2L_2 = 2-hydroxy-3-methoxybenzaldehyde(pyrazin-2-ylcarbonyl)hydrazone),based on the N-N bridged ligands were prepared and structurally characterized.Compound 1represents the[2*2]molecular squares,in which both N atoms belonging to the N-N bridged ligands are connected to the Zn centers.The emission of compound 1 exhibits a blue shift,which can be assigned to strong electrostatic interaction between Zn~Ⅱ ions and the L_1~(-1).Compound 2represents a rare phenol-O bridged Mn_2~Ⅱ complex.The magnetic investigation indicates weak antiferromagnetic interactions between the Mn~Ⅱ centers.     

Synthesis, Crystal Structure and Luminescence Property of a 2D Mn（II） Coordination Polymer Based on Isoniazid

A novel 2D Mn(Ⅱ) coordination polymer [Mn(CH3COO)2(INH)]n(INH=isoniazid) has been synthesized in DMF solution with isoniazid and Mn(CH3COO)2 . The polymer was characterized by single-crystal X-ray diffraction analysis, FTIR and X-ray powder diffraction (XRPD). The crystal belongs to the monoclinic system, space group P2 1 /c with a=9.3251(18), b=16.340(3), c=8.8096(17) , β=94.747(3)°, V=1337.7(4) 3 , Z=4, μ(MoKα)=1.006 mm -1 , F(000)=636, R=0.0754 and wR=0.1375 (I > 2σ(I)). In the complex, each Mn(Ⅱ) atom is coordinated to three CH3COO- groups and two INH ligands. The Mn(Ⅱ) atoms locate in a distorted coordination octahedron and are bridged by CH3COO- ions to form a 1D S shaped chain extending along the c direction. The INH molecules act as bridges to link the Mn(Ⅱ) atoms of adjacent chains and further construct a lamellar polymer. The remaining coordination site is occupied by an O atom of the other CH3COO-. The experimental results show that the title complex has good luminescence property and could be used as potential optical materials.     

Structural Diversity and Photoluminescent Properties of Two Mn(Ⅱ) Sulfoterephthalate Complexes from Multi-pyridine N-containing Ligands

Solvothermal reaction of manganese(II) salt with monosodium 2-sulfoterephthalate(2-NaH_2stp) and two multi-pyridine N-containing auxiliary ligands results in the formation of two new complexes formulated with [Mn_2(Hstp)_2(bpp)_2(H_2O)_4](1) and [Mn_3(stp)_2(tpy)_3(H_2O)](H_2O)_5(2)(bpp = benz-2,3-pyrimidine-[2,3-f]-1,10-phenanthroline, tpy = 2,2?:6?,2??-terpyridine). X-ray diffraction structural analyses of two complexes reveal their structural diversity(0D and 1D) due to the difference of auxiliary ligands. 1 is a discrete structure, in which the Mn(Ⅱ) ion is hexa-coordinated with one stp, one bpp ligand and two water molecules. Complex 2 is a one-dimensional(1D) chain-like structure with three crystallographically independent Mn(Ⅱ) ions. The photoluminescent properties could be assigned to the π-π* transition of 2-sulfoterephthalate ligands.     

Synthetic Assembly of Inorganic-organic Polyoxometalate Hybrid Structures Employing Noncovalent Interactions between 5,6-Substituted 1,10-Phenanthroline Derivative Ligands

A new strategy for the synthesis of polyoxometalate-based(POM-based) metalorganic materials was developed. The approach takes the advantage of the ability of phenanthroline derivative base to build strong noncovalent interactions. Three POM-based metal-organic compounds, [Mn(MOPIP)_2(OH)_2][Mn(MOPIP)_2(OH)(SiW _(12)O_(40))]·6H_2O(1), [Cu_2(MOPIP)_2(OH)2(H_2O)]2-(Si W_(12)O_(40))·5H_2O(2) and [Co(Mo2O7)(MOPIP)]n(3)(MOPIP = 2-(4-methoxyphenyl)-1H-imidazo[4,5-f][1,10]phenanthroline), were synthesized under hydrothermal conditions. Single-crystal X-ray analysis reveals that compound 1 displays a mononuclear cluster. These clusters are interconnected by a framework of π···π stacking interactions to from a chain and layer structure. Compound 2 shows a multinuclear cluster with Keggin-type polyoxoanions [Si W_(12)O_(40)]4- as building blocks. Strong hydrogen bonding interactions extend these multinuclear clusters into a two-dimensional layer. Compound 3 is a coordination polymer, in which [Mo_2O_7]2- polyoxoanions connect the Co(Ⅱ) ions running along the direction of one of the crystallographic axes to from a linear chain. Adjacent chains are further assembled into a two-dimensional network by strong hydrogen bonding interactions. The main structural traits in all of the compounds are that polyoxometalate acts as inorganic building blocks and connect metal ions to form cluster structure and coordination polymer. In addition, the photocatalytic activities and mechanism of compounds 1~3 on the degradation of Rhodamine B(Rh B) under UV irradiation have been investigated in detail.     

A New Pillared-layer Framework with Rare Mn（II）-triazole-carboxylate Magnetic Layer Exhibiting an Antiferromagnetic Ordering

A novel pillared-layer framework with a (52.6)(53.63.73.8) Schl fli symbol, [Mn(H2O)(Htrz)(Hbtc)]n (1), was prepared by the reaction of 1,2,4-triazole (Htrz), 1,3,5-benzenetricarboxylic acid (H3 btc), and Mn Ⅱ salt and structurally and magnetically characterized. It crystallizes in the orthorhombic system, space group P212121 with a=7.1618(5), b=9.0356(6), c=10.9740(13) , V=1292.54(15) 3 , D c=1.799 g/cm3 , Mr=350.15, Z=4, F(000)=708, μ=1.064 mm -1 , and the final R=0.0177 and wR=0.0462 for 2273 observed reflections with I > 2σ(I). The unique octahedral Mn Ⅱ ion in 1 is periodically linked into a two-dimensional (2D) magnetic layer by μ2 -N1 , N4 -Htrz and syn, anti-COO of doubly deprotonated Hbtc 2anion, which is further supported by the phenyl backbone of Hbtc 2ligand to generate a 3D pillared-layer framework. Magnetically, complex 1 displays an antiferromagnetic ordering below 5.0 K due to the cooperative antiferromagnetic couplings mediated by the mixed heterobridges within the magnetic layer.     

Mn(Ⅱ) Based Coordination Polymer Involving 1,2,4,5-Benzenetetraboxylic Acid and 4,4-Bis(imidazol-1-ylmethyl)biphenyl: Synthetic,Structure and Magnetic Property

A novel Mn(Ⅱ)coordination polymer(CP),[Mn(BBA)_(0.5)(BIYB)]_n(1),was gained by the 1,2,4,5-benzenetetracarboxylic acid(H_4BBA),4,4-bis(imidazol-1-ylmethyl)biphenyl(BIYB),and Mn(CH_3COO)_2·4H_2O under hydrothermal reaction.CP 1 was characterized and structurally determined by elemental analyses,PXRD,IR spectra,thermal behaviors,and X-ray single-crystal diffraction.The framework structure of 1 shows a novel(2,5,6)-connected 3Dnetwork with a Schlafli symbol of(4~3.6~6.8)~2(4~6.6~9)(6)~2.It crystallizes in triclinic system,space group ■,with a=7.5898(5),b=9.8201(6),c=14.1307(9)?,α=97.5850(10),β=99.6810(10),γ=111.6580(10)o,V=943.01(10)?~3,Z=2,C_(23)H_(15)MnN _4O_4,M_r=466.33,D_c=1.462 g/cm~3,F(000)=476,S=1.082,R=0.0361 and wR=0.1008.The magnetic property of CP 1 was investigated.The weak antiferromagnetic interactions are observed between the Mn(Ⅱ)ions.     

A 3D Homochiral Mn(Ⅱ) Coordination Polymer Based on the Ligand 2,2?-(Ethane-1,2-diylbis(oxy)) Dicinnamic Acid

A 3D homochiral coordination polymer [Mn(edca)]n(1) was synthesized from a flexible coupled cinnamic acid ligand, 2,2?-(ethane-1,2-diylbis(oxy)) dicinnamic acid(H_2 edca) and MnCl_2×4 H_2 O under solvothermal conditions. The complex crystallizes in orthorhombic, space group P2_12_12_1 with a = 5.5785(8), b = 13.0393(18), c = 23.133(3) ?, V = 1682.7(4) ?~3, M_r = 407.27, D_c = 1.608 Mg/cm~3, F(000) = 836, Z = 4, the final R = 0.0240 and wR = 0.0590 for 2983 observed reflections(I 2σ(I)). In 1, the edca2+ anions alternately bridge the Mn(Ⅱ) cations to form one-dimensional(1 D) infinite helical chains of [Mn(edca)]n, which are further connected by the ligands generating a three-dimensional(3D) homochiral network. The photoluminescence of 1 was also investigated in solid state at ambient temperature.     

Solvothermal Synthesis,Crystal Structure and Characterizations of a Novel 2D Organic Decorated Manganese Thiostannate:MnSnS3(1,2-DACH)

A novel 1,2-diaminocyclohexane(1,2-DACH) decorated manganese thiostannate,namely MnSnS_3(1,2-DACH)(1),has been solvothermally synthesized by the reaction of Mn(CH_3COO)_2·4H_2O,Sn and S in the stoichiometric ratio in 1,2-DACH,which acted as an efficient structure-directing agent(SDA) and reactive solvent in the formation of the title compound. Single-crystal X-ray diffraction studies revealed that the title compound crystallizes in the monoclinic space group P2_1/c with a = 12.2458(7),b = 13.8588(7),c = 7.2292(4) ?,β = 99.460(6)°,V = 1210.20(12) ?~3,Z = 4,Dc = 2.108 g·cm~(-3),F(000) = 748,μ = 3.584 mm~(-1),R = 0.0348 and wR = 0.0823(I 2σ(I)). The structure features a neutral two-dimensional(2D) network constructed by the unsaturated [Mn(1,2-DACH)] complexes interconnecting [SnS_3]_n~(2n-) chains via sharing S. Thermal stability and optical property of compound 1 were characterized.     

Synthesis and Spectroscopic Properties of Cyclotriphosphazenes Containing 6-(4-Hydroxyphenyl)-2,2''-bipyridine Side Groups

Two novel cyclotriphosphazene derivatives containing 6-(4-hydroxyphenyl)-2,2'-bipyridine(hopbp)side groups,N_3P_3(dobp)_2(hopbp)_2(1)and N_3P_3(dobp)(hopbp)_4(2)(dobp=2,2'-dioxybiphenyl),were synthesized and characterized.These compounds display strong fluorescent emission both in solution and in solid state.Their absorption and emission spectra are sensitive to proton:the addition of HBF4 to the methanol and dichloromethane solution(9∶1,volume ratio)of compound 1 led to a red-shift from 350 to 460 nm for the emission spectrum,and the process was also characterized by isosbestic points of absorption spectra at 267,287 and 313 nm.     

SYNTHESIS, MAGNETIC PROPERTY AND X-RAY CRYSTAL STUCTURE OF MIXED VALENT COBALT COMPLEX SALT [Co~Ⅲ Cl_2(py)_4][Co~Ⅱ Cl_3(py)]

Complex salt Co_2Cl_5(py)_5 (py=pyridine) was obtained by the reaction of CoCl_2·6H_2O with Bu_4NMnO_4 in pyridine in the presence of benzoic acid. It is monoclinic and crystallizes in space group P2_1/n, fw=690.64, a=28.652(5), b=14.108(4), c=7.424(3) ;β=90.09(1); V=3001(2)~3; Z=4, Dc=1.53g/cm~3. Final R factor is 0.041. The structure consists of a discrete cation [Co~ⅢCl_2(py)_4]~+ and an anion [Co~Ⅱ Cl_3(py)]~-. The Co~Ⅲ ion is coordinated by two Cl~- and four pyridine nitrogen atoms to form an octahedral geometry, and Co~Ⅱ is coordinated by three Cl~- and one pyridine nitrogen atom to form the apices of a tetrahedron. The variable-temperature magnetic susceptility measurement shows no magnet-exchange interaction between Co~Ⅲ and Co~Ⅱ ions.     

Cyanide-bridged One-dimensional Heterobimetallic Complex cis-[Fe~Ⅱ(phen)_2(CN)_2Mn~Ⅲ(salen)](PF_6): Synthesis,Crystal Structure and Magnetic Properties

Dicyanide building block cis-Fe(phen)_2(CN)_2 and [Mn~Ⅲ(salen)](ClO_4) have been used to design and synthesize a cyanide-bridged complex, resulting in a heterobimetallic one-dimensional(1D) zigzag chain complex 1, [cis-Fe(phen)_2(CN)_2Mn(salen)](PF_6)(phen =1,10-phenanthroline, salen=N,N?-ethylenebis-(salicylideneaminato) dianion). Single-crystal X-ray diffraction analysis shows complex 1 crystallizes in the monoclinic P2_(1/c) space group and the asymmetric unit contains one [-NC-Fe(phen)_2(μ-CN)-Mn~Ⅲ-(salen)-]~+ cation and one PF_6~- anion. In the cationic structure of 1, each Fe~Ⅱ(phen)_2(CN)_2 connects two [Mn~Ⅲ(salen)]~+ with two cyanide groups in a cis-conformation, and in turn each [Mn~Ⅲ(salen)]~+ unit links two Fe~Ⅱ(phen)2(CN)_2 building blocks in a trans-conformation, resulting in a 1D [-NC-Fe~Ⅱ-CN-Mn~Ⅲ-]n chain. Furthermore, the electronic absorption spectra and electrochemical and magnetic properties of complex 1 have also been studied.     

5,10,15,20-Tetrakis （p-4-fluorobenzoyloxy） phenyl Porphyrin and Its Transition Metal Complexes

The properties of porphyrins can be changed through the choice of peripheral substituents and inserted metal ions. To obtain porphyrin complexes with novel structures, 5,10,15,20-tetrakis(p-4-fluorobenzoyloxy) phenyl porphyrin(TFBOPPH2) and its transition metal complexes {TFBOPPM [M=Mn(Ⅲ), Fe(Ⅲ), Co(Ⅱ), Ni(Ⅱ), Cu(Ⅱ) and Zn(Ⅱ)]} were synthesized and characterized by means of UV-Vis, IR photoacoustic spectrometry, 1H NMR, elemental analyses, molar conductance, and XPS methods. A structure is proposed, in which one porphyrin molecule is coordinated with a transition metal ion in a tetradentate fashion, while the chlorine ion is the balanceable anion in Fe(Ⅲ) and Mn(Ⅲ) complexes.     

An Organic-inorganic Hybrid Assembly Based on Novel Arsenatomolybdate and Cu~Ⅰ-Organic Units

A novel organic-inorganic hybrid arsenatomolybdate based on infrequent[AsMo_4O_(14)(OH)_2]~(3-)unit,[Cu ~I(phen)_2]_3[AsMo_4O_(14)(OH)_2]·3H_2O(1,phen=1,10-phenanthroline),has been hydrothermally synthe-sized.This structure was determined by single-crystal X-ray diffraction analysis,and further characterized by elemental analysis,and IR and UV spectra.To the best of our knowledge,it is the first report of a novel arsenatomolybdate subunit[AsMo_4O_(14)(OH)_2]~(3-).Photoluminescence of 1 is ascribed to???*emission of the aromatic rings derived from the phen ligand.     

Synthesis, crystal structure and magnetic properties of a novel manganese(II)-nitronyl nitroxide-azido(μ_(1,1) and μ_(1,3)) one-dimensional complex

A novel one-dimensional manganese(Ⅱ) complex containing nitronyl nitroxide radical [Mn2(IM2-py)2(Ac)2((μ1.1-N3)(μ1,3-N3) . EtOH]n was synthesized and characterized structurally and magnetically. It crystallizes in the monoclinic space group p21/n. Each Mn(Ⅱ) ion is six-coordinated in a distorted octahedral environment. The two N atoms of the nitronyl nitroxide radical and the two O atoms of acetate ligands are in the equatorial plane, whereas the two different azido bridging ligands are in trans axial position. Mn(Ⅱ) ions are linked by nitrogen atom of μ1,1-azido and oxygen atoms of two carboxy groups to form a Mn-Mn unit. Mn-Mn units are linked by azido ligands through u1,3 bridging style to form a one-dimensional chain. The compound is connected by the coordination bonds,π-π interactions and hydrogen bonds as a three-dimensional structure. Magnetic susceptibility data support that there are stronger antiferromagnetic interactions between the radical and Mn(Ⅱ) ion, weak antiferromagnetic inter     

Synthesis and Crystal Structure of a Novel Three-dimensional Manganese(Ⅱ)Coordination Polymer:[Mn(pdc)]n(pdc=Pyridine-2,4-dicarboxylate)

A novel manganese(Ⅱ)coordination polymer[Mn(pdc)]n(pdc=pyridine-2,4-dicarboxylate)has been synthesized under hydrothermal conditions.The crystal is of monoclinic,space group P21/n with a=6.506(4),b=9.392(6),c=11.217(7)(A),β=105.650(12)°,V=660.0(7)(A)3,z=4,Mr=220.04.Dc=2.215 g/cm3,μ=1.971 mm-1,F(000)=436,Rint=0.0345,R=0.0360 and wR=0.0778 for 1259 observed reflections with I＞2a(I).In the structure.the Mn(Ⅱ)atom is coordinated in a distorted octahedral arrangement by one pyridine N and five carboxylate O atoms from five pac ligands,each of which coordinates to five Mn atoms to propagate a three-dimensional layered framework.     

Synthesis,Crystal Structure and Spectroscopic Properties of Cyanide-bridged Complex [Ru~Ⅱ(ttpy)(CN)_3Mn~Ⅲ(salen)]

Tricyanide building block K[Ru(ttpy)(CN)_3] and [Mn~Ⅲ(salen)](ClO_4) have been used to design and synthesize a heterobimetallic one-dimensional(1D) zigzag chain complex 1,[Ru~Ⅱ(ttpy)(CN)_3 Mn~Ⅲ(salen)](ttpy = 4?-(p-tolyl)-2,2?:6?,2??-terpyridine, salen = N,N?-ethylenebis-(salicylideneaminato)dianion). Single-crystal X-ray diffraction analysis shows complex 1 crystallizes in orthorhombic Pbca space group and the asymmetric unit of 1 contains one[-NC-Ru~Ⅱ(ttpy)(CN)(m-CN)-Mn ~Ⅲ-(salen)-] molecule. In the structure of 1, each [Ru ~Ⅱ(ttpy)(CN)_3]~-connects two [Mn~Ⅲ(salen)]~+ with two cyanide groups in a cis-conformation, and in turn each[Mn~Ⅲ(salen)]~+ unit links two [Ru~Ⅱ(ttpy)(CN)_3]~-building blocks in a trans-conformation, resulting in a 1D [-NC-Ru~Ⅱ-CN-Mn~Ⅲ-]_n chain. Furthermore, the electronic absorption spectra and luminescence spectroscopy of complex 1 have also been studied.