Cobalt and manganese nets via their wires: facile transformation in metal-diorganophosphates

The manganese and cobalt complexes [M(dtbp)2]n (M=Mn, Co; dtbp=di-tert-butyl phosphate), which exist as one-dimensional molecular wires, transform to [M(dtbp)2(bpy)2.2H2O]n by the addition of 4,4-bipyridine (bpy) at room temperature; the latter compounds form noninterpenetrating rectangular grid structures.     

Di-tert-butyl phosphate as synthon for metal phosphate materials via single-source coordination polymers [M(dtbp)(2)](n) (M = Mn,Cu) and [Cd(dtbp)(2)(H2O)](n) (dtbp-H = (tBuO)(2)P(O)OH)

Reaction of M(OAc)(2).xH(2)O (M = Mn, Cu, or Cd) with di-tert-butyl phosphate (dtbp-H) in a 1:2 molar ratio in methanol followed by slow crystallization of the resultant solid in MeOH/THF medium results in the formation of three new polymeric metal phosphates [M(dtbp)(2)](n)() [M = Mn, 1 (beige); M = Cu, 2 (blue)] and [Cd(dtbp)(2)(H(2)O)](n)(), 3 (colorless)] in good yields. The formation of [Mn(dtbp)(2)](n) (1) proceeds via tetrameric manganese phosphate [Mn(4)(O)(dtbp)(6)] (4), which has been isolated in an analytically pure form. Perfectly air- and moisture-stable compounds 1-4 were characterized with the aid of analytical, thermoanalytical, and spectroscopic techniques. The molecular structures of 1-3 were further established by single-crystal X-ray diffraction studies. Crystal data for 1: C(32)H(72)Mn(2)O(16)P(4), monoclinic, P2(1)/c, a = 19.957(4) A, b = 13.419(1) A, c = 18.083(2) A, beta = 91.25(2) degrees, Z = 4. Crystal data for 2: C(16)H(36)CuO(8)P(2), orthorhombic, Pccn, a = 23.777(2) A, b = 10.074(1) A, c = 10.090(1) A, Z = 4. Crystal data for 3: C(48)H(114)Cd(3)O(27)P(6), triclinic, P1, a = 12.689(3) A, b = 14.364(3) A, c = 22.491(5) A, alpha = 84.54(3) degrees, beta = 79.43(3) degrees, gamma = 70.03(3) degrees, Z = 2. The diffraction studies reveal three different structural forms for the three compounds investigated, each possessing a one-dimensional coordination polymeric structure. While alternating triple and single dtbp bridges are found between the adjacent Mn(2+) ions in 1, uniform double dtbp bridges across the adjacent Cu(2+) ions are present in 2. The cadmium ions in the structure of 3 are pentacoordinated. Thermal analysis (TGA and DSC) indicates that compounds 1-3 convert to the corresponding crystalline metaphosphate materials M(PO(3))(2), in each case at temperatures below 500 degrees C. Similarly, the thermal decomposition of 4 results in the formation of Mn(PO(3))(3) and Mn(2)P(2)O(7). The final materials obtained by independent thermal decomposition of bulk samples have been characterized using IR spectroscopic, powder diffraction, and N(2) adsorption studies.     

Di-tert-butyl phosphate complexes of cobalt(II) and zinc(II) as precursors for ceramic M(PO3)2 and M2P2O7 materials: synthesis, spectral characterization, structural studies, and role of auxiliary ligands

Reaction of the metal acetates M(OAc)2xH2O with di-tert-butyl phosphate (dtbp-H) (3) in a 4:6 molar ratio in methanol or tetrahydrofuran followed by slow evaporation of the solvent results in the formation of metal phosphate clusters [M4(mu 4-O)(dtbp)6] (M = Co (4, blue); Zn (5, colorless)) in nearly quantitative yields. The same reaction, when carried out in the presence of a donor auxiliary ligand such as imidazole (imz) and ethylenediamine (en), results in the formation of octahedral complexes [M(dtbp)2(imz)4] (M = Co (6); Ni (7); Zn (8)) and [Co(dtbp)2-(en)2] (9). The tetrameric clusters 4 and 5 could also be converted into mononuclear 6 and 8; respectively, by treating them with a large excess of imidazole. The use of slightly bulkier auxiliary ligand 3,5-dimethylpyrazole (3,5-dmp) in the reaction between cobalt acetate and 3 results in the isolation of mononuclear tetrahedral complex [Co(dtbp)2(3,5-dmp)2] (10) in nearly quantitative yields. Perfectly air- and moisture-stable samples of 4-10 were characterized with the aid of analytical, thermoanalytical, and spectroscopic techniques. The molecular structures of the monomeric pale-pink compound 6, colorless 8, and deep-blue 10 were further established by single-crystal X-ray diffraction studies. Crystal data for 6: C28H52CoN8O8P2, a = 8.525(1) A, b = 9.331(3) A, c = 12.697(2) A, alpha = 86.40(2) degrees, beta = 88.12(3) degrees, gamma = 67.12(2) degrees, triclinic, P1, Z = 1. Crystal data for 8: C28H52N8O8P2Zn, a = 8.488(1) A, b = 9.333(1) A, c = 12.723(2) A, alpha = 86.55(1) degrees, beta = 88.04(1) degrees, gamma = 67.42(1) degrees, triclinic, P1, Z = 1. Crystal data for 10: C26H52CoN4O8P2, a = b = 18.114(1) A, c = 10.862(1) A, tetragonal, P4(1), Z = 4. The Co2+ ion in 6 is octahedrally coordinated by four imidazole nitrogens which occupy the equatorial positions and oxygens of two phosphate anions on the axial coordination sites. The zinc derivative 8 is isostructural to the cobalt derivative 6. The crystal structure of 10 reveals that the central cobalt atom is tetrahedrally coordinated by two phosphate and two 3,5-dmp ligands. In all structurally characterized monomeric compounds (6, 8, and 10), the dtbp ligand acts as a monodentate, terminal ligand with free P=O phosphoryl groups. Thermal studies indicate that heating the samples at 171 (for 4) or 93 degrees C (for 5) leads to the loss of twelve equivalents of isobutene gas yielding carbon-free [M4(mu 4-O)(O2P(OH)2)6], which undergoes further condensation by water elimination to yield a material of the composition Co4O19P6. This sample of 4 when heated above 500 degrees C contains the crystalline metaphosphate Co(PO3)2 along with amorphous pyrophosphate M2P2O7 in a 2:1 ratio. Similar heat treatment on samples 6-8 results in the exclusive formation of the respective metaphosphates Co(PO3)2, Ni(PO3)2, and Zn(PO3)2; the tetrahedral derivative 10 also cleanly converts into Co(PO3)2 on heating above 600 degrees C.     

A bridge between pillared-layer and helical structures: a series of three-dimensional pillared coordination polymers with multiform helical chains

Rational self-assembly of a long V-shaped 3,3',4,4'-benzophenonetetracarboxylate (bptc) ligand and metal salts in the presence of linear bidentate ligand yield a series of novel pillared helical-layer complexes, namely, [Cu2(bptc)(bpy)2] (1), [M3(Hbptc)2(bpy)3(H2O)4].2 H2O (M = Fe(2) and Ni(3)), [Co2(bptc)(bpy)(H2O)].0.5 bpy (4), [Cd2(bptc)(bpy)(H2O)2].H2O (5), [Mn2(bptc)(bpy)1.5(H2O)3] (6) and [M2(bptc)(bpy)0.5(H2O)5].0.5 bpy (M = Mn(7), Mg(8) and Co(9), bpy=4,4'-bipyridine). Their structures were determined by single-crystal X-ray diffraction analyses and further characterized by elemental analyses, IR spectra, and thermogravimetric (TG) analyses. The structure of 1 consists of two types of chiral layers, one left-handed and the other right-handed, which are connected by bpy pillars to generate a novel 3D open framework featuring four distinct helical chains. Compounds 2 and 3 are isostructural and feature 3D structures formed from the interconnection of arm-shaped helical layers with bpy pillars. Compound 4 is a pillared helical double-layer complex containing four different types of helices, among which the nine-fold interwoven helices constructed from triple-stranded helical motifs are unprecedented. Compound 5 exhibits a novel 3D covalent framework which features nanosized tubular channels. These channels are built from helical layers pillared by bptc ligands. The structure of 6 is constructed from {Mn(bptc)(H2O)}n2n- layers, which consist of left- and right-handed helical chains, pillared by [Mn2(bpy)3(H2O)4]4+ complexes into a 3D framework. To the best of our knowledge, compounds 1-6 are the first examples of pillared helical-layer coordination polymers. Compounds 7-9 are isostructural and exhibit interesting 2D helical double-layer structures, which are constructed from {M(bptc)(H2O)2}n2n- ribbons cross-linked by [M2(bpy)(H2O)6]4+ complexes. Furthermore, the 3D supramolecular structures of 7-9 are similar to the 3D structure of 6, and the 2D structure of 7 can be transformed into the 3D structure of 6 at higher reaction temperature. By inspection of the structures of 1-9, it is believed that the V-shaped bptc ligand and V-shaped phthalic group of the bptc ligand are important for the formation of the helical structures. The magnetic behavior of compounds 1, 2, 4, 6, and 9 was studied and indicated the existence of antiferromagnetic interactions. Moreover, compound 5 shows intense photoluminescence at room temperature.     

溶剂热法合成新型锑硒化合物[M~1(C_4H_(13)N_3)_2]_n[M~2Sb_2Se_5]_n(M~1=Mn、Co,M~2=Zn、Cd)及结构

以二乙烯三胺为模板剂,通过溶剂热法制备了一种新型有机无机杂化锑硒化合物:[M1(C4H13N3)2]n[M2Sb2Se5]n(M1=Mn、Co,M2=Zn、Cd).相比传统的有机无机杂化锑硒化合物,过渡金属Zn和Cd参与了这种化合物主框架的构建,使化合物的主框架由传统的SbSex单元转变为Zn(Cd)SbSe5的配位单元.据我们所知,这是第一次合成出Zn和Cd参与SbSex骨架配位的有机无机杂化锑硒化合物.同时,由于结构中CdSe4和ZnSe4单元的存在,使得该化合物表现出荧光性质.这种化合物的出现,使得我们有可能通过相同的途径合成出一系列具有该类型结构特征,在发光领域有潜在应用前景的新型锑硒化合物.     

Tetranuclear clusters containing a CrIII-doped MnIII4O2 core: syntheses, structures, and magnetic properties

The oxidation of MnII carboxylates by (NBu4)Cr2O7 in the presence of different phosphonic acids and chelating ligands results in six CrIII-doped tetranuclear manganese clusters formulated [Mn3CrO2(O2CCH3)4(O3PC5H4N)2(bpy)2] (1), [Mn3CrO2(O2CCH3)4(O3PC5H4N)2(phen)2] (2), [Mn3CrO2(O2CPh)4(O3PC5H4NO)2(phen)2] (3), [Mn3CrO2(O2CPh)4(O3PC6H11)2(bpy)2] (4), [Mn 3CrO2(O2CPh)4(O3PC6H11)2(phen) 2] (5), and [Mn3CrO2(O2CCH3)4(O3PC6H11)2(bpy)2] (6). Single-crystal X-ray analyses reveal that all the compounds contain similar [M4O2]8+ cores with the four metal sites arranged in planar topologies. The metal ions within the core are bridged by both carboxylate and phosphonate ligands. Temperature-dependent magnetic measurements show that in all cases dominant antiferromagnetic interactions are propagated between the metal centers. The ac magnetic measurements on compounds 5 and 6 reveal that both the in-phase and the out-of-phase signals are frequency dependent, characteristic of single-molecule magnet behaviors.     

Nonlinear optically active polymeric coordination networks based on metal m-pyridylphosphonates

A family of polymeric coordination networks based on meta-pyridylphosphonate bridging ligands has been synthesized and characterized by single-crystal X-ray crystallography. Compounds [M(2)(L-Et)(4)(mu-H(2)O)] (M = Mn, 1; Co, 2; Ni, 3; L-Et = ethyl-4-[2-(3-pyridyl)ethenyl]phenylphosphonate) were obtained by hydro(solvo)thermal reactions between diethyl-4-[2-(3-pyridyl)ethenyl]phenylphosphonate (L-Et(2)) and corresponding metal salts, while [Cd(L-H)(2)], 4 (L-H is monoprotonated 4-[2-(3-pyridyl)ethenyl]phenylphosphonate), was obtained by a hydro(solvo)thermal reaction between (L-H(2)).HBr and Cd(CF(3)SO(3))(2).6H(2)O. Compounds 1-3 are isostructural and crystallize in noncentrosymmetric space group Fdd2, and they adopt a complicated 3D framework structure composed of [M(2)(L-Et)(4)(mu-H(2)O)] building units, while compound 4 adopts a centrosymmetric 3D network structure resulted from linking 1D sinusoidal cadmium phosphate chains with L-H bridging ligands. Consistent with their polar structures, compounds 1-3 exhibit powder second harmonic generation signals larger than that of potassium dihydrogen phosphate.     

Monomeric, tetrameric, and polymeric copper di-tert-butyl phosphate complexes containing pyridine ancillary ligands

The reaction of di-tert-butyl phosphate (((t)BuO)(2)P(O)(OH), dtbp-H) with copper acetate in the presence of pyridine (py) and 2,4,6-trimethylpyridine (collidine) has been investigated. Copper acetate reacts with dtbp-H in a reaction medium containing pyridine, DMSO, THF, and CH(3)OH to yield a one-dimensional polymeric complex [Cu(dtbp)(2)(py)(2)(mu-OH(2))](n) (1) as blue hollow crystalline tubes. The copper atoms in 1 are octahedral and are surrounded by two terminal phosphate ligands, two pyridine molecules, and two bridging water molecules. The mu-OH(2) ligands that are present along the elongated Jahn-Teller axis are responsible for the formation of the one-dimensional polymeric structure. Recrystallization of 1 in a DMSO/THF/CH(3)OH mixture results in the reorganization of the polymer and its conversion to a more stable tetranuclear copper cluster [Cu(4)(mu(3)-OH)(2)(dtbp)(6)(py)(2)] (2) in about 60% yield. The molecular structure of 2 is made up of a tetranuclear core [Cu(4)(mu(3)-OH)(2)] which is surrounded by six bidentate bridging dtbp ligands. While two of the copper atoms are pentacoordinate with a tbp geometry, the other two copper atoms exhibit a pseudooctahedral geometry with five normal Cu-O bonds and an elongated Cu-O linkage. The pentacoordinate copper centers bear an axial pyridine ligand. The short Cu.Cu nonbonded distances in the tetranuclear core of 2 lead to magnetic ordering at low temperature with an antiferromagnetic coupling at approximately 20 K (J(P) = -44 cm(-1), J(c) = -66 cm(-1), g = 2.25, and rho = 0.8%). When the reaction between di-tert-butyl phosphate (dtbp-H) and copper acetate was carried out in the presence of collidine, large dark-blue crystals of monomeric copper complex [Cu(dtbp)(2)(collidine)(2)] (3) formed as the only product. A single-crystal X-ray diffraction study of 3 reveals a slightly distorted square-planar geometry around the copper atom. Thermogravimetric analysis of 1-3 revealed a facile decomposition of the coordinated ligands and dtbp to produce a copper phosphate material around 500 degrees C. An independent solid-state thermolysis of all the three complexes in bulk at 500-510 degrees C for 2 days produced copper pyrophosphate Cu(2)P(2)O(7) along with small quantities of Cu(PO(3))(2) as revealed by DR-UV spectroscopic and PXRD studies.     

过渡金属二取代三元杂多酸盐的制备和表征

在水中由Na2 WO4 ·2H2 O ,Na2 MoO4 ·2H2 O和KH2 PO4 ·2H2 O反应生成具有半Dawson结构的钨钼混配杂多阴离子Na9PW6Mo3O34 ·1 0H2 O。以阴离子和过渡金属硝酸盐为原料在水溶液中合成了一系列过渡金属二取代的具有Keggin结构的杂多酸四丁基铵盐 [TBA]4 Hn[PW7Mo3M2 O38(H2 O) 2 ]·C3H6O(n =1 ,M =Fe3+;n =3,M =Mn2 +,Co2 +,Ni2 +,Cu2 +) ,用元素分析和波谱进行了表征。     

Self-assembly, crystal structures, and properties of metal-2-sulfoterephthalate frameworks based on [M4(μ3-OH)2]6+ clusters (M = Co, Mn, Zn and Cd)

Hydro- and solvo-thermal reactions of d-block metal ions (Mn(2+), Co(2+), Zn(2+) and Cd(2+)) with monosodium 2-sulfoterephthalate (NaH(2)stp) form six 3D coordination polymers featuring cluster core [M(4)(μ(3)-OH)(2)](6+) in common: [M(2)(μ(3)-OH)(stp)(H(2)O)] (M = Co (1), Mn (2) and Zn (3)), [Zn(2)(μ(3)-OH)(stp)(H(2)O)(2)] (4), [Zn(4)(μ(3)-OH)(2)(stp)(2)(bpy)(2)(H(2)O)]·3.5H(2)O (5) and [Cd(2)(μ(3)-OH)(stp) (bpp)(2)]·H(2)O (6) (stp = 2-sulfoterephthalate, bpy = 4,4'-bipyridine and bpp = 1,3-di(4-pyridyl)propane). All these coordination polymers were characterized by single crystal X-ray diffraction, IR spectroscopy, thermogravimetric and elemental analysis. Complexes 1-3 are isostructural coordination polymers with 3D frameworks based on the chair-like [Zn(4)(μ(3)-OH)(2)](6+) core and the quintuple helixes. In complex 4, there exist double helixes in the 3D framework based on the chair-like cluster cores. Complex 5 possesses a 2-fold interpenetration structure constructed from boat-like cluster core and the bridging ligands stp and bpy. For complex 6, the chair-like cluster cores and stp ligands form a 2D (4,4) network which is further pillared by bpp linkers to a 3D architecture. Magnetic studies indicate that complex 1 exhibits magnetic ordering below 4.9 K with spin canting, and complex 2 shows weak antiferromagnetic coupling between the Mn(II) ions with g = 2.02, J(wb) = -2.88 cm(-1), J(bb) = -0.37 cm(-1). The fluorescence studies show that the emissions of complexes 3-6 are attributed to the ligand π-π* transition.     

Mono- and Dinuclear Transition Metal Complexes of the Hexadentate Ligand Tris(4-tert-butyl-2-mercaptobenzyl)-1,4,7-triazacyclononane (L)

The hexadentate, pendant arm macrocycle 1,4,7-tris(4-tert-butyl-2-mercaptobenzyl)-1,4,7-triazacyclononane (H(3)L) has been synthesized and isolated as its trihydrochloride, H(3)L.3HCl, or sodium salt, Na(3)L, and its coordination chemistry with first-row transition metals has been studied. Mononuclear complexes of the type [LM(III)] (M = Ga (1), In (2), V (3), Cr (4), Mn (5), Fe,Co (6)) have been isolated as have the one-electron-oxidized forms [LM]PF(6) (M = V(IV) (3a), Mn(IV) (5a)). The crystal structure of 6 has been determined by single-crystal X-ray crystallography. Complex 6 crystallizes in the orthorhombic space group Iba2, with cell constants a = 14.206(8) ?, b = 22.53(1) ?, c = 26.07(1) ?, V = 8344.0(3) ?(3), and Z = 8. The cobalt(III) ion is in a distorted octahedral fac-N(3)S(3) donor set. The reaction of L with divalent metal chlorides in a 1:2 ratio in methanol affords the homodinuclear complexes [LM(II)(2)Cl] (M = Mn (7), Co (8), Ni (9), Zn (10), Cd (11)) where one metal is six- (N(3)MS(3)) and the other is four-coordinate (S(3)MCl); the two polyhedra are linked by three &mgr;(2)-thiolato bridges. Heterodinuclear complexes of the type [LM(1)M(2)Cl] have been obtained from [LM(2)Cl] species by abstraction of the four-coordinate metal ion and replacement by a different metal ion. The complexes [LZn(II)M(II)Cl] (M = Fe (12), Co (13), Ni (14)), [LNi(II)M(II)Cl] (M = Co (15), Zn (16)), and [LMn(II)M(II)Cl] (M = Fe (17), Co (18), Ni (19), Zn (20), Cd (21), Hg (22)) have been isolated as solid materials. The crystal structure of 14 has been determined by X-ray crystallography. Complex 14 crystallizes in the orthorhombic space group P2(1)2(1)2(1), with cell constants a = 15.45(1) ?, b = 17.77(1) ?, c = 17.58(1) ?, V = 4826.5(4) ?(3), and Z = 4. The linkage isomers 14 and 16 show characteristic electronic spectra for octahedrally and tetrahedrally coordinated Ni(II), respectively. The electronic structures of new complexes have been investigated by UV-vis spectroscopy; their magnetochemistry and electrochemistry are reported.     

Cubic and rhombohedral heterobimetallic networks constructed from uranium, transition metals, and phosphonoacetate: new methods for constructing porous materials

Four heterobimetallic U(vi)/M(ii) (M = Mn, Co, Cd) carboxyphosphonates have been synthesized. M(2)[(UO(2))(6)(PO(3)CH(2)CO(2))(3)O(3)(OH)(H(2)O)(2)]·16H(2)O (M = Mn(ii), Co(ii), and Cd(ii)) adopt cubic three-dimensional network structures with large cavities approximately 16 ? in diameter that are filled with co-crystallized water molecules. [Cd(3)(UO(2))(6)(PO(3)CH(2)CO(2))(6)(H(2)O)(13)]·6H(2)O forms a rhombohedral channel structure with hydrated Cd(ii) within the channels. The cubic compound (Co) displays differential gas absorption with a surface area for CO(2) uptake of 40 m(2) g(-1) at 273 K, and no uptake of N(2) at 77 K.     

Metal aminocarboxylate coordination polymers with chain and layered structures

The synthesis and structures of metal aminocarboxylates prepared in acidic, neutral, or alkaline media have been explored with the purpose of isolating coordination polymers with linear chain and two-dimensional layered structures. Metal glycinates of the formulae [CoCl2(H2O)2(CO2CH2NH3)] (I), [MnCl2(CO2CH2NH3)2] (II), and [Cd3Cl6(CO2CH2NH3)4] (III) with one-dimensional chain structures have been obtained by the reaction of the metal salts with glycine in an acidic medium under hydro/solvothermal conditions. These chain compounds contain glycine in the zwitterionic form. 4-Aminobutyric acid transforms to a cyclic amide under such reaction conditions, and the amide forms a chain compound of the formula [CdBr2(C4H7NO)2] (IV). Glycine in the zwitterionic form also forms a two-dimensional layered compound of the formula [Mn(H2O)2(CO2CH2NH3)2]Br2 (V). 6-Aminocaproic acid under alkaline conditions forms layered compounds with metals at room temperature, the metal being coordinated both by the amino nitrogen and the carboxyl oxygen atoms. Of the two layered compounds [Cd{CO2(CH2)5NH2}2]2 H2O (VI) and [Cu{CO2(CH2)5NH2}2]2 H2O (VII), the latter has voids in which water molecules reside.     

Synthesis, Crystal Structure and Property of a Series of Supramolecular Polymers Based on Novel 3,5-Dimethyl- 2,6-bis（3-（pyrid-2-yl）-1,2,4-triazolyl）pyridine Ligand

Solvothermal reactions of 3,5-dimethyl-2,6-bis(3-(pyrid-2-yl)-1,2,4-triazolyl) pyridine (L), 1,4-benzendicarboxylic acid (H2bdc), and transitional metal cations of MII (M = Mn, Co, Cd) in the presence of oxalic acid (H2ox) afford three novel supramolecular polymers (CPs), namely, {[M2(ox)(L)2][bdc][M2(Hox)2(OH)2(H2O)4].3H2O}n (M=Mn for 1, Co for 2, Cd for 3). Single-crystal X-ray diffraction analysis reveals that complexes 1-3 are isostructural and the 3D supramolecular structure was connected through non-covalent interactions. With the help of H2ox, the L ligands cheated with center atoms forming a butterfly [M2(ox)(L)2]2+ building block. The bdc2- ligand linked with the unprecedented [M2(Hox)2(OH)2(H2O)4] units through strong O-H…O hydrogen bonds forming a zigzag chain, which are further connected through π…π interactions between L and bdc2- ligands to form a 3D supramolecular structure. Moreover, elemental analyses, IR, thermogravimetric, PXRD and luminescence have been investigated.     

Rationally designed, polymeric, extended metal-ciprofloxacin complexes

Reactions of the antimicrobial fluoroquinolone ciprofloxacin (cfH) with metal salts in the presence of aromatic polycarboxylate ligands or under basic conditions produce fourteen new metal-cfH complexes, namely, [Ba2(cf)2(1,4-bdc)(H2O)2] x H2O (1), [Sr6(cf)6(1,4-bdc)3(H2O)6] x 2H2O (2), [M2(cfH)2(bptc)(H2O)2] x 8H2O (M = Mn3 and Cd4), [M(cfH)(1,3-bdc)] (M = Mn5, Co6, and Zn7), [Zn2(cfH)4(1,4-bdc)](1,4-bdc) x 13H2O (8), [Ca(cfH)2(1,2-Hbdc)2] x 2H2O (9) and [M(cf)2] x 2.5H2O (M = Mn10, Co11, Zn12, Cd13, and Mg14) (1,4-bdc = 1,4-benzenedicarboxylate, bptc = 3,3',4,4'-benzophenonetetracarboxylate, 1,3-bdc = 1,3-benzenedicarboxylate, 1,2-bdc = 1,2-benzenedicarboxylate). Their structures were determined by single-crystal X-ray diffraction analyses and further characterized by elemental analyses, IR spectra, and thermogravimetric analyses. The structures of 1 and 2 consist of unique two-dimensional arm-shaped layers. Compounds 3 and 4 are isostructural and feature one-dimensional structures formed from the interconnection of [M2(cfH)2(H2O)2] dimers with bptc ligands. Compounds 5-7 are isostructural and contain double-chain-like ribbons constructed from [M2(cfH)2(CO2)2] dimers and 1,3-bdc. Compound 8 consists of a pair of [Zn(cfH)2]2+ fragments bridged by a 1,4-bdc into a dinuclear dumbbell structure. Compound 9 is a neutral monomeric complex. To the best of our knowledge, compounds 1-9 are the first examples of metal-quinolone complexes that contain aromatic polycarboxylate ligands. Compounds 10-14 are isostructural and exhibit interesting two-dimensional rhombic grids featuring large cavities with dimensions of 13.6x13.6 A. Up to now, polymeric extended metal-cfH complexes have never been reported.     

Structure of Metal Aluminophosphates:Al9-xMxP12O48(TREN)4·yNH4·zH2O[TREN=N(CH2CH2NH3)Hm, M=Mn, Co]

Two large-pore metal-doped aluminophosphates, Mn4Al5(PO4)12[N(C2H4NH3)3]3[N(C2H4NH3)2·(C2H4NH2)](NH4)2·14H2O(Mn4-NJU) and Co4Al5(PO4)12[N(C2H4NH3)3][N(C2H4NH3)2(C2H4NH2)]3·(NH4)4·13H2O(Co4-NJU), which have the same open framework structures, were hydrothermally synthesized. The structures of these compounds consist of TO4 tetrahedra, which are linked together by corner-sharing to form an open framework with unique intersecting twelve-membered ring channels in three dimensions. The compounds crystallize in cubic space group I(-4)3m with a=1.6795(2) nm and V=4.7374(9) nm3 for Mn4-NJU, and a=1.67372(19) nm and V=4.6887(9) nm3 for Co4-NJU, respectively. Single crystal structure analyses show that the protruding O atoms of the frameworks of the compounds are linked to protonated 4-(2-aminoethyl)diethylenetriamine(TREN, C6H18N4) ions in the windows by means of hydrogen-bonding under the hydrothermal condition. It is also found that the components inside the super cages of the compounds are changeable, and the metal ions M2 (M=Mn, Co) and Al3 disorderedly occupy the same crystallographic positions.     

Impact of metal-ion dependence on the porous and electronic properties of TCNQ-dianion-based porous coordination polymers

A series of TCNQ-dianion-based porous coordination polymers [M(TCNQ)bpy] (M = Fe, Zn, Mn, Co, Cd) have been synthesized and characterized. The synthesis reactions of these compounds are promoted by the addition of ascorbic acid, which is the key to obtaining a high yield. They form almost identical three-dimensional pillared layer structures with the M-TCNQ two-dimensional layers linked by bpy pillar ligands. The electronic properties of these compounds vary depending on the constitutional metal ions and guest molecules. We found that the electronic interaction between metal ions and TCNQ moieties in the frameworks strongly impacted the electronic properties of the compounds.     

Three-dimensional open-framework cobalt(II) phosphates by novel routes

Two new three-dimensional open-framework cobalt phosphates, [C2N2H10]2[Co4(PO4)4]H2O, I, and [C4N3H16]3-[Co6(PO4)5(HPO4)3]H2O, II, have been prepared by the reaction of amine phosphates with Co2+ salts. I could also be prepared by the reaction of the cobalt tris amine complex with H3PO4. The crystal data for I and II are as follows: phosphate I, orthorhombic, space group P2(1)2(1)2(1) (no. 19), a = 10.277 (1) A, b = 10.302 (1) A, c = 18.836 (1) A, V = 1994.2 (2) A3, Z = 4; phosphate II, monoclinic, space group P2(1)/c (No. 14), a = 31.950 (1) A, b = 8.360 (1) A, c = 15.920 (1) A, beta = 96.6 (1) degrees V = 4223.4 (2) A3, Z = 4. The structures of both I and II are constructed from alternating CoO4 and PO4 tetrahedra. The connectivity leads to the formation of eight-membered channels in all the crystallographic directions resembling the aluminosilicate zeolite, merlinoite in the case of I and to a rather large, one-dimensional 16-membered channel in II. Strong hydrogen-bond interactions involving the amine and framework oxygen are present in both I and II.     

A series of pillar-layer metal-organic frameworks based on 5-aminoisophthalic acid and 4,4'-bipyridine

Four new compounds, [Cd(5-aip)(bpy)]·1.5DMA (1), [Cu(5-aip)(bpy)]·1.3DMA (2), [Co(5-aip)(bpy)]·1.6DMA (3), and [Cd(5-aip)(bpy)(0.5)(H(2)O)]·1.3DMA (4), based on 5-aminoisophthalic acid and 4,4'-bipyridine, have been synthesized by the solvothermal method and structurally determined using single crystal X-ray diffraction. Compounds 1-3 are structurally similar and show non-interpenetrating three-dimensional (3D) pillar-layer frameworks, while compound 4 displays a two-dimensional (2D) (3,4)-connected parallel non-interpenetrating architecture. In all these compounds, 1D rectangular channels are observed and the ligand 5-aminoisophthalic acid exhibits three kinds of coordination modes. Furthermore, 1 displays a single-crystal-to-single-crystal transformation when immersed in a methanol solution. More significantly, 1 can absorb and deliver I(2) molecules by means of its channels, and could induce a reversible luminescent transformation from quenching to the initial state. The luminescent properties of 1 and 4 have also been studied.     

二茂铁基取代酰腙的一些过渡金属配合物

本文制备了两个金属有机配位体,肉桂醛二茂铁基甲酰腙(HL^1)和二[(1-肉桂酰肼基乙基)环戊二烯基]铁(H~2L^2)及它们与一些过渡金属的配合物:ML~2^1[M=Cu(II)],ML^2[(M=Cu(II)和Zn(II)],M(HL^1)~2Cl~2[M=Cd(II),Co(II)和Ni(II)],M(H~2L^2)Cl~2[M=Mn(II),Zn(II),Co(II)和Cd(II)]。这两个配位体以烯醇式与M(OAc)~2.nH~2O中心离子配位,与MCl~2.nH~2O则以酮式配位。