Novel manganese(II) sulfonate-phosphonates with dinuclear, tetranuclear, and hexanuclear clusters

Hydrothermal reactions of manganese(II) salts with m-sulfophenylphosphonic acid (m-HO3S-Ph-PO3H2, H3L) and 1,10-phenanthroline (phen) led to six novel manganese(II) sulfonate-phosphonates, namely, [Mn2(HL)2(phen)4][Mn2(HL)2(phen)4(H2O)](2).6H2O (1), [Mn4(L)2(phen)8(H2O)2][ClO4](2).3H2O (2), [Mn(phen)(H2O)4]2[Mn4(L)4(phen)4].10H2O (3), [Mn6(L)4(phen)8(H2O)2].4H2O (4), [Mn6(L)4(phen)8(H2O)2].24H2O (5), and [Mn6(L)4(phen)6(H2O)4].5H2O (6). The structure of 1 contains two types of dinuclear manganese(II) clusters, and 2-3 exhibit two types of tetranuclear manganese(II) cluster units. 4-5 feature two different types of isolated hexanuclear manganese(II) clusters, whereas the hexanuclear manganese(II) clusters in 6 are bridged by sulfonate-phosphonate ligands into a 1D chain. Magnetic property measurements indicate that there exist weak antiferromagnetic interactions between magnetic centers in all six compounds.     

Self-encapsulation of [MII(phen)2(H2O)2]2+ (M=Co, Zn) in one-dimensional nanochannels of [MII(H2O)6(BTC)2]4- (M=Co, Cu, Mn): a high HQ/CAT ratio catalyst for hydroxylation of phenols

Four novel three-dimensional (3D) microporous supramolecular compounds containing nanosized channels, namely, [Co(phen)2(H2O)2]2[Co(H2O)6].2BTC.21.5H2O (1), [Co(phen)2(H2O)2]2[Cu(H2O)6].2BTC.21.5H2O (2), [Co(phen)2(H2O)2]2[Mn(H2O)6].2BTC.18H2O (3), and [Zn(phen)2(H2O)2]2[Mn(H2O)6].2BTC.22.5H2O (4), were synthesized from 1,3,5-benzenetricarboxylate (BTC), 1,10-phenanthroline (phen), and the transition-metal salt(s) by self-assembly. Single-crystal X-ray structural analysis showed that the resulting 3D microporous supramolecular frameworks consist of a two-dimensional (2D) hydrogen-bonded host framework of [MII(H2O)6(BTC)2]4- (M=Co for 1, Cu for 2, Mn for 3, 4) with rectangular-shaped cavities containing [MII(phen)2(H2O)2]2+ (M=Co for 1-3, Zn for 4) guests. The guest complex is encapsulated in the 2D hydrogen-bonded host framework by hydrogen bonding and aromatic pi-pi stacking interactions, forming the 3D hydrogen-bonded framework. The catalytic activities of 1, 2, 3, and 4 were studied using hydroxylation of phenols with 30% aqueous H2O2 as a test reaction. The compounds displayed a good phenol conversion ratio and excellent channel selectivity in the hydroxylation reaction, with a maximum hydroquinone (HQ)/catechol (CAT) ratio of 3.9.     

Phase separation in liquid crystalline mesophases of [Co(H2O)6]X2:P65 Systems (X = NO3-, Cl-, or ClO4-)

Transition-metal aqua complex salts [M(H2O)6]X2 (where M is Mn(II), Co(II), Ni(II), Zn(II), or Cd(II) and X is NO3-, Cl-, or ClO4-) can be dissolved in triblock poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) copolymers (Pluronics, such as P65) to form homogeneous liquid crystalline (LC) mesophases. However, the [Co(H2O)6]X2:P65 LC mesophases slowly undergo phase separation into a disordered ion-free phase and an ordered ion-rich LC mesophase. The phase separation also takes place in the two-salt systems [Co(H2O)6](NO3):[Co(H2O)6](ClO4)2:P65 in which the ion-free disordered domains separate out from the initially ordered homogeneous mesophase. The phase separation results in a physical mixture of a hexagonal nitrate-rich and cubic perchlorate-rich LC and disordered ion-free domains in the mixed salt systems. The driving force in the phase separation in the [Co(H2O)6]X2:P65 system is Co(II)-catalyzed aerobic oxidation of P65 into ester and/or other oxidation products. The separation of ions in the [Co(H2O)6](NO3)2:[Co(H2O)6](ClO4)2:P65 system is related to the mesostructures of the two-salt systems that are different, hexagonal in the [Co(H2O)6](NO3)2:P65 system and cubic in the [Co(H2O)6](ClO4)2:P65 system. There is no visible phase separation in the other transition-metal salt:P65 systems. The phase separation in the [Co(H2O)6]X2:P65 systems can also be eliminated by keeping the mesophase under a N2 atmosphere.     

Coordination networks with fluorinated backbones

Fluorine-containing ligands 2,3,5,6-tetrafluoro-1,4-bis(imidazol-1-yl-methyl)benzene (1) and 2,3,5,6-tetrafluoro-1,4-bis(2-methylimidazol-1-yl-methyl)benzene (2) were prepared and coordinated with AgNO3, Co(ClO4)2 x 6 H2O, and Cd(NO3)2 x 4 H2O, respectively, to form the following structures: 3D channel polymer [Ag2(1)2(NO3)2 x H2O x MeOH]n (3), 2D sheet polymer [Co(1)3(ClO4)2]n (4), 1D chain polymer [Cd(1)3(NO3)2 x 4 H2O]n (5), and a 2D herringbone sheet polymer [Ag(2)NO3 x 1.5 MeOH]n (6). The solid-state crystal structures of 3-6 were studied by single-crystal X-ray crystallography.     

2-Aminoisobutyric acid in Co(II) and Co(II)/Ln(III) chemistry: homometallic and heterometallic clusters

The synthesis and magnetic properties of 13 new homo- and heterometallic Co(II) complexes containing the artificial amino acid 2-amino-isobutyric acid, aibH, are reported: [Co(II)(4)(aib)(3)(aibH)(3)(NO(3))](NO(3))(4)·2.8CH(3)OH·0.2H(2)O (1·2.8CH(3)OH·0.2H(2)O), {Na(2)[Co(II)(2)(aib)(2)(N(3))(4)(CH(3)OH)(4)]}(n) (2), [Co(II)(6)La(III)(aib)(6)(OH)(3)(NO(3))(2)(H(2)O)(4)(CH(3)CN)(2)]·0.5[La(NO(3))(6)]·0.75(ClO(4))·1.75(NO(3))·3.2CH(3)CN·5.9H(2)O (3·3.2CH(3)CN·5.9H(2)O), [Co(II)(6)Pr(III)(aib)(6)(OH)(3)(NO(3))(3)(CH(3)CN)(6)]·[Pr(NO(3))(5)]·0.41[Pr(NO(3))(3)(ClO(4))(0.5)(H(2)O)(1.5)]·0.59[Co(NO(3))(3)(H(2)O)]·0.2(ClO(4))·0.25H(2)O (4·0.25H(2)O), [Co(II)(6)Nd(III)(aib)(6)(OH)(3)(NO(3))(2.8)(CH(3)OH)(4.7)(H(2)O)(1.5)]·2.7(ClO(4))·0.5(NO(3))·2.26CH(3)OH·0.24H(2)O (5·2.26CH(3)OH·0.24H(2)O), [Co(II)(6)Sm(III)(aib)(6)(OH)(3)(NO(3))(3)(CH(3)CN)(6)]·[Sm(NO(3))(5)]·0.44[Sm(NO(3))(3)(ClO(4))(0.5)(H(2)O)(1.5)]·0.56[Co(NO(3))(3)(H(2)O)]·0.22(ClO(4))·0.3H(2)O (6·0.3H(2)O), [Co(II)(6)Eu(III)(aib)(6)(OH)(3)(NO(3))(3)(CH(3)OH)(4.87)(H(2)O)(1.13)](ClO(4))(2.5)(NO(3))(0.5)·2.43CH(3)OH·0.92H(2)O (7·2.43CH(3)OH·0.92H(2)O), [Co(II)(6)Gd(III)(aib)(6)(OH)(3)(NO(3))(2.9)(CH(3)OH)(4.9)(H(2)O)(1.2)]·2.6(ClO(4))·0.5(NO(3))·2.58CH(3)OH·0.47H(2)O (8·2.58CH(3)OH·0.47H(2)O), [Co(II)(6)Tb(III)(aib)(6)(OH)(3)(NO(3))(3)(CH(3)CN)(6)]·[Tb(NO(3))(5)]·0.034[Tb(NO(3))(3)(ClO(4))(0.5)(H(2)O)(0.5)]·0.656[Co(NO(3))(3)(H(2)O)]·0.343(ClO(4))·0.3H(2)O (9·0.3H(2)O), [Co(II)(6)Dy(III)(aib)(6)(OH)(3)(NO(3))(2.9)(CH(3)OH)(4.92)(H(2)O)(1.18)](ClO(4))(2.6)(NO(3))(0.5)·2.5CH(3)OH·0.5H(2)O (10·2.5CH(3)OH·0.5H(2)O), [Co(II)(6)Ho(III)(aib)(6)(OH)(3)(NO(3))(3)(CH(3)CN)(6)]·0.27[Ho(NO(3))(3)(ClO(4))(0.35)(H(2)O)(0.15)]·0.656[Co(NO(3))(3)(H(2)O)]·0.171(ClO(4)) (11), [Co(II)(6)Er(III)(aib)(6)(OH)(4)(NO(3))(2)(CH(3)CN)(2.5)(H(2)O)(3.5)](ClO(4))(3)·CH(3)CN·0.75H(2)O (12·CH(3)CN·0.75H(2)O), and [Co(II)(6)Tm(III)(aib)(6)(OH)(3)(NO(3))(3)(H(2)O)(6)]·1.48(ClO(4))·1.52(NO(3))·3H(2)O (13·3H(2)O). Complex 1 describes a distorted tetrahedral metallic cluster, while complex 2 can be considered to be a 2-D coordination polymer. Complexes 3-13 can all be regarded as metallo-cryptand encapsulated lanthanides in which the central lanthanide ion is captivated within a [Co(II)(6)] trigonal prism. dc and ac magnetic susceptibility studies have been carried out in the 2-300 K range for complexes 1, 3, 5, 7, 8, 10, 12, and 13, revealing the possibility of single molecule magnetism behavior for complex 10.     

Two-dimensional networks based on Mn4 complex linked by dicyanamide anion: from single-molecule magnet to classical magnet behavior

Three two-dimensional (2D) network compounds based on Mn(III)/Mn(II) tetranuclear single-molecule magnets (SMMs) connected by dicyanamide (dcn-) linkers have been synthesized: [Mn4(hmp)4(Hpdm)2(dcn)2](ClO4)2 x 2 H2O x 2 MeCN (2), [Mn4(hmp)4Br2(OMe)2(dcn)2] x 0.5 H2O x 2 THF (3), [Mn4(hmp)6(dcn)2](ClO4)2 (4), where Hhmp and H2pdm are 2-hydroxymethylpyridine and pyridine-2,6-dimethanol, respectively. The [Mn4]/dcn- system appears very versatile, but enables its chemistry to be rationalized by a fine-tune of the synthetic conditions. The double cuboidal [Mn4] unit is preserved in the whole family of compounds, despite strong modifications of its Mn(II) coordination sphere. The chemical control of the coordination number of dcn- on the Mn(II) sites has been the key to obtain the following series of compounds: a discrete cluster, [Mn4(hmp)6(NO3)2(dcn)2] x 2 MeCN (1), 2D networks (2, 3, and 4), and the previously reported 3D compound, [Mn4(hmp)4(mu3-OH)2][Mn(II)(dcn)6] x 2 MeCN x THF. Direct current magnetic measurements show that both Mn2+-Mn3+ and Mn3+-Mn3+ intra-[Mn4] magnetic interactions are ferromagnetic leading to an S(T) = 9 ground state for the [Mn4] unit. Despite the very similar 2D lattices in 2-4, the two kinds of orientation of the [Mn4] unit (i.e., angle variations between the two easy axes) lead to different magnetic properties ranging from SMM behavior for 2 and 1 to a long-range canted antiferromagnetic order for 4. Compound 3 is more complicated as the magnetic measurements strongly suggest the presence of a canted antiferromagnetic order below 2.1 K, although the magnetization slow relaxation is simultaneously observed. Heat capacity measurements confirm the long-range magnetic order in 4, while in 3, the critical behavior is frozen by the slow relaxation of the anisotropic [Mn4] units.     

Synthesis and structure of manganese(ii) coordination polymers with 1,4-diazabicyclo[2.2.2]octane N,N′-dioxide: solvent and template effects

Russian Chemical Bulletin - New metal-organic frameworks [Mn(DMF)2(odabco)2](ClO4)2 · H2O (1), [Mn(H2O)2? (HCOO)2] · odabco (2), and [Mn(Hodabco)2(odabco)3](NO3)4 (3) were...     

Pentanuclear homoleptic M(5)L(6) (M = Mn(II), Co(II), Zn(II)) complexes formed by strict self-assembly

A series of trigonal bipyramidal pentanuclear complexes involving the alkoxo-diazine ligands poap and p3oap, containing the M(5)[mu-O](6) core is described, which form by a strict self-assembly process. [Co(5)(poap-H)(6)](ClO(4))(4).3H(2)O (1), [Mn(5)(poap-H)(6)](ClO(4))(4).3.5CH(3)OH.H(2)O (2), [Mn(5)(p3oap-H)(6)](ClO(4))(4).CH(3)CH(2)OH.3H(2)O (3), and [Zn(5)(poap-H)(6)](ClO(4))(4).2.5H(2)O (4) are homoleptic pentanuclear complexes, where there is an exact match between the coordination requirements of the five metal ions in the cluster, and the available coordination pockets in the polytopic ligand. [Zn(4)(poap)(poap-H)(3)(H(2)O)(4)] (NO(3))(5).1.5H(2)O (5) is a square [2 x 2] grid with a Zn(4)[mu-O](4) core, and appears to result from the presence of NO(3), which is thought to be a competing ligand in the self-assembly. X-ray structures are reported for 1, 4, and 5. 1 crystallized in the monoclinic system, space group P2(1)/n with a = 13.385(1) A, b = 25.797(2) A, c = 28.513(3) A, beta = 98.704(2) degrees, and Z = 4. 4 crystallized in the triclinic system, space group P1 with a = 13.0897(9) A, b = 18.889(1) A, c = 20.506(2) A, alpha = 87.116(1) degrees, beta = 74.280(2) degrees, gamma = 75.809(2) degrees, and Z = 2. 5 crystallized in the monoclinic system, space group P2(1)/n with a = 14.8222(7) A, b = 21.408(1) A, c = 21.6197(9) A, beta = 90.698(1) degrees, and Z = 4. Compounds 1-3 exhibit intramolecular antiferromagnetic coupling.     

Self-assembly of a series of extended architectures based on polyoxometalate clusters and silver coordination complexes

Three unusual compounds based on polyoxometalate building blocks, [(H2O)5Na2(C6NO2H4)(C6NO2H5)3Ag2][Ag2IMo6O24(H2O)4] x 6.25H2O (1), [(H2O)4Na2(C6NO2H5)6Ag3][IMo6O24] x 6H2O (2), and (C6NO2H6)2[(C6NO2H5)2Ag][Cr(OH)6Mo6O18] x 4H2O (3), have been synthesized and characterized by elemental analysis; IR, XPS, and ESR spectroscopy; TG analysis; and single-crystal X-ray diffraction. Compound 1 is constructed from the cationic two-dimensional (2D) coordination polymer sheets which are constituted of [(H2O)5Na2(C6NO2H4)(C6NO2H5)3Ag2]3+ and anionic [Ag2IMo6O24(H2O)4]3- chains as pillars, forming a three-dimensional (3D) supramolecular framework via weak Ag-O interactions. Compound 2 is composed of the well-defined [IMo6O24]5- building blocks, which are linked through trinuclear Ag-pyridine-3-carboxylic acid, [(C6NO2H5)6Ag3]3+, fragments into a one-dimensional (1D) hybrid chain; adjacent chains are further connected by sodium cations to yield a novel 2D network. Compound 3 has a 1D chainlike structure constructed from [Cr(OH)6Mo6O18]3- building blocks and Ag-pyridine-4-carboxylic acid coordination units. The crystal data for these compounds are the following: 1, triclinic, P1, a = 13.280(3) A, b = 13.641(3) A, c = 16.356(3) A, alpha = 89.68(3) degrees, beta = 88.31(3) degrees, gamma = 75.87(3) degrees, Z = 2; 2, triclinic, P1, a = 11.978(2) A, b = 12.008(2) A, c = 13.607(3) A, alpha = 116.14(3) degrees, beta = 108.85(3) degrees, gamma = 93.86(3) degrees, Z = 1; 3, triclinic, P1, a = 10.458(2) A, b = 10.644(2) A, c = 12.295(3) A, alpha = 97.40(3) degrees, beta = 112.38(3) degrees, gamma = 113.59(3) degrees, Z = 1.     

Metal ion-controlled self-assembly using pyrimidine hydrazone molecular strands with terminal hydroxymethyl groups: a comparison of Pb(II) and Zn(II) complexes

Metal complexation studies were performed with the ditopic pyrimidine-hydrazone (pym-hyz) strand 6-hydroxymethylpyridine-2-carboxaldehyde (2-methyl-pyrimidine-4,6-diyl)bis(1-methylhydrazone) (1) and Pb(ClO(4))(2)·3H(2)O, Pb(SO(3)CF(3))(2)·H(2)O, Zn(SO(3)CF(3))(2), and Zn(BF(4))(2) to examine the ability of 1 to form various supramolecular architectures. X-ray crystallographic and NMR studies showed that coordination of the Pb(II) salts with 1 on a 2:1 metal/ligand ratio in CH(3)CN and CH(3)NO(2) resulted in the linear complexes [Pb(2)1(ClO(4))(4)] (2), [Pb(2)1(ClO(4))(3)(H(2)O)]ClO(4) (3), and [Pb(2)1(SO(3)CF(3))(3)(H(2)O)]SO(3)CF(3) (4). Two unusually distorted [2 × 2] grid complexes, [Pb1(ClO(4))](4)(ClO(4))(4) (5) and [Pb1(ClO(4))](4)(ClO(4))(4)·4CH(3)NO(2) (6), were formed by reacting Pb(ClO(4))(2)·6H(2)O and 1 on a 1:1 metal/ligand ratio in CH(3)CN and CH(3)NO(2). These grids formed despite coordination of the hydroxymethyl arms due to the large, flexible coordination sphere of the Pb(II) ions. A [2 × 2] grid complex was formed in solution by reacting Pb(SO(3)CF(3))(2)·H(2)O and 1 on a 1:1 metal/ligand ratio in CH(3)CN as shown by (1)H NMR, microanalysis, and ESMS. Reacting the Zn(II) salts with 1 on a 2:1 metal/ligand ratio gave the linear complexes [Zn(2)1(H(2)O)(4)](SO(3)CF(3))(4)·C(2)H(5)O (7) and [Zn(2)1(BF(4))(H(2)O)(2)(CH(3)CN)](BF(4))(3)·H(2)O (8). (1)H NMR studies showed the Zn(II) and Pb(II) ions in these linear complexes were labile undergoing metal ion exchange. All of the complexes exhibited pym-hyz linkages in their cisoid conformation and binding between the hydroxymethyl arms and the metal ions. No complexes were isolated from reacting either of the Zn(II) salts with 1 on a 1:1 metal/ligand ratio, due to the smaller size of the Zn(II) coordination sphere as compared to the much larger Pb(II) ions.     

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.     

Homoleptic zinc(II) complexes with first and second coordination shells of 5-tert-butylpyrazole

Reaction of hydrated Zn[NO3]2 or Zn[BF4]2 with four or more equivalents of 3{5}-tert-butylpyrazole (L(tBu)) yields [Zn(L(tBu))4]X2 (X- = NO3- or BF4-). The nitrate complex contains C2-symmetric four-coordinate zinc(II) centers with a slightly flattened tetrahedral geometry, and each nitrate anion hydrogen bonds to two pyrazole N-H groups. Similar reactions with Zn[ClO4]2 or ZnCl2 in the presence of 2 equiv of AgPF6 or AgSbF6 yield instead [{Zn(L(tBu))4}(L(tBu))4][ClO4]2 and [{Zn(L(tBu))4}(L(tBu))2]Y2 (Y- = PF6- or SbF6-). Crystals of [{Zn(L(tBu))4}(L(tBu))4][ClO4]2 are composed of discrete [{Zn(L(tBu))4}(L(tBu))4]2+ supramolecules that are formed from N-H...N hydrogen bonding between zinc-bound and uncoordinated pyrazole rings. The [{Zn(L(tBu))4}(L(tBu))4]2+ moieties are linked into planar 4(4) nets by hydrogen bonding to bridging ClO4- anions. The ClO4- ions are almost perfectly encapsulated in near-spherical cavities of approximate dimensions 5.0 x 5.0 x 4.5 A that are formed by two interlocked supramolecular dications. Similarly, [{Zn(L(tBu))4}(L(tBu))2][PF6]2 crystallizes as discrete supramolecules in the crystal with the PF6- anions occupying a shallow bowl-shaped cavity on the surface of the complex that is formed by two zinc-bound and one uncoordinated pyrazole ligands. (1)H NMR and IR studies of [{Zn(L(tBu))4}(L(tBu))4][ClO4]2 in CD2Cl2 imply that the second-sphere L(tBu) ligands dissociate from the [Zn(L(tBu))4]2+ center in this solvent and that free and metal-bound L(tBu) are in rapid chemical exchange.     

(英)两个基于大环配体五员瓜环的异核金属配合物的合成及晶体结构

设计并合成了两个五员瓜环(Q[5])桥联K+和Na+形成的新型配合物[K(H2O)2Na(H2O)Q[5]](ClO4)2·6H2O(1),[KNaH(H2O)4Q[5]]n(ClO4)3n·3nH2O(2)。利用单晶X射线衍射进行结构测定,结果表明,配合物1中Q[5]起着一个双五齿配体的作用,每个端口的5个羰基氧原子分别和钾离子和钠离子配位,形成分子胶囊;配合物2中每个钾离子分别通过与相邻的2个Q[5]端口的相邻一对羰基氧原子配位,使得配合物形成一维链状结构,同时Q[5]还提供1个羰基氧原子与Na+配位,氢键使得配合物形成三维超分子结构。     

Syntheses and structures of Ag(I)-containing coordination polymers and Co(II)-containing supramolecular complex based on novel fulvene ligands

Three new rigid conjugated fulvene ligands L1-L3 were synthesized. L1 and L3 have been prepared by an aroylation reaction of cyclohexyl-substituted cyclopentadienyl anions. L2 was prepared by the reaction of L1 with PhNHNH2 in hot enthanol. Six new coordination polymers, namely [Ag(C25H20N2O2)(ClO4)] x 3.5C6H6 (1), [Ag2(mu-C31H24N4)(eta2-C6H6)(H2O)](ClO4)2 x (C6H6) x (H2O)0.5 (3), [Ag(C31H24N4)]SbF6 x solvate (4), [Ag(C31H24N4)](SbF6)2 x 2C6H6 x CH2Cl2 (5), [Ag(C25H20N2O2)2]SbF6 (6), and [Ag(C25H20N2O2)2]SbF6 (7), and one seven-membered cobaltacycle-containing complex, namely Co(C25H20N2O2)2(C2H5OH)2 (2), were obtained through self-assembly based on these three new fulvene lignads. L2-L3 and compounds 1-7 have been fully characterized by infrared spectroscopy, elemental analysis, and single-crystal X-ray diffraction. The results indicate that the coordination chemistry of new fulvene ligands is versatile. They can bind metal ions not only through the terminal N-donors and fulvene carbon atoms into organometallic coordination polymers but also through the two chelating carbonyl groups into unusual seven-membered metallo-ring supramolecular complexes. In the solid state, ligands L1-L3 are luminescent. A blue-shift in the emission was observed between the free ligand L1 and the one incorporated into Co(II)-containing complex 2, and a red-shift in the emission was observed between the free ligand L3 and the one incorporated into Ag(I)-containing polymeric compounds 6 and 7.     

Design and crystal structures of triple helicates with crystallographic idealized D3 symmetry: the role of side chain effect on crystal packing

Novel crystallographic D3-symmetric binuclear triple molecular helices [Co2L(1)3][BF4]4 (1), [Zn2L(1)3][BF4]4 (2), [Mn2L(1)3][BF4]4 (3), [Co2L(2)3][BF4]4 (4), [Zn2L(2)3][BF4]4 (5), and [Mn2L(2)3][BF4]4 (6) have been achieved to establish the side chain effect on molecular packing, where L1 is [(C5H4N)C(CH3)=N-(C6H4)-]2CH2 and L2 is [(C5H4N)C(CH3)=N-(C6H4)-]2O, respectively. Crystal structure analyses show that each helix crystallizes in a hexagonal crystal system with space group Pc1 and the general axis of the helix occupies the crystallographic 3-fold axial position with the other three crystallographic 2-fold symmetries perpendicular to it. Each metal center is bound to three pyridylimine units to attain C3 pseudooctahedral coordination geometry with respective equivalent metal-N (CH=N) and metal-N (pyridyl) bonds. It is speculated that the existence of the methyl group might minimize the potential intermolecular interactions, which would be the essential factor controlling the helices formed in idealized crystallographic D3 symmetry. Moreover, crystallographic idealized C3-symmetric helicates [Co2L(3)3][BF4]4 (7), [Zn2L(3)3][BF4]4 (8), [Ni2L(3)3][BF4]4 (9), and [Cu2L(3)3][BF4]4 (10) were also structurally characterized for comparison, where L3 is [(C5H4N)C(CH3)=N-]2. All the results indicate that the existence of the methyl group in the side chain of aromatic ligands could effectively reduce the potential - intermolecular interactions and the side chain effect of the methyl group in crystal packing is robust enough to be exchanged from one network structure to another, which ensures the generality and predictability of the crystallographic idealized symmetry formation to a certain extent.     

Assembly of azido- or cyano-bridged binuclear complexes containing the bulky [Mn(phen)2]2+ building block: syntheses, crystal structures, and magnetic properties

Two new cyano-bridged heterobinuclear complexes, [Mn(II)(phen)2Cl][Fe(III)(bpb)(CN)2] x 0.5CH3CH2OH x 1.5H2O (1) and [Mn(II)(phen)2Cl][Cr(III)(bpb)(CN)2] x 2H2O (2) [phen = 1,10-phenanthroline; bpb(2-) = 1,2-bis(pyridine-2-carboxamido)benzenate], and four novel azido-bridged Mn(II) dimeric complexes, [Mn2(phen)4(mu(1,1)-N3)2][M(III)(bpb)(CN)2]2 x H2O [M = Fe (3), Cr (4), Co (5)] and [Mn2(phen)4(mu(1,3)-N3)(N3)2]BPh4 x 0.5H2O (6), have been synthesized and characterized by single-crystal X-ray diffraction analysis and magnetic studies. Complexes 1 and 2 comprise [Mn(phen)2Cl]+ and [M(bpb)(CN)2]- units connected by one cyano ligand of [M(bpb)(CN)2]-. Complexes 3-5 are doubly end-on (EO) azido-bridged Mn(II) binuclear complexes with two [M(bpb)(CN)2]- molecules acting as charge-compensating anions. However, the Mn(II) ions in complex 6 are linked by a single end-to-end (EE) azido bridging ligand with one large free BPh4(-) group as the charge-balancing anion. The magnetic coupling between Mn(II) and Fe(III) or Cr(III) in complexes 1 and 2 was found to be antiferromagnetic with J(MnFe) = -2.68(3) cm(-1) and J(MnCr) = -4.55(1) cm(-1) on the basis of the Hamiltonian H = -JS(Mn)S(M) (M = Fe or Cr). The magnetic interactions between two Mn(II) ions in 3-5 are ferromagnetic in nature with the magnetic coupling constants of 1.15(3), 1.05(2), and 1.27(2) cm(-1) (H = -JS(Mn1)S(Mn2)), respectively. The single EE azido-bridged dimeric complex 6 manifests antiferromagnetic interaction with J = -2.29(4) cm(-1) (H = -JS(Mn1)S(Mn2)). Magneto-structural correlationship on the EO azido-bridged Mn(II) dimers has been investigated.     

具有非正规自旋态结构的新型Mn(Ⅱ)-Cu(Ⅱ)-Mn(Ⅱ)三核配合物的合成和磁性

合成和表征了四种新的异三核配合物, {[Mn(L)2]2[Cu(bpa)]{(ClO4)2,其中pba表示为亚丙基-1, 3-双(草胺酸根); L表示1, 10-菲咯啉(phen)、5-硝基-1, 10-菲咯啉(NO2-phen)、2, 2'-联吡啶(bpy)、4, 4'-二甲基-2, 2'-联吡啶(Me2bpy)。基于{[Mn(phen)2]2[Cu(pba)]}(ClO4)2.H2O的变温磁化率测量(4.2~300K), 求出交换积分J=41.5cm^-^1, 表明Mn(Ⅱ)和Cu(Ⅱ)离子间为反铁磁耦合。在XMT-T图上, XMT在175K附近呈现出一极小值, 这是具有非正规自旋态结构的多金属耦合体系的典型特征。     

Magnetic properties of cyano-bridged Ln3+-M3+ complexes. Part I: trinuclear complexes (Ln3+ = La, Ce, Pr, Nd, Sm; M3+ = FeLS, Co) with bpy as blocking ligand

The reaction of Ln(NO3)3(aq) with K3[Fe(CN)6] or K3[Co(CN)6] and 2,2'-bipyridine in water/ethanol led to eight trinuclear complexes: trans-[M(CN)4(mu-CN)2{Ln(H2O)4(bpy)2}2][M(CN)6].8H2O (M = Fe3+ or Co3+, Ln = La3+, Ce3+, Pr3+, Nd3+, and Sm3+). The structures for the eight complexes [La2Fe] (1), [Ce2Fe] (2), [Pr2Fe] (3), [Nd2Fe] (4), [Ce2Co] (5), [Pr2Co] (6), [Nd2Co] (7), and [Sm2Co] (8) have been solved; they crystallize in the triclinic space group P and are isomorphous. They exhibit a supramolecular 3D architecture through hydrogen bonding and pi-pi stacking interactions. A stereochemical study of the nine-vertex polyhedra of the lanthanide ions, based on continuous shape measures, is presented. No significant magnetic interaction was found between the lanthanide(III) and the iron(III) ions.     

Synthesis and characterization of a series of novel heptanuclear trigonal-prismatic polyhedra with different edge-ligands

Five novel heptanuclear trigonal-prismatic polyhedra, Na4[PrNi6(Gly)9(mu 3-OH)3(H2O)6].(ClO4)7 (1), Na2[PrNi6(Gly)8(mu 3-OH)3(mu 2-OH2)-(H2O)6].(ClO4)6.(H2O)2 (2), Na[DyNi6(Gly)7(mu 3-OH)3(mu 2-OH2)2(H2O)6].(ClO4)6.H2O (3), [SmNi6(Gly)6-(mu 3-OH)3Cl3(H2O)6].Cl3.(H2O)9 (4), and [ErNi6(Gly)6(mu 3-OH)3Cl3(H2O)6].Cl3.(H2O)9 (5), were synthesized through self-assembly and characterized by X-ray structure analysis. Complex 1 crystallizes in the trigonal P3 space group (a = b = 18.1121(2), c = 11.987(0) A, and Z = 2). Complex 2 belongs to the triclinic P1 space group (a = 16.0145(3), b = 20.58650(10), c = 20.8452(3) A, alpha = 78.0590(10), beta = 67.9200(10), gamma = 68.1540(10) degrees, and Z = 4). Complex 3 belongs to the monoclinic P2(1)/m space group (a = 14.9863(3), b = 13.533, c = 15.6171(3) A, beta = 116.8970(10) degrees, and Z = 2). Complexes 4 and 5 are isomorphous (4: trigonal, P3; a = b = 11.8661(4), c = 18.2034(10) A, Z = 2; 5: a = b = 11.9001(5), c = 18.1229(11) A, Z = 2). A Ln3+ ion is in the center of the prism formed by six nickel atoms. It coordinates to nine oxygen atoms. Its coordination polyhedron may be best described as a tricapped trigonal prism. The five complexes all have a core of [LnNi6(Gly)6-(mu 3-OH)3(H2O)6]6+ and were obtained through the edge-ligand exchange of the three mu 2-OH2 ligands of [LnNi6(Gly)6-(mu 3-OH)3(H2O)6(mu 2-OH2)3]6+ partly or wholly by glycine or Cl-. Magnetic measurements reveal that 1 and 4 exhibit antiferromagnetic interaction, while 5 exhibits a ferromagnetic interaction.