Solid state coordination chemistry of metal oxides: structural consequences of fluoride incorporation into the oxovanadium-copper-bisterpy-{O3P(CH2)nPO3}4- system, n= 1-5 (bisterpy = 2,2':4',4":2",2"'-quaterpyridyl-6', 6"-di-2-pyridine)

Hydrothermal reactions of a vanadate source, an appropriate Cu(II) source, bisterpy and an organodiphosphonate, H2O3P(CH2)nPO3H2(n= 1-5), in the presence of HF, yielded a family of materials of the type oxyfluorovanadium/copper-bisterpy/organodiphosphonate. Under similar reaction conditions, variations in diphosphonate tether length n provided the one-dimensional [{Cu2(bisterpy)}V2F2O2{HO3PCH2PO3}{O3PCH2PO3}](1) and [{Cu2(bisterpy)}V2F4O4{HO3P(CH2)2PO3H}](3), the two-dimensional [{Cu2(bisterpy)}V2F2O2(H2O)2{HO3P(CH2)2PO3}2] x 2H2O (2 x 2H2O), [{Cu2(bisterpy)(H2O2}V2F2O2{O3P(CH2)3PO3}{HO3P(CH2)3PO3H}(4) and [{Cu2(bisterpy)}V4F4O4(OH)(H2O){HO3P(CH2)5PO3}{O3P(CH2)5PO3}] x H2O (9 x H2O) and the three-dimensional [{Cu2(bisterpy)}3V8F6O17{HO3P(CH2)3PO3}4]0.8H2O (5 x 0.8H2O), [{Cu2(bisterpy)}V4F2O6{O3P(CH2)4PO3}2](8) and [{Cu2(bisterpy)(H2O)}2V8F4O8(OH)4{HO3P(CH2)5PO3H}2{O3P(CH2)5PO)}3] x 4.8H2O (10 x 4.8H2O). In addition, two members of the oxovanadium/Cu2(bisterpy)/organodiphosphonate family [{Cu2(bisterpy)}V2O4{HO3P(CH2)3PO3}2](6) and [{Cu2(bisterpy)}3V4O8(OH)2{O3P(CH2)3PO3}2{HO3P(CH2)3PO3}2] x 5H2O (7 x 5H2O) cocrystallized from the reaction mixture which provided 5. The overall architectures reveal embedded substructures based on V/P/O(F) clusters, chains, networks, and frameworks. In contrast to the oxovanadium/Cu2(bisterpy)/ organodiphosphonate family, several of the materials of this study also exhibit the direct condensation of vanadium polyhedra to produce binuclear and/or tetranuclear building units.     

Evolution of the structural chemistry of vanadium organodiphosphonate networks and frameworks: structural consequences of fluoride incorporation in the development of stable phases with void channels

Hydrothermal reactions of solutions containing a vanadate source, an organodiphosphonate, an organonitrogen component, and HF (V/P/O/F) yield a series of oxyfluorovanadium-diphosphonates with charge-compensation provided by organoammonium cations or hydronium cations. While V/P/O/F networks provide the recurrent structural motif, the linkage between the layers and the details of the polyhedral connectivities within the layers are quite distinct for the five structures of this study. [H2pip][V4F4O2(H2O)2{O3P(CH2)3PO3}2] (1) (pip = piperazine) is a conventional three-dimensional (3D) "pillared" layer structure, whose V/P/O/F networks are buttressed by the propylene chains of the diphosphonate ligands. In contrast, [H2en][V2O2F2(H2O)2{O3P(CH2)4PO3}] (2) and [H2en]2[V6F12(H2O)2{O3P(CH2)5PO3}2 {HO3P(CH2)5PO3H}] (3) are two-dimensional (2D) slablike structures constructed of pairs of V/P/O/F networks sandwiching the pillaring organic tethers of the diphosphonate ligands. Despite the common overall topology, the layer substructures are quite different: isolated {VO5F} octahedra in 2 and chains of corner-sharing {VO(3)F(3)} octahedra in 3. The 3D structure of [H2en]2[V7O6F4(H2O)2{O3P(CH2)2PO3}4].7H2O (4.7H2O) exhibits a layer substructure that contains the ethylene bridges of the diphosphonate ligands and are linked through corner-sharing octahedral {VO6} sites. The connectivity requirements provide large channels that enclose readily removed water of crystallization. The structure of [H3O][V3F2(H2O)2{O3P(CH2)2PO3}2].3.5H2O (5.3.5H2O) is also 3D. Because of the similiarity with 4.7H2O, it exhibits V/P/O/F layers that include the organic tethers of the diphosphonates and are linked through corner-sharing {VO6} octahedra. In contrast to the network substructure of 4.7H2O, which contains binuclear and trinuclear vanadium clusters, the layers of 5.3.5 H2O are constructed from chains of corner-sharing {VO4F2} octahedra. Thermal studies of the open framework materials 4 and 5 reveal that incorporation of fluoride into the inorganic substructures provides robust scaffoldings that retain their crystallinity to 450 degrees C and above. In the case of 4, dehydration does not change the powder X-ray diffraction pattern of the material, which remains substantially unchanged to 450 degrees C. In the case of 5, there are two dehydration steps, that is, the higher temperature process associated with loss of coordinated water. This second dehydration results in structural changes as monitored by powder X-ray diffraction, but this new phase is retained to ca. 450 degrees C. The materials of this study exhibit a range of reduced oxidation states: 1 is mixed valence V(IV)/V(III) while 2 and 4.7H(2)O are exclusively V(IV) and 3 and 5.3.5H2O are exclusively V(III). These oxidation states are reflected in the magnetic properties of the materials. The paramagnetism of 1 arises from the presence of V(III) and V(IV) sites and conforms to the Curie-Weiss law with C = 2.38 em K/(Oe mol) and = -66 K with mu(eff) (300 K) = 4.33 mu(B). Compounds 3-5 exhibit Curie-Weiss law dependence of magnetism on temperature with mu(eff) (300 K) = 5.45 mu(B) for 3 (six V(III) sites), mu(eff) = 4.60 mu(B) for 4 (seven V(IV) sites) and mu(eff) = 4.13 mu(B) for 5 (two V(III) sites). Compound 2 exhibits antiferromagnetic interactions, and the magnetism may be described in terms of the Heisenberg linear antiferromagnetic chain model for V(IV). The effective magnetic moment at 300 K is 2.77 mu(B) (two V(IV) sites).     

[NH3(CH2)5NH3][Fe2{O3PC(CH3)(OH)(PO3H)}2]@2H2O:一个新的二膦酸亚铁化合物的合成、结构与性质研究（英文）

通过水热合成得到一个新的有机二膦酸亚铁化合物[NH3(CH2)5NH3][Fe2Ⅱ(O3PC(CH3)(OH)(PO3H)}2]·2H2O,该化合物包含阴离子型共价双链[Fe2Ⅱ{O3PC(CH3)(OH)PO3H}2]n2n-,质子化的戊二胺和结晶水,双链之间通过强氢键构成一个开放型的骨架结构.另外,观察到亚铁离子之间存在弱铁磁性相互作用.     

New types of metal squarato-phosphonates: condensation of aminodiphosphonate with squaric acid under hydrothermal conditions

The syntheses and crystal structures of the first copper(I) phosphonate, Cu2(H3L)(bipy)(2).2H2O 1 (H5L = C4HO3N(CH2PO3H2)2), which is also the first example of metal phosphonates formed by a type of organic reaction, and a novel luminescent Mn(II) squarate diphosphonate, {Mn[NH(CH2PO3H)2](H2O)2}2{Mn(C4O4)(H2O)4}.(C4H2O4) 2, have been reported. The structure of 1 features a layer architecture in which the Cu(I) centers are three coordinated, and the newly formed ligand acts as a bidentate metal linker. Compound 2 is composed of 1D chains of Mn[NH(CH2PO3H)2](H2O)2, 1D chains of {Mn(C4O4)(H2O)4}, as well as the neutral squaric acid molecules. These three types of building units are interconnected via hydrogen bonding.     

Structural Variability of the Vanadium-Organodiphosphonate System: Hydrothermal Syntheses and Structural Characterizations of One-Dimensional, Two-Dimensional, and Three-Dimensional Phases

The hydrothermal chemistry of the CsVO(3)/methylenediphosphonate system was investigated. Variations in reaction temperatures, heating times, and stoichiometries of reactants resulted in the isolation of mononuclear, one-, two-, and three-dimensional species: Cs[VO(HO(3)PCH(2)PO(3)H)(2)(H(2)O)] (1), Cs[VO(HO(3)PCH(2)PO(3))] (2), Cs[(VO)(2)V (O(3)PCH(2)PO(3))(2)(H(2)O)(2)] (3), and [V(HO(3)PCH(2)PO(3))(H(2)O)] (4), respectively. The structure of the anion of 1 consists of isolated V(IV) octahedra. Phase 2 adopts a chain structure constructed from corner-sharing V(IV) octahedra, forming infinite {-V=OV=O-} linkages. The layer structure of 3 contains trinuclear units of corner-sharing {VO(6)} octahedra with the central V site in the III oxidation state and V(IV) centers at the extremities of the cluster. The diphosphonate ligands serve to link neighboring trinuclear motifs into a layer structure three octahedra in depth. The Cs(+) cations occupy cavities within the layers, rather than the more common interlamellar positions. The structure of 4 consists of isolated {V(III)O(6)} octahedra linked by diphosphonate groups into a three-dimensional framework. Crystal data: for 1, CH(6)O(7)P(2)V(0.5)Cs, monoclinic C2, a = 10.991(2) ?, b = 10.161(2) ?, c = 7.445(1) ?, beta = 92.97(3) degrees, Z = 4; for 2, CH(3)O(7)P(2)VCs, monoclinic C2, a = 10.212(2) ?, b = 10.556(2) ?, c = 14.699(3) ?, beta = 94.57(2) degrees, Z = 8; for 3, C(2)H(8)O(16)P(4)V(3)Cs, monoclinic C2/m, a = 9.724(2) ?, b = 8.136(2) ?, c = 10.268(2) ?, beta = 103.75(3) degrees, Z = 2; for 4, CH(5)O(7)P(2)V, monoclinic P2(1)()/n, a = 5.341(1) ?, b = 11.516(2) ?, c = 10.558(2) ?, beta = 99.89(1) degrees, Z = 4.     

Hydrothermal Syntheses and Characterizations of Two One-dimensional Molybdenum 1,4-Butylenediphosphonates

1 INTRODUCTION Interest in metal phosphonate chemistry has in- creased in recent years, not only because of their rich structural chemistry[1～3] but also owing to their potential applications in catalysis, absorption and intercalation reaction[4～6]. The introduction of a se- cond metal-ligand component as a charge-compen- sating unit and structure-directing component into polyoxomolybdenum/oxovanadium organodi-phos- phonates has provided us a powerful method to syn- thesize this family o…     

Solid state coordination chemistry: structural consequences of variations in tether length in the oxovanadium-copper-bisterpy-[O3P(CH2)nPO3]4- system, n= 1-6 (bisterpy = 2,2':4',4'':2'',2'''-quarterpyridyl-6',6''-di-2-pyridine)

Hydrothermal reactions of Na3VO4, an appropriate Cu(II) source, bisterpy and an organodiphosphonate, H2O3P(CH2)nPO3H2 (n = 1-6) yielded a family of materials of the type [Cu2(bisterpy)]4+/VxOy(n-)/[O3P(CH2)nPO3]4-. This family of bimetallic oxides is characterized by an unusual structural diversity. The oxides [[Cu2(bisterpy)]V2O4[O3PCH2PO3H]2] (1), [[Cu2(bisterpy)(H2O)]VO2[O3P(CH2)3PO3][HO3P(CH2)3PO3H2]] (4) and [[Cu2(bisterpy)]V2O4[O3P(CH2)6PO3H]2].2H2O (7.2H2O) are one-dimensional, while [[Cu2(bisterpy)(H2O)2]V2O4[O3P(CH2)2PO3][HO3P(CH2)2PO3H]2] (2), [[Cu2(bisterpy)]V4O8[O3P(CH23PO3]2].4H2O (3.4H2O) and [[Cu2(bisterpy)]V2O4(OH)2[O3P(CH2)4PO3]].4H2O (5.4H2O) are two-dimensional. The V(IV) oxide [[Cu2(bisterpy)]V4O4[O3P(CH2)5PO3H]4].7.3H2O (6.7.3H2O) provides a relatively unusual example of a three-dimensional bimetallic oxide phosphonate. The structures reveal a variety of V/P/O substructures as building blocks.     

Rational design and synthesis of porous organic-inorganic hybrid frameworks constructed by 1,3,5-benzenetriphosphonic acid and pyridine synthons

1,3,5-Benzenetriphosphonic acid, H6BTP, 1,3,5-[(HO)2OP]3C6H3, was reacted hydrothermally with copper salts in the absence and presence of 4,4'-bipyridine (bpy) and 4,4'-trimethlyenedipyridine (tbpy) in a 1:1 molar ratio leading to three new organic-inorganic hybrid frameworks. Compound 1, {Cu6[C6H3(PO3)3]2(H2O)8} x 5.5 H2O, has three different copper ions that are interconnected by the highly charged [1,3,5-(PO3)3C6H3]6- anionic moieties. These moieties self-assemble through tetra-copper units to give a cagelike motif with two benzene rings parallel to each other at a distance of 3.531 A which extend along the a axis and link with a grouping of four-coordinated copper units in the b axis direction to give the cross-linked layered structure. In compound 2, Cu{C6H3[PO(OH)O]2[PO(OH)2]}(C10H8N2), the copper ions are in square pyramidal geometries and are interconnected via chelating and bridging BTP ligands into layers which are further cross-linked by bpy ligands into a pillared layered architecture. Compound 3, {Cu2C6H3[PO(OH)O]2[PO3](C13H14N2)} x 3 H2O x 0.5 HCON(CH3)2, contains tetra-copper units that are linked by BTP ligands and further linked by tbpy linkers in the c axis direction to produce a large channel-sized 3D framework.     

A building block approach to the synthesis of organic-inorganic oxide materials: the hydrothermal synthesis and network structure of [[Ni4(tpypyz)3][Mo5O15(O3PCH2CH2PO3)]2] x 23H2O (tpypyz = tetra-2-pyridylpyrazine)

The hydrothermal reaction of MoO3, [Ni(CH3CO2)2] x 4H2O, tpypyz, ethylenediphosphonic acid and water yields the 2D material [[Ni4(tpypyz)3][Mo5O15(O3PCH2CH2PO3)]2] x 23H2O (1 x 23H2O), constructed from [Mo5O15(O3PCH2CH2PO3)]4- clusters linked in one-dimension through the ethylene tethers of the diphosphonate component; these molybdodiphosphonate chains are in turn linked into a 2D network through the tetranuclear secondary metal-ligand subunit [Ni4(tpypyz)3]8+.     

Nitrilotris(methylenephosphonic) Complexes of Lanthanides [Na(H2O)x]2[LnIIINa6H(H2O)10{N(CH2PO3)3}2] · nH2O (LnIII = Pr,Nd)

Russian Journal of Coordination Chemistry - The sodium salts of lanthanide nitrilotris(mehylenephosphonate) complexes [Na(H2O)x]2[LnIIINa6H(H2O)10{N(CH2PO3)3}2] · nH2O, where LnIII = Pr (I),...     

Pillared layered structures based upon M(III) ethylene diphosphonates: the synthesis and crystal structures of M(III)(H(2)O)(HO(3)P(CH(2))(2)PO(3)) (M = Fe, Al, Ga)

A three-dimensional iron(III) diphosphonate, Fe(III)(H(2)O)(HO(3)P(CH(2))(2)PO(3)), I, has been synthesized hydrothermally and characterized by single-crystal X-ray diffraction. The compound crystallizes in the orthorhombic space group Pbca (no. 61) where a = 9.739(5) A, b = 9.498(5) A, c = 15.940(8) A, V = 1474.4(1) A(3), Z = 8, and R(1) = 0.0380. The structure consists of inorganic sheets pillared by the 1,2-ethylenediphosphonate groups. The sheets are composed of Fe(H(2)O)O(5) octahedra connected through PO(3)C tetrahedra. The corresponding isostructural aluminum (II) and gallium (III) compounds were also synthesized and indexed: II, a = 9.534(1) A, b = 9.255(2) A, c = 15.724(1) A, V = 1387.5(1) A(3); III, a = 9.670(1) A, b = 9.357(2) A, c = 15.862(4) A, V = 1435.4(1) A(3).     

[π-C5H5N（CH2）15CH3]3[PMoW3O24]／H2O2：高效的环境友好且可再生的烯烃环氧化磷钼钨杂多酸催化体系

研究了一种可循环并且环境友好的催化体系：[π-C5H5N（CH2）15CH3]3[PMoW3O24]／过氧化氢／乙酸乙酯／烯烃．此体系不仅可以催化烯烃的环氧化反应,而且避免了对含氯溶剂的使用．反应在过氧化氢／乙酸乙酯的两相体系中进行,可以将多种烯烃转化为相应的环氧化物,且产率较高．此催化剂具有反应控制相转移的特征,反应结束后可以回收再利用．采用Raman,IR,^31P MAS NMR和^31P NMR等手段对新鲜及重复使用过的催化剂进行表征．结果表明：新鲜催化剂[π-C5H5N（CH2）15CH3]3[PMoW3O24]是一种混合物,含有多种过氧磷钼钨酸盐,如{PO4[MoO（O2）2]4}^3-,[（PO4）{Mo3WO20}]^3-,[（PO4）{Mo2W2O20}]^3-,[（PO4）{MoW3O20}]^3-和{PO4[WO（O2）2]4}^3-．当过氧化氢被完全消耗后,这些小的活性物种就会聚合成具有混合多原子的Keggin型杂多阴离子,形成M-Ob—M（M=W或Mo）和M-Oc-M键．     

Hydrothermal Synthesis and Crystal Structure of a New Sandwich—type Molybdenum Phosphate

1 INTRODUCTION The synthesis of porous and open-framework transition metal phosphates has received great in- terest due to their various compositions and topolo- gyies, as well as their useful properties such as con- trollable size- and shape-selectivity, rigid frame- works and chemical/thermal stability[1]. Of these phosphates constructed from oxometal polyhedra and PO4 tetrahedron, the most interesting is the [MoV6P4X31]n－ (X=O, OH) family with the dimen- sionalities ranging from …     

Heterometallic MIIRuIII2 compounds constructed from trans-[Ru(Salen)(CN)2]- and trans-[Ru(Acac)2(CN)2]-. Synthesis, structures, magnetic properties, and density functional theoretical study

The synthesis, structures, and magnetic properties of four cyano-bridged M(II)Ru(III)2 compounds prepared from the paramagnetic Ru(III) building blocks, trans-[Ru(salen)(CN)2]- 1 [H2salen = N,N'-ethylenebis(salicylideneimine)] and trans-[Ru(acac)2(CN)2]- (Hacac = acetylacetone), are described. Compound 2, {Mn(CH3OH)4[Ru(salen)(CN)2]2}.6CH3OH.2H2O, is a trinuclear complex that exhibits antiferromagnetic coupling between Mn(II) and Ru(III) centers. Compound 3, {Mn(H2O)2[Ru(salen)(CN)2]2.H2O}n, has a 2-D sheetlike structure that exhibits antiferromagnetic coupling between Mn and Ru, leading to ferrimagnetic-like behavior. Compound 4, {Ni(cyclam)[Ru(acac)2(CN)2]2}.2CH3OH.2H2O (cyclam = 1,4,8,11-tetraazacyclotetradecane), is a trinuclear complex that exhibits ferromagnetic coupling. Compound 5, {Co[Ru(acac)2(CN)2]2}n, has a 3-D diamond-like interpenetrating network that exhibits ferromagnetic ordering below 4.6 K. The density functional theory (DFT) method was used to calculate the molecular magnetic orbitals and the magnetic exchange interaction between Ru(III) and M(II) (Mn(II), Ni(II)) ions.     

Synthesis, structural, and magnetic studies on a redox family of tetrametallic vanadium clusters: {VIV4}, {VIII2VIV2}, and {VIII4} butterfly complexes

The synthesis, crystal structures, and magnetic properties are reported for a redox family of butterfly-type tetrametallic vanadium alkoxide clusters, namely [V2(VO)2(acac)4(RC{CH2O}3)2] (R=Me 1, Et 2, CH2OH 3), [V2(VO)2(acac)2(O2CPh)2(MeC{CH2O}3)2] (5), [(VO)4(MeOH)2(O2CPh)2({HOCH2}C{CH2O}3)2] (6), [V4Cl2(dbm)4(RC{CH2OH}3)2] (R=Me 7, Et 8, CH2OH 9), and [V4Cl2(dbm)4(MeO)6] (10). The cluster cores are {VIV4} (6), {VIII2VIV2} (1-5), and {VIII4} (7-10), with examples of both isomeric forms of the of the mixed-valence cores (either VIII or VIV ions forming the butterfly body). Magnetic studies reveal the clusters to be dominated by antiferromagnetic exchange interactions in each case. The magnetic exchange parameters are determined for representative examples of each core type. {VIV4} and {VIII4} have diamagnetic ground states. The two isomeric {VIII2VIV2} types are found to give rise to either an S=0 ground state with a number of low-lying excited states due to competing antiferromagnetic exchange interactions (VIII2 butterfly body) or to a well-isolated S=1 ground state (VIV2 butterfly body).     

Molybdophosphonate clusters as building blocks in the oxomolybdate-organodiphosphonate/cobalt(II)-organoimine system: structural influences of secondary metal coordination preferences and diphosphonate tether lengths

Hydrothermal conditions have been used in the preparation of a series of organic-inorganic hybrid materials of the cobalt-molybdophosphonate family. The reactions of MoO(3), cobalt(II) acetate or cobalt(II) acetylacetonate, tetra-2-pyridylpyrazine (tpyprz), and organodiphosphonic acids H(2)O(3)P(CH(2))nPO(3)H(2) (n = 1-5 and 9) of varying tether lengths yielded compounds of the general type {Co(2)(tpyprz)(H(2)O)(m)}4+/MoxOy{O(3)P(CH(2))(n)PO(3)}z. The recurring theme of the structural chemistry is the incorporation of {Mo(5)O(15)(O(3)PR)(2)}(4-) clusters as molecular building blocks observed in the structures of nine phases (compounds 2-9 and 11). The structural consequences of variations in reaction conditions are most apparent in the series with propylene diphosphonate, where four unique structures 4-7 are observed, including two distinct three-dimensional architectures for compounds 5 and 6 whose formulations differ only in the number of water molecules of crystallization. With pentyldiphosphonate, a second phase 10 is obtained which exhibits a unique cluster building block, the hexamolybdate [Mo(6)O(18){O(3)P(CH(2))(5)PO(3)}](4-). In the case of methylenediphosphonic acid, a third structural motif, the trinuclear {(Mo(3)O(8))(O(3)PCH(2)PO(3))}2- subunit, is observed in compound 1. The structural chemistry of compounds 1-11 of this study is quite distinct from that of the {Ni(2)(tpyprz)(H(2)O)(m)}(4+)/Mo(x)O(y){O(3)P(CH(2))(n)PO(3)}z family, as well as that of the copper-based family. The structural diversity of this general class of materials reflects the coordination preferences of the M(II) sites, the extent of aqua ligation to the M(II) sites, the participation of both phosphate oxygen atoms and molybdate oxo-groups in linking to the M(II) sites, and the variability in the number of attachment sites at the molybdophosphonate clusters. Since the charge densities at the peripheral oxygen atoms of the clusters are quite uniform, the attachment of {M(2)(tpyprz)}(4+) subunits to the molybdophosphonates appears to be largely determined by steric, coulombic, and packing factors, as shown by extensive density functional theory calculations.     

Cobalt diphosphonate with a new double chain structure exhibiting field-induced magnetic transition

A cobalt diphosphonate Co(H(2)O){C(5)H(5)N-CH(2)CH(OH)(PO(3))(PO(3)H)} (1) has been synthesized under hydrothermal conditions. It shows a novel type of double chain structure in which one of the two CPO(3) terminus caps on top of the {Co(2)(micro-O)2} dimer while the other connects the adjacent {Co(2)(micro-O)2} dimers into a chain. The magnetization measurements reveal that dominant antiferromagnetic interactions are mediated between the magnetic centers and the compound experiences a field-induced magnetic transition at low temperature with H(c) of ca. 15 kOe at 1.8 K.     

三维骨加{[Cu（1,2—pn）2]4[V18O42（H2O）]}n·8nH2O化合物的水热合成和晶体结构

物材多孔材料广泛应用于吸附、形状和尺寸选择性的多相催化和离子交换．利用有机胺分子的模板和结构导向作用已设计合成了许多沸石分子筛、中孔MCM－41和非致密过渡金属磷酸盐等多孔性氧化料[’－“．过渡金属氧簇结构中普遍存在金属－金属键,业已证明金属氧簇合物具有催化活     

Zn7{(2-C5H4N)CH(OH)PO3}6 (H2O)6]SO4 x 4H2O: a zinc phosphonate cluster with a drum-like cage structure

Direct reaction of hydroxy(2-pyridyl)methylphosphonic acid with zinc sulfate under hydrothermal conditions results in the formation of the novel heptanuclear cluster compound [Zn7{(2-C5H4N)CH(OH)PO3}6 (H2O)6]SO4 x 4H2O (1). The inorganic core of the cluster can be described as a cylindrical drum made up of six Zn atoms bridged by six {CPO3} units that is centered by a seventh Zn atom. Crystal data: monoclinic, C2/c, a = 22.690(2) A, b = 16.675(2) A, c = 18.151(2) A, beta = 93.390(2) degrees.     

New types of blue, red or near IR luminescent phosphonate-decorated lanthanide oxalates

Hydrothermal reactions of the lanthanide chlorides with MeN(CH2CO2H)(CH2PO3H2), (H3L1) (or Me2NCH2PO3H2, H2L2) and sodium oxalate lead to seven new lanthanide oxalate phosphonate hybrids with three types of 3D network structures, namely, [Ln(C2O4){MeNH(CH2CO2)(CH2PO3H)}]0.5 H2O (Ln=Nd: 1; Eu: 2; Gd: 3), [Ln4(C2O4)5(Me2NHCH2PO3)2(H2O)4]2 H2O (Ln=La: 4, Nd: 5), [Ln3(C2O4)4(Me2NHCH2PO3)(H2O)6]6 H2O (Gd: 6, Er: 7). Their structures have been established by X-ray single-crystal diffraction. Complexes 1-3 are isostructural and feature a 3D network formed by the interconnection of 3D network of {Ln(H2L1)}2+ with 1D chains of {Ln(C2O4)}+. Complexes 4 and 5 are isostructural and feature a complex 3D network built from 3D network of lanthanide oxalate and {Ln4(HL2)2} units. The isostructural 6 and 7 form another type of 3D network composed of porous lanthanide-oxalate network inserted by 1D chains of lanthanide-oxalate phosphonate. Compounds 1, 5 and 7 are luminescent materials in the near IR region. Compounds 3 and 6 exhibit a broad blue fluorescent emission band at 451 and 467 nm, respectively. Compound 2 displays very strong and sharp emission bands at 592, 616 and 699 nm with a long luminescent lifetime of 1.13 ms.