Showing papers on "Coordination polymer published in 2005"

Temperature- or guest-induced drastic single-crystal-to-single-crystal transformations of a nanoporous coordination polymer.

Abstract: Aside from a temperature-induced structural transformation, a new nanoporous coordination polymer [Ag6Cl(atz)4]·OH·6H2O (Hatz = 3-amino-1,2,4,-triazole) comprised of interpenetrated Ag3(atz)2 coordination nets exhibits a single-crystal-to-single-crystal transformation of a 5-fold to 6-fold net interpenetration change triggered by guest desorption/absorption.

Spin Canting and Metamagnetism in a 3D Homometallic Molecular Material Constructed by Interpenetration of Two Kinds of Cobalt(II)‐Coordination‐Polymer Sheets

Abstract: O(1),a3Dnetworkconsistingoftwodifferent,interpenetrating2D neutral polymers. With strong anisotropyfrom single ions arranged in the chains, sheets, and finally the3D structure, 1 exhibits spin canting and typical metamag-netism.Crystal-structure determination by X-ray crystallographyshowed that each of the four Co

Metallosupramolecular approach toward functional coordination polymers

Abstract: An appropriate definition of metallosupramolecular coordination polymer is offered, and the relationship between the polymer length, binding constant, and concentration is clarified. The possibility of influencing the binding constant with chelating ligands is discussed on the basis of examples of different Zn 2+ complexes and their respective binding constants. In the main part, coordination polymers constructed by a supramolecular approach from different metal ions and pyridine-ligand systems are highlighted, and their applications as functional materials for artificial membrane and enzyme models, responsive gels, light-harvesting systems, and organic light-emitting diodes are discussed on the basis of individual examples.

A twelve-connected Cu6S4 cluster-based coordination polymer.

Abstract: Hydrothermal reaction of Cu(MeCO2)2, (4-pyridylthio)acetic acid, and NH4SCN resulted in a metal-organic framework [Cu3(4-pyridinethiolate)2(CN)] which has twelve-connected face-centered cubic topology with Cu6S4 clusters as nodes.

Direct Observation of Hydrogen Molecules Adsorbed onto a Microporous Coordination Polymer

Abstract: design and synthesis of high-performance hydrogenstorage materials. Although the weakest X-ray scattering amplitude of hydrogen made it difficult to determine their structure, we have succeeded in the first direct observation of elusive H2 molecules adsorbed in the nano-channels of a metal-organic porous material by the in situ synchrotron powder diffraction experiment of gas adsorption and by MEM (maximum entropy method)/Rietveld charge-density analysis [4]. The sample used in this study is microporous coordination polymer 1 with a pillared layer structure (CPL-1) with uniform ordered nano-channels of 4 Å × 6 Å. The in situ synchrotron powder diffraction experiment for hydrogen gas adsorption was carried out using the large Debye-Scherrer camera installed at beamline BL02B2. The hydrogen gas was dosed into the capillary sample through a stainless steel tube connected to the gas-handling system. The amount of adsorbed gas was controlled by adjusting the sample temperature under a constant hydrogen gas pressure of 102 kPa. The structure was investigated by MEM/Rietveld analysis [5]. The amount of H2 molecules adsorbed in CPL-1 at 90 K at 102 kPa was determined to be 0.3 molecules per Cu atom from the hydrogen adsorption isotherm. The reliability (R) factors based on the powder profile RWP and the Bragg integrated intensities RI were 2.45% and 3.33%, respectively. The cell parameters for CPL-1 with H2 gas were determined as a = 4.7101(1) Å, b = 20.0289(2) Å, c = 10.7704(1) Å, and β = 95.472(2)° (space group P21/c). The R factor based on the structure factors in the final MEM analysis RF was 1.86%. In the MEM charge density of CPL-1 without H2 molecules shown in Fig. 1(a), only the nano-channel structure was clearly seen and no electron density was observed in the nano-channels, even at lower electron-density levels. On the other hand, in the MEM charge density of CPL-1 with H2 molecules (Fig. 1(b)), the small peak maxima of the electron densities with an elongated shape distribution, which are due to the adsorbed H2 molecules, were observed in the nano-channels. It should be noted that the posit ion and orientation of the H2 molecules are mean values obtained by statistical analysis. The

Self-Assembly of a Series of Extended Architectures Based on Polyoxometalate Clusters and Silver Coordination Complexes

Abstract: Three unusual compounds based on polyoxometalate building blocks, [(H2O)5Na2(C6NO2H4)(C6NO2H5)3Ag2][Ag2IMo6O24(H2O)4]·6.25H2O (1), [(H2O)4Na2(C6NO2H5)6Ag3][IMo6O24]·6H2O (2), and (C6NO2H6)2[(C6NO2H5)2Ag][Cr(OH)6Mo6O18]·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 [C...

Novel Two-Dimensional Network Constructed from Polyoxomolybdate Chains Linked through Copper−Organonitrogen Coordination Polymer Chains: Hydrothermal Synthesis and Structure of [H2bpy][Cu(4,4‘-bpy)]2[HPCuMo11O39]

Abstract: A novel compound, [H2bpy][Cu(4,4‘-bpy)]2[HPCuMo11O39] (1), has been prepared under mild hydrothermal conditions and has been structurally characterized by single-crystal X-ray diffraction. Compound 1 exhibits a novel two-dimensional network constructed from the interconnecting of polyoxomolybdate chains, {HPCuMo11O39}n4n-, and transition metal coordination polymer chains, {Cu(4,4‘-bpy)}nn+. It is the first example of a two-dimensional structure formed by a polyoxomolybdate chain through the linkage of a transition metal coordination polymer chain.

A Novel Pillar-Layered Organic−Inorganic Hybrid Based on Lanthanide Polymer and Polyomolybdate Clusters: New Opportunity toward the Design and Synthesis of Porous Framework

Abstract: An unprecedented microporous lanthanum polymolybdate, [{La(H2O)5(dipic)}{La(H2O)(dipic)}]2{Mo8O26}·10H2O (H2dipic = pyridine-2,6-dicarboxylic acid) 1, which is constructed from lanthanum−organic coordination polymer sheets pillared by individual octamolybdate clusters, is reported.

Molecular and multidimensional polyoxotungstates functionalized by {Cu(bpy)}2+ groups

Abstract: Five new materials built from polyoxotungstates and Cu(II) ions as linkers have been synthesized by hydrothermal reactions from a mixture of sodium tungstate, copper chloride and bipyridine. The value of the initial pH, the nature of the heteroelement (P or Si) and of the ligand (2,2′- and/or 4,4′-bipyridine) permit the control of the nature of the polyoxotungstate clusters and their connectivity via the copper ions, and hence the dimensionality of the framework. A single phase has been obtained with silicon as heteroelement at an initial pH of 5, namely the 2D material [SiW12O40][Cu(2,2′-bpy)2]2·10H2O (1) with saturated Keggin polyoxotungstates linked by {Cu(2,2′-bpy)2}2+ groups. With phosphorous as heteroelement and at the same initial pH, three different structures have been isolated according to the nature of the ligand. Indeed, the two 1D materials [{Cu5(2,2′-bpy)5(H2O)(HPO4)(PO4)}PW11CuO39]·6H2O (2) with 2,2′-bpy and [4,4′-Hbpy][{Cu2(2,2′-bpy)2(4,4′-bpy)2.5}PW11CuO39]·16H2O (3) with a mixture of 2,2′- and 4,4′-bpy have been characterized, and a coordination polymer with polyoxometalate guests Na3[4,4′-Hbpy]{Cu4(4,4′-bpy)8(H2O)8}[PW11CuO39(H2O)][PW10Cu2O38(H2O)2]·38H2O (4) with 4,4′-bpy has been obtained. Finally, in basic medium (pH = 10) the unprecedented molecular cluster Na2[{Cu8(2,2′-bpy)8}(PW8O31)2]·15H2O (5) has been evidenced. Magnetic studies of compound 2 revealed that the predominant interactions involve only 4 paramagnetic centers, which are interacting within pairs, among the 6 Cu(II) centers. The χMT = f(T) curve can be fitted using the dinuclear expression appropriate to the HDVV isotropic exchange Hamiltonian H = −JS1×S2, with S1 = S2 = ½ and J = −105.4 cm−1, showing strong antiferromagnetic interactions within the two Cu(II) pairs.

1,4-Di(1,2,3-triazol-1-yl)butane as building block for the preparation of the iron(II) spin-crossover 2D coordination polymer.

Abstract: The novel bidentate ligand 1,4-di(1,2,3-triazol-1-yl)butane (bbtr) reacts with Fe(ClO4)2·6H2O to form the 2D coordination polymer with (3,6) network topology. The {[Fe(bbtr)3](ClO4)2}∞ represents an example of spin-crossover material based on 1,2,3-triazole as donor group, and displays an abrupt spin transition accompanied by a thermal hysteresis loop (T1/2↓ = 101 K and T1/2↑ = 109 K).

Coordination polymers of La(III) as bunched infinite nanotubes and their conversion into an open-framework structure.

Abstract: Pyridine-2,6-dicarboxylic acid (pdcH2) reacts with LaCl3 x 7H2O under hydrothermal conditions followed by evaporation at room temperature to give a metal-organic framework structure of the empirical formula, [La(pdc)(H2O)4] x Cl (1), in the form of infinitely long bunched nanotubes. The chloride ions and water molecules occupy the tubular as well as the inter-tubular spaces. When La(NO3)3 x 7H2O is used in place of LaCl3 x 6H2O, a similar structure is formed with the empirical formula, [La(pdc)(H2O)4] x NO3 (2), where water molecules and the nitrate anions occupy the voids as in the case of 1. When an aqueous solution of AgNO3 is added to an aqueous solution of 1, the Cl- ions are replaced completely by NO3- ions to form 2; thus, the tubular structure is conserved. However, when AgBF4 is used in place of AgNO3, the tubular structure breaks down, and a new 3-D MOF structure, [La(pdc)(pdcH)(H2O)2] x 4H2O (3), is formed where the cavities are occupied by hexameric and dimeric water clusters. Structure 3 is also formed as the sole product when La(OAc)3 x xH2O is treated with pyridine-2,6-dicarboxylic acid following the method adopted for 1 and 2. Formation of the tubular structure depends on the molar ratio of the ligand and the metal. When higher than 1 equiv of the metal is taken, a linear coordination polymer, [La2(pdc)3(H2O)6] x 2H2O (4), is formed. This study provides the first nanotubular structure of a pure lanthanide metal.

Rational design and construction of the first tetrahedral net with photoluminescent Cu4I4 cubane cluster as the tetrahedral node

Abstract: Solvothermal reaction of CuI with flexible 1,3-bis(4-pyridyl)propane generated the first three-dimensional coordination polymer constructed with the rigid tetrahedrally connected Cu4I4 cluster unit. The net is a rare chiral triple-interpenetrated, quartz net with of vertex symbol 64.82. The solid-state luminescence spectrum displays a strong red emission band at room temperature (λmax = 601 nm), characteristic of the Cu4I4 cluster centers.

Mn(II) Staircase Structures Stitched by Water Clusters to a 3D Metal-Organic Open Framework: X-ray Structural and Magnetic Studies

Abstract: 4-Hydroxypyridine-2,6-dicarboxylic acid (chelidamic acid, cdaH2) reacts with Mn(OAc)2·4H2O to form a 1D staircase structure with dimeric Mn(II) units connected by water clusters to form a 3D framework, {[Mn2(cda)2·4H2O]·4H2O}n, 1, in aqueous pyridine at room temperature. The compound crystallizes in the triclinic space group P1 with a = 9.495(3), b =10.733(5), c = 11.065(4) A, α = 87.42(5), β = 74.14(5), γ = 80.07(2)°, U = 1068.5(9) A3, Z = 2, ρcalcd = 1.915 g cm-3, T = 100 K, μ = 1.28 mm-1, R1 = 0.0453 (I > 2σ(I)), wR2 = 0.1046, GOOF = 1.282. Upon removal of the water molecules by heating, the 3D structure breaks down. Thermogravimetric analysis, infrared, X-ray powder diffraction studies, and X-ray crystallography were performed to characterize this compound. Since the coordination polymer has diaqua-bridged Mn(II) centers, it was subjected to variable-temperature magnetic studies.

A mixed-valence coordination polymer featuring two-dimensional ferroelectric order: {[Cu(I)4Cu(II)(Et2dtc)2Cl3][Cu(II)(Et2dtc)2]2(FeCl4)}n (Et2dtc- = diethyldithiocarbamate).

Abstract: The first mixed-valence coordination polymer indicating ferroelectric properties, {[CuI4CuII(Et2dtc)2Cl3][CuII(Et2dtc)2]2(FeCl4)}n (Et2dtc- = diethyldithiocarbamate), has been synthesized and crystallographically characterized. This complex has a two-dimensional infinite square lattice structure, including both Cu(I) and Cu(II) ions, which is confirmed by XPS and SQUID measurements. In addition, the ferroelectric behaviors are revealed by the dielectric measurements with a LCR meter and a ferroelectric tester.

Multidimensional Networks Constructed with Isomeric Benzenedicarboxylates and 2,2‘-Biimidazole Based on Mono-, Bi-, and Trinuclear Units

Abstract: Three new complexes of [Co(H2biim)2(1,2-bdc)] (1), [Cd(H2biim)(1,3-bdc)]2 (2), and [Cd3(H2biim)2(1,4-bdc)3]·2H2O (3) (bdc = benzenedicarboxylate, H2biim = 2,2‘-biimidazole) have been synthesized and characterized by single-crystal X-ray diffraction. Complex 1 exhibits a 2-D herringbone architecture with mononuclear building blocks assembled via a robust hydrogen-bonded synthon R22(9). The homo- and heterochiral assemblies were observed in 1 between the H2biim ligand and carboxylate group via single and double hydrogen-bonded synthons R22(9). Complex 2 is a ribbonlike polymer based on a binuclear unit, and the ribbons are alternately decorated by H2biim ligands on both sides and further packed through intercalation of the lateral H2biim ligands and hydrogen bonds between the H2biim and carboxylate oxygen atoms into 2-D networks. These layers extend into a 3-D architecture via π−π stacking interactions. Complex 3 is a 3-D coordination polymer with a α-Po net topology based on linear trinuclear {Cd3O14N4} cl...

Stable, Water-Soluble Pta-Based Ru–Ag Organometallic Polymers†

Abstract: One of the latest trends in supramolecular chemistry is the quest for reproducible methods to achieve controlled selforganization of discrete units to form homoand heterometallic coordination networks, aggregates, and polymers. This development is based on the use of appropriate organic, inorganic, and organometallic building blocks that allow the synthesis of 1D linear or twisted chains, 2D squares and polygons, and 3D cubes and polyhedra. Among the organic spacers, nitrogen-based aromatic heterocycles are the most widely used due to their good donor properties and rigidity. These ligands can act as corner units (bipy, phen) and spacers (pyrazines, terpy, porphyrinates, tetraazamacrocycles). P-donor ligands as spacers have received less attention: P2 and P5 ligands have been studied by Scheer and co-workers, whereas the use of multidentate phosphanes has been reviewed recently. To the best of our knowledge, the use of mixed N,P ligands as metal-coordinating spacers has not been reported to date. Very few coordination polymers are water soluble, an example being the poly(ferrocenylsilane)-b-poly(aminomethacrylate) copolymer recently described by Manners and coworkers as part of their ongoing study on metallocenebased polymers, which can be prepared by ring-opening polymerization to afford either macromolecules with pendant ferrocenyl substituents in the polymer side chains or poly(ferrocenylsilane)s. Other examples of ligands that afford coordination polymers with various topologies and applications are ferrocenyl ligands bearing bipyridines or carboxylates. Herein we describe the first known case of a watersoluble, air-stable, heterobimetallic polymeric structure based on two metal-containing moieties ([CpRu] and [AgCl2] ) bridged by a cagelike, water-soluble monodentate phosphane, 1,3,5-triaza-7-phosphaadamantane (pta), in an unprecedented N,P coordinating mode. We recently reported the synthesis and characterization of the water-soluble cyclopentadienylruthenium complex [CpRuCl(pta)2] (1), which is stabilized by the phosphaadamantane-like pta ligand, and described its catalytic and biological properties. As part of our studies on new water-soluble organometallic derivatives based on the [CpRu(pta)2] + moiety, we treated 1 with one equivalent of AgOTf (OTf=OSO2CF3) in DMSO to remove the chloro ligand. Unexpectedly, noAgCl precipitated from the resulting orange solution, and neither did it contain the expected product [CpRu(OTf)(pta)2] (2), which was obtained by treatment of 1 with TlOTf. Intrigued by this apparently odd result, we repeated the experiment in an NMR tube. P{H} NMR analysis in [D6]DMSO indicated the formation of a 1:1 mixture of the new complex [CpRu(pta)2(dmso-kS)]OTf (3 ; singlet at d= 28.13 ppm) and the bimetallic neutral coordination polymer [{CpRu(pta)2(dmso-kS)}{AgCl2}]¥ (4 ; singlet at d= 23.19 ppm), as shown in Scheme 1. Quantitative formation of 4 could be attained by adding one equivalent of NH4Cl to a reaction mixture containing 1 and AgOTf. The elemental analysis and spectroscopic data are consistent with one molecule of DMSO being incorporated in the compound (see Experimental Section). Upon repetition of the latter experiment in noncoordinating CDCl3 instead of [D6]DMSO, a similar Ru–Ag polymeric structure was obtained with the coordination sphere of Ru completed by an h-O-coordinated triflate anion, as suggested by the corresponding IR stretching frequency nOSO at n= 1261 cm 1 [20] and F{H} NMR chemical shift at d= 78.77 ppm. The negative charge of the repeating unit in this coordination polymer is likely to be balanced by the ammonium cation (Scheme 2). The complex {NH4[{CpRu(OTf)(pta)2}{AgCl2}]}¥ (5) is characterized by a singlet at d= 20.85 ppm (CDCl3) in the P{H} NMR spectrum. When dissolved in DMSO, 5 is quantitatively converted into 4 with elimination of NH4OTf. [*] Dipl.-Chem. C. Lidrissi, Prof. Dr. A. Romerosa, Dr. M. Saoud, Dipl.-Chem. M. Serrano-Ruiz rea de Quimica Inorganica Universidad de Almer a 04071 Almer a (Spain) Fax: (+34)950-015-008 E-mail: romerosa@ual.es

Synthesis of Conjugated Polymers Containing Terpyridine−Ruthenium Complexes: Photovoltaic Applications

Abstract: We report the synthesis of (E)-3-(4-bromo-2,5-dioctylphenyl)-2-(4-vinylphenyl)acrylonitrile (5). We further report the synthesis of conjugated polymer materials by palladium-catalyzed Heck coupling polymerization of 5 and 4-bromo-2,5-dioctyl-4‘-vinylstilbene (3) in the presence of 4‘-(4-bromophenyl)-2,2‘:6‘,2‘ ‘-terpyridine (8), giving poly(dioctylstilbenevinylene)s terminated by a terpyridine moiety. Their assembly using ruthenium complexation led to coordination homopolymers and copolymer with tetrafluoroborate counterions. The materials were characterized using SEC, MALDI, NMR, UV−vis, and fluorescence spectroscopy. The polymers were found to transfer energy to the complexes as seen through the complexes ability to quench fluorescence. The coordination polymers were applied to photovoltaics, and two types of devices were prepared: polymer solar cells obtained by spin-coating of the coordination polymer solution onto PEDOT:PSS-covered ITO substrates and dye-sensitized solar cells obtained by absorption...

3D Supramolecular Array Assembled by Cross-like Arrangement of 1D Sandwich Mixed Molybdenum−Vanadium Polyoxometalate Bridged Coordination Polymer Chains: Hydrothermal Synthesis and Crystal Structure of {[MoVI5MoV3VIV8O40(PO4)][Ni(en)2]}[Ni(en)2]2·4H2O

Abstract: A novel organic−inorganic hybrid material constructed from mixed molybdenum−vanadium polyoxoanion clusters and [Ni(en)2]2+ complex groups {[MoVI5MoV3VIV8O40(PO4)][Ni(en)2]}[Ni(en)2]2·4H2O (1) (en = ethylenediamine), has been prepared under hydrothermal conditions and structurally characterized by single-crystal X-ray diffraction. Complex 1 exhibits an interesting three-dimensional supramolecular array through cross-like arrangement of a one-dimensional coordination polymer anion chain {[MoVI5MoV3VIV8O40(PO4)][Ni(en)2]}4-, which is sandwiched by discrete cation complex fragments [Ni(en)2]2+. It is the first example of a three-dimensional organic/inorganic hybrid polyoxometalate formed by cross-like arrangement of a one-dimensional polyoxometalate bridged coordination polymer chain.

Multiple Regulated Assembly, Crystal Structures and Magnetic Properties of Porous Coordination Polymers with Flexible Ligands

Abstract: Four novel coordination polymers of NiII and CoII with flexible ligands, namely [Ni(oba)(bpe)]n·nH2O (1), [Co(oba)(bpe)]n (2), [Ni2(oba)2(bpy)2(H2O)2]n·nbpy (3), and [Co(oba)(bpy)1/2]n (4) [H2oba = 4,4′-oxybis(benzoic acid), bpe = 1,2-bis(4-pyridyl)ethane, bpy = 4,4′-bipyridine] were synthesised by hydrothermal reactions and characterised by single-crystal X-ray diffraction, elemental analysis and IR spectroscopy. The NiII ions in complex 1 are linked by flexible oba and bpe ligands to form square-grid-like corrugated sheets. These sheets are interpenetrated with each other, resulting in the formation of a 3D porous network with lattice water molecules in the channels. The variable temperature X-ray diffraction analysis shows that the framework is stable up to 300 °C despite the complete removal of the lattice water molecules during the heat treatment. Complex 2 can be regarded as possessing a α-polonium-related topology. Triple interpenetration occurs to form a nonporous structure. In complex 3, the oba and bpy ligands link NiII ions into 1D train-like boxes. These boxes are entangled, with the aid of hydrogen bonds, leading to the formation of a 3D porous supramolecular architecture. Free bpy ligands reside in the channels. The CoII ions in complex 4 are linked by oba and bpy ligands to form a complicated 3D coordination polymer. The lattice water molecules in complex 1 and free bpy ligands in complex 3 can be regarded as templates that play an important role in the formation of the porous structures of complexes 1 and 3. The magnetic properties of complexes 1, 2, and 4 have also been investigated. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005)

A series of single, double, and triple Me2biim-bridged dinuclear, trinuclear, and polymeric complexes: syntheses, crystal structures, and luminescent properties.

Abstract: Reaction of ZnCl2 and Me2biim (Me2biim = N,N‘-dimethyl-2,2-‘-biimidazole) in acidic or neutral aqueous solutions gave the noncoordinated ZnCl4·H2Me2biim (1) or the double Me2biim bridged [Zn2Cl4(μ-Me2biim)2] (2). Use of CdX2 (X = Cl, Br, I) instead of ZnCl2 yielded the single Me2biim bridged one-dimensional coordination polymer [CdX2(μ-Me2biim)]n (X = Cl, 3; Br, 4; I, 5). The stacking of the infinite chains are dominated by C−H···X interactions in 3 and 4 but by I···I interactions in 5, responsible for their different crystal structures. Use of Zn(NO3)2 instead of ZnCl2 produced the novel triple Me2biim-bridged [Zn2(μ-Me2biim)3(H2O)2](NO3)4·H2O (6). The unprecedented hexa-Me2bim bridged trinuclear [Cd3(μ-Me2biim)8]2(ClO4)12(H2O)6 (7) was obtained by using Cd(CH3CO2)2 in the presence of NaClO4. Compounds 1−7 were characterized by X-ray crystallography and IR. Examination of photophysical properties of 1−7 indicates that the fluorescence emission of Me2biim has been effectively enhanced, quenched, or shifte...

Polynuclear Lanthanide Hydroxo Complexes : New Chemical Precursors for Coordination Polymers

Abstract: The synthesis of hexanuclear lanthanide hydroxo complexes by controlled hydrolysis led to polymorphic compounds. The hexanuclear entities crystallize in four different ways that depend on the extent of their hydration. The four structures can be described as hexanuclear lanthanide entities with formula [Ln(6)(mu(6)-O)(mu(3)-OH)(8)(NO(3))(6)(H(2)O)(12)](2+). Two additional NO(3)(-) ions intercalate between the hexanuclear entities in order to ensure the electroneutrality of the crystal structure. Some crystallization water molecules fill the intermolecular space. The three first families of compounds (1-3) exhibit crystal structures that have previously been reported. The fourth family of compounds (4) is described here for the first time. Its chemical formula is [Ln(6)(mu(6)-O)(mu(3)-OH)(8)(NO(3))(6)(H(2)O)(12)](NO(3))(2).2H(2)O (Ln = Gd, Er, and Y). In this paper, the chemical and thermal stabilities of the hexanuclear lanthanide compounds are reported together with the magnetic properties of the Gd(III)-containing species. To use these entities as precursors for new materials, the substitution of the nitrato groups by chloride ions has been studied. Two byproduct compounds have so been obtained: The first (compound 5) is a nitrato/chloride hexanuclear compound of chemical formula [Er(6)(mu(6)-O)(mu(3)-OH)(8)(NO(3))(6)(H(2)O)(12)](NO(3))Cl.2H(2)O. The second one (compound 6) is a polymeric compound in which the hexanuclear entities are linked by an unexpected and original N(2)O(4) bridge. Its chemical formula is [Er(6)(mu(6)-O)(mu(3)-OH)(8)(NO(3))(4)(H(2)O)(11)(OH)(ONONO(2))]Cl(3).2H(2)O. Its crystal structure can be described as the juxtaposition of chainlike molecular motifs. To the best of our knowledge, this is the first example of a coordination polymer synthesized from an isolated polylanthanide hydroxo complex.