Showing papers on "Coordination polymer published in 1999"
TL;DR: In this paper, a highly porous metal coordination polymer [Cu3(TMA)2(H2O)3]n (where TMA is benzene-1,3,5-tricarboxylate) was formed in 80 percent yield.
Abstract: Although zeolites and related materials combine nanoporosity with high thermal stability, they are difficult to modify or derivatize in a systematic way. A highly porous metal coordination polymer [Cu3(TMA)2(H2O)3]n (where TMA is benzene-1,3,5-tricarboxylate) was formed in 80 percent yield. It has interconnected [Cu2(O2CR)4] units (where R is an aromatic ring), which create a three-dimensional system of channels with a pore size of 1 nanometer and an accessible porosity of about 40 percent in the solid. Unlike zeolites, the channel linings can be chemically functionalized; for example, the aqua ligands can be replaced by pyridines. Thermal gravimetric analysis and high-temperature single-crystal diffractometry indicate that the framework is stable up to 240 degreesC.
5,061 citations
279 citations
TL;DR: The rigidity of the coordination polymer framework of Ni2(4,4′-bipy)3(NO3)4 is demonstrated quantitatively by determination of the structures of both ethanol-loaded and desolvated forms, showing only a small relaxation of the structure on guest loss.
262 citations
TL;DR: X-ray crystallography reveals that hydrogen bonding plays a key role in this process of solid-state supramolecular conversion of the helical coordination polymer into the chiral three-dimensional covalent open network.
Abstract: Thermal dehydration results in the solid-state supramolecular conversion of the helical coordination polymer [{[Cu(sala)]2(H2O)}n] into the chiral three-dimensional covalent open network [{Cu(sala)}n] (shown schematically). X-ray crystallography reveals that hydrogen bonding plays a key role in this process. H2sala=N-(2-hydroxybenzyl)-L-alanine
205 citations
TL;DR: This self-assembled, configurationally predetermined coordination polymer is built up from enantiopure chiral bipyridine-type ligands and silver ions.
Abstract: Its information content is infinitely smaller than that of DNA, but its structure (see picture) ressembles the double-stranded helix produced by nature. This self-assembled, configurationally predetermined coordination polymer is built up from enantiopure chiral bipyridine-type ligands and silver ions.
171 citations
TL;DR: The polymeric compound [Ag2(bpethy)5]-BF4)2, obtained from AgBF4 and 1,2-bis(4-pyridyl)ethyne (BPethy) in molar ratio 1:3, contains infinite molecular ladder motifs with monodentate ligands as sidearms on both sides, that are threaded through the squares of adjacent polymeric units in a mutual relationship, to give infinite "polythreaded" bidimensional layers as discussed by the authors.
139 citations
TL;DR: A honeycomb structure is shown by the one-dimensional coordination polymer comprising D6h -symmetric cucurbituril molecules and rubidium ions (see picture).
Abstract: A honeycomb structure is shown by the one-dimensional coordination polymer comprising D6h -symmetric cucurbituril molecules and rubidium ions (see picture). The cucurbituril molecules stack atop one another and show coordination of their carbonyl groups to the rubidium ions in between. The shape and symmetry of the building blocks encourage the coordination polymer chains to be arranged in such a way as to produce an open-framework structure with large, linear, hexagonal channels.
138 citations
TL;DR: The first terephthalato bis-tridentate bridging cadmium coordination polymer, [(TPT)(py)Cd] 1, with blue fluorescent emission, was synthesized by a hydrothermal reaction between Cd(ClO4)2· 6H2O, 1,4-dicyanobenzene and pyridine (py) as discussed by the authors.
Abstract: The first terephthalato (TPT) bis-tridentate bridging cadmium coordination polymer, [(TPT)(py)Cd] 1, with blue fluorescent emission, was synthesized by a hydrothermal reaction between Cd(ClO4)2· 6H2O, 1,4-dicyanobenzene and pyridine (py).
129 citations
TL;DR: The reaction of Zn2+ salts with the terephthalate dianion results in a herringbone motif coordination polymer; the orientation of the spacer ligands and the coordination geometry about the Zn 2+ ion is crucially dependent on hydrogen bonding to ancillary ligands; replacement of coordinated water with ethylenediamine results in marked changes to the polymer orientation without disruption of the fundamental features as mentioned in this paper.
110 citations
87 citations
TL;DR: The coordination polymer [CuSCN(bpa)] [bpa = 1,2-bis(4-pyridyl)ethane] consists of two interpenetrating three-dimensional four-connected frameworks of rare 42638 topology, each being constructed from the cross-linkage of infinite zigzag chains by bpa ligands as mentioned in this paper.
TL;DR: In this paper, the synthesis and X-ray characterization of the first example of an L-lactic acid two-dimensional metal coordination polymer with an additional bridging ligand was reported.
Abstract: The synthesis and X-ray characterization of the first example of an L-lactic acid two-dimensional metal coordination polymer with an additional bridging ligand, (S-(-)-lactate)(isonicotinato)zinc(II), (S-µ-2-hydroxypropanoinato)zinc(II), 1 is reported. It crystallizes in the acentric orthorhombic space group P212121 and displays powder SHG efficiencies ca. 1.2 times that of urea.
TL;DR: In this article, an unusual sawhorse connection is observed in the structure of a three-dimensional network formed by {[Ag(pyrazine)]NO2} with the nitrite counter-anion acting to block the cis coordination sites.
Abstract: The Ag(I) coordination networks, {[Ag(pyrazine)]NO2}∞ and {[Ag(4,4′-bipy)]NO2}∞ have been constructed in order to investigate the effect of anion upon network topology; an unusual sawhorse connection is observed in the structure of {[Ag(pyrazine)]NO2}∞ with the nitrite anion acting to ‘block’ cis coordination sites. The preparation of extended networks using inorganic coordination polymers has become an area of increasing study in recent years One of the reasons that this interest has arisen is because the synthetic procedure used to construct these materials allows a high degree of design. Ultimately this may lead to the development of materials with tuneable properties including structures with host–guest properties similar to those observed with zeolites and compounds with interesting electronic or magnetic properties. The high degree of design arises from the coupling of the well understood coordination properties of individual metal ions and highly-developed ligand syntheses with the newer areas of supramolecular chemistry and crystal engineering We have been studying the effect of individual building-blocks upon network structure. This has included the control of network topology and interpenetration in adamantoid networks via ligand desig and studies on the effect of variation of solvent of crystallisation upon network structure The nature of the counter-anion has also been shown to have a dramatic effect upon network topology and this is particularly noticeable in Ag(I) chemistry Recently we have demonstrated that replacement of AgBF4 or AgPF6 with AgNO3 results in a fundamental change of the extended structure of a coordination polymer with the ligand 3,6-di-4-pyridyl-1,2,4,5-tetrazine due to interactions between the Ag(I) centre and the NO3- anion to give a ‘helical staircase’ structure We now report the extension of these investigations to the use of AgNO2, and report an unusual example of a sawhorse connection within an extended network.{[Ag(pyz)]NO2}∞ (pyz=pyrazine) and {[Ag(4,4′-bipy)] NO2}∞ (4,4′-bipy=4,4′-bipyridyl) were prepared as colourless microcrystalline samples by adding a solution of the appropriate ligand in EtOH to a solution of AgNO2 in H2O.† In order to assess the effect of the nitrite counter-anion upon network topology single crystals of both complexes were grown by slow diffusion between an aqueous solution of AgNO2 and an ethanolic solution of the ligand. {[Ag(pyz)]NO2}∞‡ exists as a three-dimensional network in which each Ag(I) ion adopts a distorted octahedral environment (Fig. 1): each Ag(I) centre is coordinated by two pyrazine ligands, Ag–N 2.277(5) A, which bridge adjacent Ag(I) ions, and by the chelating nitrite counter-anion, Ag–O 2.487(6) A, in the equatorial sites. The two remaining axial coordination sites are occupied by weak Ag···Ag interactions (Fig. 1). The Ag···Ag separation of 3.2168(3) Ais a typical value for Ag···Ag interactions unsupported by ligands Ag···Ag interactions have been found to be significant in the extended structures of inorganic supramolecular networks. This is perhaps best illustrated by the formation of short interactions [Ag···Ag 2.970(2) AL in the extended three-dimensional network formed by {[Ag(4,4′-bipy)]NO3}∞ in which each Ag(I) centre is coordinated by one N-donor from each of two 4,4′-bipy ligands and participates in one Ag···Ag interaction to give a T-shaped motifIt can be seen that in {[Ag(pyz)]NO2}∞ each Ag(I) ion acts as a sawhorse junction in the network, with the nitrite blocking two cis sites of the junction (Fig. 2). To our knowledge this represents the first example of such a junction within a coordination polymer array. Sawhorse junctions are extremely rare in inorganic framework structures with the most notable examples being IrF4, RhF4 and PtF4 Therefore the overall network topology (Fig. 2) can be thought of as being related to the solid-state structure of IrF4 which has been described as ‘{IrF6} octahedra which share 4 F atoms, each with one other {IrF6} group leaving a pair of cis vertices unshared’ Similarly the network of {[Ag(pyz)]NO2}∞ is built from octahedra with cis vertices unshared.The structure of {[Ag(pyz)]NO2}∞ contrasts with that observed in the corresponding NO3- salt, {[Ag(pyz)]NO3}∞ Extended chains of alternating Ag(I) ions and pyrazine ligands are observed in {[Ag(pyz)]NO3}∞12 and significantly the nitrate anion is non-coordinating, in contrast to the behaviour of the nitrite anion observed in {[Ag(pyz)]NO2}∞.Single crystal X-ray studies of {[Ag(4,4′-bipy)]NO2}∞‡ reveal that a different network structure is adopted to that observed for {[Ag(pyz)]NO2}∞. The structure consists of slightly distorted linear chains of alternating Ag(I) ions and 4,4′-bipy ligands, N–Ag–N 171.98(10)° (Fig. 3) with the NO2- anions sitting between adjacent {[Ag(4,4′-bipy)]+}∞ chains so that each Ag(I) centre forms two weak Ag···O interactions of 2.667(2) Aand one weak Ag···N interaction of 2.978(3) A. Significantly, no Ag···Ag interactions are observed in {[Ag(4,4′-bipy)]NO2}∞, in contrast to {[Ag(pyz)]NO2}∞. The bridging 4,4′-bipy ligands in {[Ag(4,4′-bipy)]NO2}∞ adopt a very twisted arrangement, with a dihedral angle between the pyridyl rings of 41.3°. This value compares with observed values of 4.3° in [{Cu(cnge)2}2(µ-4,4′-bipy)][BF4]213 (cnge=2-cyanoguanidine), and 28.0, 30.0° observed in [Cu(4,4′-bipy)(MeCN)2]BF4 Both twisted and flat 4,4′-bipy molecules are incorporated in [Cu(µ-4,4′-bipy)- (H2O)2(FBF3)2]·4,4′-bipy, with a dihedral angle of 9.29° being observed for the coordinated 4,4′bipy ligands. In contrast the non-coordinated 4,4′-bipy ligands are constrained to be ideally planar by crystallographic symmetryThe IR spectra of the two complexes {[Ag(pyz)]NO2}∞ and {[Ag(4,4′-bipy)]NO2}∞ are consistent with the non-coordinating nitrite anion in {[Ag(4,4′-bipy)]NO2}∞ [νsym(NO2)=1243 cm-1] and the chelating mode of coordination for the anion in {[Ag(pyz)]NO2}∞ [νsym(NO2)=1269 cm-1] IR spectra of both the precipitated (microcrystalline) products and single crystals were found to be identical confirming the crystal structures to be representative of the bulk.Of the few previously reported examples of structurally characterised AgNO2 complexes both strongly coordinate and uncoordinated/weakly interactin NO2- have been reported. In the former Ag–O bond lengths are comparable to those observed hereCurrent work is aimed at studying the wider application of the nitrite anion as a fundamental building-block of extended coordination polymers and investigating the use of anions as a controlling factor in Ag(I) supramolecular networks. Acknowledgements
TL;DR: In this paper, six thiophene-2,5-dicarboxylic acid-based coordination polymers have been synthesized and structurally characterised and the physical and thermal properties of these complexes have also been studied.
Abstract: Six thiophene-2,5-dicarboxylic acid incorporated and self-assembled zinc(II), cobalt(II) and manganese(II) coordination polymers [Zn(Tda)(py)]n (1), [Zn(Tda)(bipy)(H2O)·1.5H2O]n (2), [Zn(Tda)(phen)(H2O)]n (3), [Co(Tda)(phen)(H2O)]n (4), [Mn(Tda)(phen)]n (5) and [Mn(Tda)(H2O)2]n (6) have been synthesised and structurally characterised. Complex 1 is characterised as a two-dimensional parallelogram with a cavity of about 10.4×10.4 A, while complexes 2 and 3 (4) are one-dimensional linear and zig-zag coordination polymers with mainly hydrogen-bonding and stacking interactions contributing to their crystal packing, respectively. Complex 5 is a two-dimensional porous sheet with alternating 16- and 8-membered rings, while complex 6 is a three-dimensional porous coordination polymer. The diverse coordination properties of thiophene-2,5-dicarboxylate make it a good building block for the construction of coordination polymers of different architectures, which are dependent on both the end-capping ligand and the coordination geometry of the metal ions. Physical and thermal properties of these complexes have also been studied.
TL;DR: The three-dimensional coordination polymer [Cd 2 (4,4′-bipy) 2 (H 2 O) 3 (SO 4 ) 2 ]·3 H 2 O (1 ) was synthesized by the hydrothermal reaction of 4, 4′-Bipyridine with CdSO 4 ·8/3H 2O in 1:1 mole ratio in a sealed tube at 120°C as discussed by the authors.
TL;DR: Ferromagnetic and antiferromagnetic alternating interactions within and between chains, respectively, were interpreted for a one-dimensional coordination polymer having high-spin MnII centers bridged by azido ligands.
Abstract: Ferromagnetic and antiferromagnetic alternating interactions within and between chains, respectively, were interpreted for a one-dimensional coordination polymer having high-spin (S = 5/2) MnII centers bridged by azido ligands, namely, [Mn(bpm)(N3)2]n (bpm = bis(pyrazol-1-yl) methane)
TL;DR: The connection of square-planar [Ni(CN)4]2- ions with Ph3Sn+ ions results in 1, a noninterpenetrated three-dimensional coordination polymer with an expanded NbO structure.
Abstract: The connection of square-planar [Ni(CN)4]2− ions with Ph3Sn+ ions results in 1, a noninterpenetrated three-dimensional coordination polymer with an expanded NbO structure. The (Ph3Sn)2Ni(CN)4 framework (shown schematically without phenyl groups and solvent molecules) displays a large central cavity that is occupied by Ph3SnOH, acetonitrile, and water molecules.
TL;DR: The first metal coordination polymer containing 3,4′-bipyridine (3, 4′bpy) was prepared by the hydrothermal treatment of Cu(NO3)2·2.5H2O, Me3SnBr and 3, 4´bpy as mentioned in this paper.
Abstract: The first metal coordination polymer containing3,4′-bipyridine (3,4′-bpy) was prepared by the hydrothermal treatment of Cu(NO3)2·2.5H2O, Me3SnBr and3,4′-bpy and its crystal structure shows a infinite double chain composed of two 3,4′-bpy and Br as well as copper(I) ions with an approximately rectangular molecular box of 4.0 × 10.68 A.
TL;DR: The first free-base meso-tetraarylporphyrin coordination polymer is assembled from meso tetrapyridylporphyrin and HgBr2 via 4-connected peripheral ligation, and it possesses a novel one-dimensional structural motif with large interporphyrein cavities as discussed by the authors.
TL;DR: In this article, it has been shown that the reaction of chiral racemic pyrrolidine 30 (HL10(R,S)) with copper(II) acetate via the intermediate Ci-symmetric building blocks 31 (CuL 10(R)L10(S)) furnishes one-dimensional 1D-∞1[CuL10[R]L10-S](S)] 32.
Abstract: Reaction of methanolic copper(II) acetate solution with oxazolidine 21 (HL7) led to the formation of the one-dimensional coordination polymer 1D-∞1[CuL27] 23. On the contrary, reaction of copper(II) acetate in methanol with pyrrolidine 24 (HL8) yielded the two-dimensional coordination polymer 2D-∞2[CuL28] 26. A common feature of 23 and 26 are the C2h-symmetric coordinatively unsaturated building blocks 22 and 25. In 1D-∞1[CuL27] 23, the cyano groups are linked to copper in a side-on fashion and the monomers 22 are oriented parallel to one another, whereas in 2D-∞2[CuL28] 26 the cyano groups are bound to copper in the end-on mode and the monomers 25 are oriented at an angle of 117° to one another. In both 1D-23 and 2D-26, copper has a distorted octahedral coordination sphere. On the other hand, reaction of methanolic copper(II) acetate solution with enantiomerically pure (5S)-pyrrolidine 27 (HL9(S)) led to the formation of the diastereomeric helical strands (M)-/(P)-1D-∞1[CuL29] 29. (M)- and (P)-29 are present in pairs in the infinite unit cell. In helical 1D-29, copper is tetragonal-pyramidally coordinated and the C2-symmetric monomers 28 (CuL29) are linked through only one cyano group. Moreover, it has been shown that the reaction of chiral racemic pyrrolidine 30 (HL10(R,S)) with copper(II) acetate via the intermediate Ci-symmetric building blocks 31 (CuL10(R)L10(S)) furnishes one-dimensional 1D-∞1[CuL10(R)L10(S)] 32. Single-crystal X-ray diffraction analyses of the supramolecular species 23, 26, 29, and 32 unequivocally establish the structures of these coordination polymers.
TL;DR: In this paper, the synthesis and X-ray crystal structure of [Ca(terephthalate)(H2O)3] 1a and [M(Terephthalates)(H 2O)4] 1b and 1c have been investigated.
TL;DR: In this paper, a chiral 3D coordination polymer Zn{Z-[4-2-(3-pyridyl)ethenyl]benzoate} 2·0.5H2O with two intersecting sixfold helices was presented.
TL;DR: In this paper, the influence of solvent and anion on the formation of coordination polymers between silver(I) and 3,6-bis(pyridin-3-yl)-1,2,4,5-tetrazine (3,3′-pytz), a bridging ligand that can adopt both cisoid and transoid conformations, is reported.
17 Mar 1999
TL;DR: A porphryin coordination polymer, (3′-cyanophenyl) rhodium(III) 3, has been synthesized from the intermolecular C-H activation of the reaction of RhCl3 with porphyrin H2(tmp)(Ph)8, 1, and the X-ray structure shows a ziz-zag chain this article.
TL;DR: The oxidation of molybdenum hexacarbonyl, Mo(CO)(6), by antimony(V) fluoride, SbF(5), at 60 degrees C in an excess of liquid SbFs, produces polymeric polymeric cation, which is suitable for a single-crystal X-ray diffraction study.
Abstract: The oxidation of molybdenum hexacarbonyl, Mo(CO)6, by antimony(V) fluoride, SbF5, at 60 °C in an excess of liquid SbF5, produces polymeric [{Mo(CO)4}2(cis-μ-F2SbF4)3]x[Sb2F11]x as the main product....
TL;DR: The AgI(15crown-5) core moiety is a versatile supramolecular synthon, which is able to satisfy its coordination requirements using a variety of capping ligands as mentioned in this paper.
TL;DR: The reaction between AgBF4 and [Ag(C2But)]n in 1:2 mol ratio affords the novel cationic polymer [Ag3(C 2But)2+]n The crystal structure has been determined by singlecrystal X-ray diffraction study.
TL;DR: In this paper, the InN2C3 heterocycle was characterized by NMR, IR and MS techniques as well as by an X-ray structure determination, and it formed an infinite chain-like coordination polymer, along with the cooperative interactions of InN contacts and N-H…N bridges.
Abstract: Trimerization of Acetonitrile through Trimethylindium
MeCN can be trimerized in the presence of InMe3 and a trace of CsF to form the InN2C3 heterocycle [Me2In{HNC(Me)}2C(CN)] (3). 3 was characterized by NMR, IR and MS techniques as well as by an X-ray structure determination. According to the structural analysis 3 forms an infinite chain-like coordination polymer, [3]n, along [001] by the cooperative interactions of In…N contacts and N–H…N bridges.
TL;DR: In this paper, a new porous coordination polymer, H2dpds, was synthesized and structurally characterized, and X-ray analysis demonstrates that the decavanadate anions are doubly bridged by H2DPds ligands to provide a one-dimensional structure.
Abstract: New porous coordination polymer, {(H2dpds)2[V10O26(OH)2]·10H2O}n (H2dpds = bis(4-pyridinium) disulfide), was synthesized and structurally characterized. X-ray analysis demonstrates that the decavanadate anions are doubly bridged by H2dpds ligands to provide a one-dimensional structure. This network affords channeling cavities with dimension of about 2 × 4 A along the c-axis.