Showing papers on "Coordination polymer published in 2007"
TL;DR: The highly ordered amide groups in the channels play an important role in the interaction with the guest molecules, which was confirmed by thermogravimetric analysis, adsorption/desorption measurements, and X-ray crystallography.
Abstract: To create a functionalized porous compound, amide group is used in porous framework to produce attractive interactions with guest molecules. To avoid hydrogen-bond formation between these amide groups our strategy was to build a three-dimensional (3D) coordination network using a tridentate amide ligand as the three-connector part. From Cd(NO3)2·4H2O and a three-connector ligand with amide groups a 3D porous coordination polymer (PCP) based on octahedral Cd(II) centers, {[Cd(4-btapa)2(NO3)2]·6H2O·2DMF}n (1a), was obtained (4-btapa = 1,3,5-benzene tricarboxylic acid tris[N-(4-pyridyl)amide]). The amide groups, which act as guest interaction sites, occur on the surfaces of channels with dimensions of 4.7 × 7.3 A2. X-ray powder diffraction measurements showed that the desolvated compound (1b) selectively includes guests with a concurrent flexible structural (amorphous-to-crystalline) transformation. The highly ordered amide groups in the channels play an important role in the interaction with the guest molec...
883 citations
TL;DR: A new chiral coordination polymer, (BMIm)2[Ni(TMA-H)2(H2O)2, was prepared ionothermally from chiral ionic liquid and induces chirality in the resulting solid, despite the fact that the anion is not occluded by the material and that the solid itself is built from only nonchiral building blocks.
Abstract: A new chiral coordination polymer, (BMIm)2[Ni(TMA-H)2(H2O)2], was prepared ionothermally from chiral ionic liquid. The use of l-aspartate as one component of the ionic liquid induces chirality in the resulting solid, despite the fact that the anion is not occluded by the material and that the solid itself is built from only nonchiral building blocks. Without the chiral component, an achiral compound is formed under the same synthesis conditions.
385 citations
TL;DR: IR and powder X-ray diffraction of Tb1 before and after catalysis indicate the catalyst maintains an open framework structure during the catalytic reactions, indicating a catalytically active open-framework pillared layer-type coordination polymer.
Abstract: Reaction of Tb(III) and two bridging ligands, a redox-active benzoic acid-terminated hexavandate ([V6O13{(OCH2)3C(4-CONHC6H4CO2H)}2]2- (1) and 4,4‘-bis(pyridine-N-dioxide) (bpdo) produces a catalytically active open-framework pillared layer-type coordination polymer, Tb1. The network material catalyzes aerobic oxidation of PrSH to PrSSPr and the oxidation tetrahydrothiophene (THT) to tetrahydrothiophene oxide (THTO) by tert-butylhydroperoxide under ambient conditions. Tb(III) ions and bpdo units form two-dimensional (2D) coordination layers, and the 2D layers are connected by 1 to produce a three-dimensional coordination network. IR and powder X-ray diffraction of Tb1 before and after catalysis indicate the catalyst maintains an open framework structure during the catalytic reactions.
253 citations
TL;DR: The use of a reduced symmetry organic linker for the preparation of porous coordination polymers is demonstrated and a striking feature of the structure is its incorporation, in a single material, of both the ubiquitous dinuclear Cu(II) paddlewheel motif and the rarely observed trinuclear Cu (II) cluster.
Abstract: The use of a reduced symmetry organic linker for the preparation of porous coordination polymers is demonstrated. The solvothermal reaction of the unsymmetrically substituted biaryl compound biphenyl-3,4‘,5-tricarboxylic acid with Cu(II) ions produces a [3,4,6]-connected coordination polymer exhibiting very high porosity and surface area (SLangmuir = 3100 m2/g). A striking feature of the structure is its incorporation, in a single material, of both the ubiquitous dinuclear Cu(II) paddlewheel motif and the rarely observed trinuclear Cu(II) cluster. Saturation H2 uptake, measured at 77 K, shows an excess gravimetric uptake of 5.7 wt % at 45 bar with a steep rise at low pressures.
215 citations
198 citations
TL;DR: A novel 3D metal−organic coordination polymer constructed from hollow, spherical, nanometer-sized molecular faceted polyhedra and a flexible tetracarboxylate ligand designed to simultaneously assemble and cross-link these nanoballs in situ has been synthesized and structurally characterized.
Abstract: A novel 3D metal−organic coordination polymer constructed from hollow, spherical, nanometer-sized molecular faceted polyhedra and a flexible tetracarboxylate ligand designed to simultaneously assemble and cross-link these nanoballs in situ has been synthesized and structurally characterized. The crystal structure involves 2-fold interpenetration with each framework exhibiting pores of dimensions which vary from less than 1 nm to just over 2.5 nm.
196 citations
TL;DR: The dehydrated 1a demonstrated a size-selective solvent adsorption linking chemi- and physisorption processes and shrinkage/expansion of its framework, and the flexible magnetic framework incorporating removable coligands delivered multifunctions with chemical response.
Abstract: Structural flexibility is a remarkable characteristic of coordination polymers and significant for the attainment of environmental responsivity. We have prepared a 2D cyanide-bridged MnIICrIII coordination polymer, [Mn(NNdmenH)(H2O)][Cr(CN)6]·H2O (1; NNdmen = N,N-dimethylethylenediamine), with sophisticatedly arranged removable water coligands. The compound clearly showed a reversible single-crystal-to-single-crystal transformation between the 2D sheet and a 3D pillared-sheet framework of dehydrated [Mn(NNdmenH)][Cr(CN)6] (1a). The structural change was reversible and accompanied with generation/cleavage of CN−Mn bonds between 2D sheets by dehydration/hydration. Compounds 1 and 1a also exhibited a ferrimagnetic ordering at 35.2 and 60.4 K, respectively, and the magnetic characteristics were reversibly converted by guest adsorption/desorption. In addition, the dehydrated 1a demonstrated a size-selective solvent adsorption linking chemi- and physisorption processes and shrinkage/expansion of its framework. ...
195 citations
TL;DR: In this paper, the 3D spin-crossover coordination polymer Fe(pyrazine) was constructed using a combination of lift-off and bottom-up (MSA) methods.
Abstract: Molecular spin-crossover complexes of 3d–3d transitionmetal ions have been the focus of many researchers’ work because of their fascinating properties associated with the bistability of their electronic states (high spin (HS) or low spin (LS)). Although the origin of the spin-crossover phenomenon is purely molecular, the macroscopic behavior of these systems in the solid state is strongly determined by the interactions, of mainly elastic origin, between the transition-metal ions. Recently, remarkable progress has been made in the area of spin-crossover complexes with infinite one-, two-, or three-dimensional (1D, 2D, 3D) networks, the so-called coordination polymers. The purpose of this approach was the enhancement and fine tuning of cooperative properties by the strong covalent links between the metallic centers in the polymers. Indeed, a number of highly cooperative polymer systems have been reported in the recent literature that display hysteretic behavior (thermal and piezo), in some cases even at room temperature. In addition to this, we have recently demonstrated that 3D coordination polymers represent an attractive platform for growth of surface thin films with spin-crossover properties. In fact, the 3D network structure allows the sequential assembly, via stepwise adsorption reactions, of multilayer films based entirely on intraand interlayer coordination bonds. These films have opened up possibilities for investigating size-reduction effects, optical and dielectric properties, and device applications of spin-crossover materials. A further step in this direction is the generation of microand nanometer-sized lateral patterns. In fact, the multilayer sequential assembly (MSA) process (also called directed assembly or layer-by-layer assembly in the literature) has become increasingly popular not only for fabricating thin films but also many efforts have been devoted to generating distinct patterns of the multilayer films. Various lithographic and nonlithographic methods—such as deposition on chemically patterned surfaces, inkjet printing, lift-off processes, etching, direct photopatterning, and microcontact printing—have been explored with this aim. Each method has, of course, different merits, but the lift-off process remains an industry standard owing to its simplicity and reliability. Furthermore, when combined with electron-beam lithography (EBL), it allows patterns to be obtained in a wide size range down to the sub10 nm limit, and the alignment of the patterns is also possible with respect to structures that may already exist on the substrate. In this Communication, we report on a process for nanoand microscale assembly of the 3D spin-crossover coordination polymer Fe(pyrazine)[Pt(CN)4] (1) (Scheme 1) by using a combination of top-down (lift-off) and bottom-up (MSA) methods. We call attention to the 3D polymer nature of this system, which is the key aspect for 1) obtaining room-temperature hysteresis, 2) assembling multilayers, and 3) performing C O M M U N IC A IO N
192 citations
TL;DR: An interdigitated porous coordination polymer with hydrophobic pore surface shows size and affinity dependent selective gas sorption properties accompanying the reversible structure transformation.
173 citations
165 citations
TL;DR: A flexible porous coordination polymer with highly selective capacity to separate benzene from cyclohexane is designed and synthesized.
Abstract: We have designed and synthesized a flexible porous coordination polymer with highly selective capacity to separate benzene from cyclohexane. The undulating channel providing the suitable space for the benzene and the H−π interaction between the host framework and the guest molecules result in this high selectivity.
TL;DR: Confinement of electron donor guests affords an efficient, photo-induced charge transfer with the anthracene moieties of a porous coordination polymer.
TL;DR: In this article, the influence of metal ions and supramolecular interactions on the self-assembly of in situ generated tetrazolate coordination architectures was investigated, and a series of new metal−organic complexes, [Zn(pzta)2(H2O)2] (1), [Cu( pzta)-2](H 2O)3 (2), [Cd(pza)2])n (3), [Ag(pzo),n (4), and [Ccd2(pzu),SO4)]n
Abstract: This work focuses on the investigation of the influence of metal ions and supramolecular interactions on the self-assembly of in situ generated tetrazolate coordination architectures. A series of new metal−organic complexes, [Zn(pzta)2(H2O)2] (1), [Cu(pzta)2](H2O)3 (2), [Cd(pzta)2]n (3), [Ag(pzta)]n (4), and [Cd2(pzta)(OH)(SO4)]n (5) [pzta = pyrazinyl tetrazolate], have been achieved by the in situ hydrothermal reactions of pyrazinecarbonitrile, sodium azide, and different metal ions. Complexes 1 and 2 have similar mononuclear structures bearing distinct intermolecular hydrogen-bond interactions to form two different 3D supramolecular networks based on 44-subnets. Complex 3 features a 1D crossed-shape chain structure. Complex 4 is a coordination polymer comprised of mildly undulated 2D layers with a (4.82) topological network. Complex 5 is a 3D diamondoid framework constructed by pentanuclear cadmium cluster nodes and pzta linkers. The configurations of complexes 1−5 span from mononuclear (1, 2), to one-d...
TL;DR: The solvothermal reaction of Zn(II) and 4,4'-oxybis(benzoic acid) in the presence of anhydrous ethanol leads to the generation of a novel 3D chiral coordination polymer with triple helical chains that had an enantiomeric excess.
TL;DR: IR measurements show that the metal-organic coordination polymer grows in a layer-by-layer fashion and can be reversibly loaded with NH3 and is very selective and occurs only on COOH-terminated regions of an organic surface, as demonstrated by AFM measurements.
Abstract: A metal−organic coordination polymer based on benzenetricarboxylic acid ligands and Zn(II) ions was grown on a COOH-terminated organic surface in a stepwise fashion. The deposited films were characterized using a number of surface analysis techniques, including X-ray absorption spectroscopy and X-ray photoelectron spectroscopy. IR measurements show that the metal−organic coordination polymer grows in a layer-by-layer fashion and can be reversibly loaded with NH3. The deposition is very selective and occurs only on COOH-terminated regions of an organic surface, as demonstrated by AFM measurements.
TL;DR: The results show that the increase of coordination sites of the ligands is an effective route to obtaining higher-dimensional structures and anions could influence the configuration of theligand to tune the coordination network topology from those with helical chains to those without.
Abstract: The self-assembly of silver(I) salts with bitopic triazole ligands 4-(salicylideneamino)-1,2,4-triazole (L1) and 4-(2-pyridinyl)-1,2,4-triazole (L2) produced dinuclear complexes and a 1D molecular-ladder coordination polymer, while the reaction of tritopic ligand 4-(3-pyridinyl)-1,2,4-triazole (L3) with AgClO4 afforded a right-handed helical 2D network with (4,4) topology, a meso layer constructed via left- and right-handed helical chains with AgBF4, and a 2D 4.82 net containing no helical chain with AgNO3. Using a tetratopic triazole ligand 2,6-bis(4-triazolyl)pyridine (L4), a 3D coordination polymer was isolated. This complex contains a cationic 4.63 network with rhombic channels, accepting two columns of uncoordinated ClO4- anions filling into every central cavity. Our results show that (i) the increase of coordination sites of the ligands is an effective route to obtaining higher-dimensional structures and (ii) anions could influence the configuration of the ligand to tune the coordination network top...
TL;DR: Via solvothermal synthesis, the self-assembly of CuCl(2), 1,3,5-benzenetricarboxylic acid, and N,N'-bis(4-pyridylformamide)-1,4-benzene in DMF generated a novel coordination polymer containing an unprecedented (3,4)-connected network.
TL;DR: An azido-metal-1,2,4-triazolate coordination polymer was synthesized using hydrothermal methods and has a rare three-dimensional non-interpenetrated utp or (10,3)-d topological network structure and exhibits spin-canted antiferromagnetism at low temperature.
TL;DR: Hydrothermal reaction of 4,4-trimethylenedipyridine with ZnI2 under 175 degrees C yields a novel compound that has a chiral infinite double-stranded helical structure consisting of two single-Stranded helices of the same handedness.
Abstract: Hydrothermal reaction of 4,4-trimethylenedipyridine (tmdp) with ZnI2 under 175 °C yields a novel compound, {[Zn2I4(tmdp)2]n·[Zn2I4(tmdp)2]n}, which has a chiral infinite double-stranded helical structure consisting of two single-stranded helices of the same handedness.
TL;DR: In this article, a series of zinc-containing coordination polymers incorporating the kinked organodiimine 4,4′-dipyridylamine (dpa) and phenylenediacetate (phda) isomers were synthesized.
Abstract: Hydrothermal synthesis has afforded a series of zinc-containing coordination polymers incorporating the kinked organodiimine 4,4′-dipyridylamine (dpa) and phenylenediacetate (phda) isomers. {[Zn(1,4-phda)(dpa)]·H2O}∞ (1) manifests a two-dimensional (2D) corrugated layer morphology. While both {[Zn(1,2-phda)(dpa)]·2H2O}∞ (2) and [Zn(1,3-phda)(dpa)]∞ (3) contain three-dimensional 4-fold interpenetrated coordination polymer networks, 2 possesses the SrAl2 structure type (sra, 42638 topology) but the acentric material 3 adopts the diamond structure type (dia, 66 topology). The varying morphologies thus reveal a significant structure-directing effect of the position of the acetate groups during self-assembly of these coordination polymers. Hydrogen-bonding mechanisms imparted by the central amine group of the dpa ligand provide ancillary supramolecular structure-directing effects in all three cases. All three materials undergo blue–violet luminescence upon irradiation with ultraviolet light.
TL;DR: Porous bilayer open coordination polymer and 3D porous coordination polymer have been assembled from Cd(NO3)2, ferrocene-1,1′-disulfonate, and bridging ligands 1,3-bis(4-pyridyl)propane (bpp) or 4,4′-bipyridine (bpy) as discussed by the authors.
Abstract: Porous pillared bilayer open coordination polymer {[Cd(bpp)2(O3SFcSO3)]·(CH3OH)2 ·(H2O)6}n 1 (Fc = ferrocene) and 3D porous coordination polymer {[Cd(bpy)2(O3SFcSO3)]·(CH3OH)4}n 2 have been assembled from Cd(NO3)2, ferrocene-1,1′-disulfonate, and bridging ligands 1,3-bis(4-pyridyl)propane (bpp) or 4,4′-bipyridine (bpy). Both of them show very special adsorption properties to copper salts. Along with the increase in the solution concentration of Cu(NO3)2, the percentage of adsorbed copper ions falls, but the percentage of exchanged central cadmium ions and the amount of adsorbed copper ions rises. In dilute solution, there mainly exists metal ion sorption, whereas both ion sorption and exchange are in charge of the whole progress in strong solution. Meanwhile, such materials could be used as ideal metal ion adsorbent toward some other metal cations, including of Pb2+, Zn2+, Mn2+, Co2+, Ni2+. However, when all these metal ions coexist in a mixture solution, the two ferrocenyl complexes selectively adsorb la...
TL;DR: The anion-templated syntheses of a variety of supramolecular assemblies of Co(II) show remarkable results in the presence of a weakly coordinating ion and the magnetic properties of these assemblies 1 b, 2, 3, and 5 are presented and discussed.
Abstract: We report the anion-templated syntheses of a variety of supramolecular assemblies of Co(II). Remarkably in the presence of a weakly coordinating ion such as BF(4) (-), a discrete three-dimensional cage [BF(4) subset(BF(4))(2)Co(2)(L(1))(4)][BF(4)] (2) is formed with three coordinated BF(4) (-) ions, a rare example in supramolecular chemistry (L(1)=di(benzimidazole)-1,4-phenylene). Switching to stronger coordinating ions, such as NO(3) (-) or Cl(-), a one-dimensional coordination polymer [[Co(L(1))(NO(3))(2)](n)] (3) and a metallomacrocycle [Co(2)(L(1))(2)(Cl)(4)] (5) were formed, respectively. These results illustrate the powerful effect of the anion-templating chemistry. Finally the magnetic properties of these assemblies 1 b, 2, 3, and 5 are presented and discussed.
TL;DR: A topological isomer based on Zn2 paddlewheel, dicarboxylate, and diamine ligands is synthesized by solvothermal methods after careful modulation of the reaction conditions to form a framework characterized by a pillared Kagome net topology.
Abstract: A topological isomer based on Zn2 paddlewheel, dicarboxylate, and diamine ligands is synthesized by solvothermal methods after careful modulation of the reaction conditions. The new framework is characterized by a pillared Kagome net topology and possesses a sustainable pore structure with high surface area (∼2400 m2/g) and large hexagonal channels (∼15 A).
TL;DR: A diamondoid network neutral coordination polymer [Mn(NCP)2]n (HNCP = 2-(4-carboxyphenyl)imidazo(4,5-f)(1,10)phenanthroline), synthesized by the hydrothermal reaction between MnSO4 and a new designed multifunctional ligand HNCP, displays a second harmonic generation efficiency that is approximately three times as much as that of potassium dihydrogen phosphate (KDP), weak antiferromagnetic character, and strong fluorescence emission with �
Abstract: A novel 7-fold interpenetration diamondoid network neutral coordination polymer [Mn(NCP)2]n (HNCP = 2-(4-carboxyphenyl)imidazo(4,5-f)(1,10)phenanthroline), synthesized by the hydrothermal reaction between MnSO4 and a new designed multifunctional ligand HNCP, displays a second harmonic generation efficiency that is approximately three times as much as that of potassium dihydrogen phosphate (KDP), weak antiferromagnetic character, and strong fluorescence emission with λmax at 588 nm as well as high thermal stability (up to ca. 490 °C).
TL;DR: Unique bridging modes of oxalates and nitrates have unexpectedly caused a porous 3D lanthanide-based coordination polymer, which has 1D channels and displays a special luminescent property.
Abstract: Unique bridging modes of oxalates and nitrates have unexpectedly caused a porous 3D lanthanide-based coordination polymer, which has 1D channels and displays a special luminescent property.
TL;DR: The imidazolium N-heterocyclic carbene precursor containing a methyl-substituted pyridyl functionality and its X-ray crystal structures are reported, which are intensely luminescent in the solid state and exhibits an emission band at 453 nm.
Abstract: Reaction of the imidazolium N-heterocyclic carbene precursor containing a methyl-substituted pyridyl functionality [HCH3im(CH3py)]PF6, 1, with Ag2O produces the homoleptic Ag(I) complex, [Ag(CH3im(CH3py))2]PF6, 2. In a simple carbene transfer reaction the analogous Au(I) species, [Au(CH3im(CH3py))2]PF6, 3, is formed by treatment of 2 with Au(tht)Cl in dichloromethane. Both 2 and 3 are structurally similar with nearly linearly coordinated NHC ligands. The methyl group appended to the pyridyl ring inhibits rotation of the pyridyl group at room temperature. Addition of AgBF4 to a hot propionitrile solution of 3 followed by crystallization with diethyl ether yields the one-dimensional coordination polymer, {[AuAg(CH3im(CH3py))2(NCCH2CH3)](BF4)2}n, 4, which contains Au−Ag separations of 2.9845(5) and 2.9641(5) A with intermetallic angles of 167.642(14)° and 162.081(9)°. This material is intensely luminescent in the solid state and exhibits an emission band at 453 nm (λex = 350 nm). Nearly colorless [Pd(CH3im(C...
TL;DR: In this paper, the first example of a coordination polymer in which [Ru(pytpy)2]2+ plays the role of a bridging bidentate ligand was described.
Abstract: The complex cation ligand [Ru(pytpy)2]2+
(pytpy = 4′-(4-pyridyl)-2,2′∶6′,2″-terpyridine) is an expanded 4,4′-bipyridine; we describe the first example of a coordination polymer in which [Ru(pytpy)2]2+ plays the role of a bridging bidentate ligand.
TL;DR: In this paper, a 3D coordination copper polymer was synthesized under microwave heating hydrothermal conditions, which was crystallographically characterised to be a threefold interpenetrated three-dimensional coordination (10,3)-b network.