A cyanide‐bridged FeIII–MnII heterobimetallic one‐dimensional coordination polymer: synthesis,crystal structure,experimental and theoretical magnetism investigation

A new cyanide‐bridged Fe^III–Mn^II heterobimetallic coordination polymer (CP), namely catena‐poly[[[N,N′‐(1,2‐phenylene)bis(pyridine‐2‐carboxamidato)‐κ⁴N,N′,N′′,N′′′]iron(III)]‐μ‐cyanido‐κ²C:N‐[bis(4,4′‐bipyridine‐κN)bis(methanol‐κO)manganese(II)]‐μ‐cyanido‐κ²N:C], {[FeMn(C₁₈H₁₂N₄O₂)(CN)₂(C₁₀H₈N₂)₂(CH₃OH)₂]ClO₄}_n, ( 1 ), was prepared by the self‐assembly of the trans‐dicyanidoiron(III)‐containing building block [Fe(bpb)(CN)₂]^? [bpb^2? = N,N′‐(1,2‐phenylene)bis(pyridine‐2‐carboxamidate)], [Mn(ClO₄)₂]·6H₂O and 4,4′‐bipyridine, and was structurally characterized by elemental analysis, IR spectroscopy, single‐crystal X‐ray crystallography and powder X‐ray diffraction (PXRD). Single‐crystal X‐ray diffraction analysis shows that CP 1 possesses a cationic linear chain structure consisting of alternating cyanide‐bridged Fe–Mn units, with free perchlorate as the charge‐balancing anion, which can be further extended into a two‐dimensional supramolecular sheet structure via inter‐chain π–π interactions between the 4,4′‐bipyridine ligands. Within the chain, each Mn^II ion is six‐coordinated by an N₆ unit and is involved in a slightly distorted octahedral coordination geometry. Investigation of the magnetic properties of 1 reveals an antiferromagnetic coupling between the cyanide‐bridged Fe^III and Mn^II ions. A best fit of the magnetic susceptibility based on the one‐dimensional alternating chain model leads to the magnetic coupling constants J₁ = ?1.35 and J₂ = ?1.05 cm^?1, and the antiferromagnetic coupling was further confirmed by spin Hamiltonian‐based density functional theoretical (DFT) calculations.     

A three‐dimensional CuII–WIV bimetallic porous assembly containing a zigzag ladder structure

The asymmetric unit of the three‐dimensional Cu^II–W^IV polymeric assembly {[Cu(en)₂][Cu(en)][W(CN)₈]·4H₂O}_n (en is ethyl­enedi­amine, C₂H₈N₂) or {[Cu₂W(CN)₈(C₂H₈N₂)₃]·4H₂O}_n, which can be named as polymeric bis­(ethyl­enedi­amine)copper(II) (ethyl­enedi­amine)copper(II) octa­cyano­tungstate(IV) tetrahydrate or penta‐μ‐cyano‐tri­cyano­tris­(ethyl­enedi­amine)­dicopper(II)­tungsten(IV) tetra­hydrate, consists of two half [Cu(en)₂]²⁺ cations (Cu²⁺ on inversion centres), a [Cu(en)]²⁺ cation and a [W(CN)₈]^4? ion, together with four water mol­ecules. The latter Cu^II site is coordinated by five N atoms from an en ligand and by three cyanides in a distorted square‐pyramidal geometry. The Cu^II atoms of the two [Cu(en)₂]²⁺ cations reside in an elongated octahedral coordination environment, and one of them is localized at a centre of inversion. The W atom is coordinated by eight cyano groups in an irregular square antiprism. Five of these act as bridging units connecting the W and the three Cu atoms, to form an infinite three‐dimensional porous network containing a zigzag ladder structure.     

A novel tetrazolate‐ and cyanide‐bridged three‐dimensional heterometallic coordination polymer: crystal structure,thermal stability and magnetic properties

By using environmentally friendly K₃[Co(CN)₆] as a cyanide source, the solvothermal reaction of CuCl₂ and tetrazole (Htta) led to a novel tetrazolate‐ and cyanide‐bridged three‐dimensional heterometallic Cu^II–Co^III complex, namely poly[[hexa‐μ₂‐cyanido‐κ¹²C :N‐pentakis(μ₃‐tetrazolato‐κ³N ¹:N ²:N ⁴)cobalt(III)tetracopper(II)] monohydrate], {[Co^IIICu^II₄(CHN₄)₅(CN)₆]·H₂O}_n , (I). The crystal structure analysis reveals that it is the first example of a (6,8,8)‐connected three‐dimensional framework with a unique topology, constructed from anionic [Co(CN)₆]³⁻ and cationic [(Cu1)₂(tta)₂]²⁺ and [(Cu2Cu3)(tta)₃]⁺ units through μ₂‐cyanide and μ₃‐tetrazolate linkers. The compound was further characterized by thermal analysis, vibrational spectroscopy (FT–IR), scanning electron microscopy/energy‐dispersive X‐ray spectroscopy (SEM–EDS) and magnetic measurements. The magnetic investigation indicates that the complex exhibits antiferromagnetic coupling between adjacent Cu^II cations.     

Self‐assembly of long‐chain quaternary ammonium cations in a hybrid inorganic–organic material with one‐dimensional polymeric tribromidoplumbate(II)

catena‐Poly[benzyldecyldimethylammonium [plumbate(II)‐tri‐μ‐bromido]], {(C₁₉H₃₄N)[PbBr₃]}_n, crystallizes as an inorganic–organic hybrid following monoclinic space‐group symmetry P2₁/c. The structure consists of extended chains running along the [001] direction and built of [PbBr₃]⁻ units. These inorganic chains are separated by interdigitated ammonium cations which form hydrophilic layers through weak C—H...Br interactions. The architecture is essentialy the same as found for n‐alkylbenzyldimethylammonium bromides.     

A one‐dimensional chain structure based on unusual tetranuclear manganese(II) clusters

The title coordination polymer, poly[bis(μ₄‐biphenyl‐2,2′‐dicarboxylato)(dipyrido[3,2‐a:2′,3′‐c]phenazine)manganese(II)], [Mn₂(C₁₄H₈O₄)₂(C₁₈H₁₀N₄)]_n, was obtained through the reaction of MnCl₂·4H₂O, biphenyl‐2,2′‐dicarboxylic acid (H₂dpdc) and dipyrido[3,2‐a:2′,3′‐c]phenazine (L) under hydrothermal conditions. The asymmetric unit contains two crystallographically unique Mn^II ions, one unique L ligand and two unique dpdc ligands. One Mn ion is six‐coordinated by four O atoms from three different dpdc ligands and two N atoms from one L ligand, adopting a distorted octahedral coordination geometry. The distortions from ideal octahedral geometry are largely due to the presence of chelating ligands and the resulting acute N—Mn—N and O—Mn—O angles. The second Mn ion is coordinated in a distorted trigonal bipyramidal fashion by five O atoms from four distinct dpdc ligands. Four Mn^II ions are bridged by the carboxylate groups of the dpdc ligands to form an unusual tetranuclear Mn^II cluster. Clusters are further connected by the aromatic backbone of the dicarboxylate ligands, forming a one‐dimensional chain structure along the b axis. The title compound is the first example of a chain structure based on a tetranuclear Mn^II cluster.     

Infinite ladder‐like chains organized into a three‐dimensional zigzag supramolecular architecture in 9‐deazahypoxanthine

The asymmetric unit of the title compound, C₆H₅N₃O, consists of discrete molecules of 9‐deazahypoxanthine [systematic name: 3H‐pyrrolo[3,2‐d]pyrimidin‐4(5H)‐one]. The structure displays N—H...O hydrogen bonding, connecting the molecules into centrosymmetric dimers. These dimers are then connected by N—H...N hydrogen bonds into a ladder‐like chain along the c axis. The secondary structure is stabilized by weak noncovalent contacts of the C—H...O and C—H...C types, as well as by π–π stacking interactions, which organize the structure into a zigzag architecture.     

A Heterometallic FeII–DyIII Single‐Molecule Magnet with a Record Anisotropy Barrier

A record anisotropy barrier (319 cm^?1) for all d‐f complexes was observed for a unique Fe^II‐Dy^III‐Fe^II single‐molecule magnet (SMM), which possesses two asymmetric and distorted Fe^II ions and one quasi‐D_5h Dy^III ion. The frozen magnetization of the Dy^III ion leads to the decreased Fe^II relaxation rates evident in the Mössbauer spectrum. Ab initio calculations suggest that tunneling is interrupted effectively thanks to the exchange doublets.     

The synthesis,crystal structure and magnetic properties of a one‐dimensional terbium(III)–octacyanidomolybdate(V) assembly

A one‐dimensional cyanide‐bridged coordination polymer, poly[[aquadi‐μ‐cyanido‐κ⁴C:N‐hexacyanido‐κ⁶C‐(dimethylformamide‐κO)bis(3,4,7,8‐tetramethyl‐1,10‐phenanthroline‐κ²N,N′)terbium(III)molybdate(V)] 4.5‐hydrate], [MoTb(CN)₈(C₁₆H₁₆N₂)₂(C₃H₇NO)(H₂O)]·4.5H₂O}_n, has been prepared and characterized through IR spectroscopy, elemental analysis and single‐crystal X‐ray diffraction. The compound consists of one‐dimensional chains in which cationic [Tb(tmphen)₂(DMF)(H₂O)]³⁺ (tmphen is 3,4,7,8‐tetramethyl‐1,10‐phenanthroline) and anionic [Mo^V(CN)₈]³⁻ units are linked in an alternating fashion through bridging cyanide ligands. Neighbouring chains are connected by three types of hydrogen bonds (O—H...O, O—H...N and C—H...O) and by π–π interactions to form a three‐dimensional supramolecular structure. In addition, magnetic investigations show that ferromagnetic interactions exist in the compound.     

Self‐assembly of a one‐dimensional iron(II) coordination polymer with p‐phenylenebis(picolinaldimine)

catena‐Poly[[[dichloridoiron(II)]‐μ‐N,N′‐bis(2‐pyridylmethylene)benzene‐1,4‐diamine] methanol disolvate], [FeCl₂(C₁₈H₁₄N₄)]·2CH₃OH, forms a one‐dimensional coordination polymer. The polymeric chains run parallel to the c axis. O—H...Cl—Fe and C—H...O hydrogen‐bonding interactions with methanol solvent molecules stabilize the open supramolecular framework. Each Fe^II atom adopts an octahedral geometry coordinated by four N atoms from two N,N′‐bis(2‐pyridylmethylene)benzene‐1,4‐diamine ligands and completed by two cis Cl atoms. The compound has C₂ (and C_i) molecular symmetry, which is coincident with the crystallographic twofold symmetry at (0, y, ). The one‐dimensional structure is propagated via the crystallographic inversion center located at the benzene ring centroid (0, , 0).     

A one‐dimensional manganese(III)–porphyrin coordination polymer: crystal structure and photophysical properties

A novel manganese(III)–porphyrin complex, namely, catena‐poly[[chloridomanganese(III)]‐μ₂‐5,10,15,20‐tetrakis(pyridin‐3‐yl)‐21H,23H‐porphinato(2?)‐κ⁵N²¹,N²²,N²³,N²⁴:N⁵], [MnCl(C₄₀H₂₄N₈)]_n, 1 , was prepared by the hydrothermal reaction of manganese chloride with 5,10,15,20‐tetrakis(pyridin‐3‐yl)‐21H,23H‐porphine. The crystal structure was determined by single‐crystal X‐ray diffraction. The porphyrin macrocycle exhibits a saddle‐like distortion geometry. The Mn^III atom has a six‐coordination geometry. Each porphyrin unit links to two neighbouring units to yield a one‐dimensional coordination polymer. These chains are further interlinked by hydrogen bonds to form a two‐dimensional network. The complex shows red photoluminescence emission bands in ethanol solution, which can be attributed to ligand‐to‐ligand charge transfer (LLCT) accompanied by partial metal‐to‐ligand charge transfer (MLCT), as revealed by TDDFT calculations.     

Synthesis of ladder‐like polynorbornenes with n‐type perylenendiimide derivatives as bridges

Polymerizable tetrachloro‐perylenediimdes containing endo/exo‐norbornene groups on both imide sides were designed and synthesized. Endo/Exo‐type soluble ladder‐like polynorbornenes with perylenediimide (PDI) as bridges were prepared by ring‐opening metathesis polymerization (ROMP). XRD characterizations showed that the ladder‐like polynorbornenes had ordered structures similar to the supramolecular precursors assembled from the corresponding monomers. TGA measurements demonstrated great thermal stabilities for the both target P1‐Endo and P2‐Exo with T_d of about 320 °C at 5 wt % loss, respectively, which is important for further application in devices. Both polymers have good solubility in common organic solvents and easy to form thin films. Photophysical studies and cyclic voltammetry investigations reveal that polynorbornene films have wide‐range absorption from 400 nm to 600 nm and the HOMO/LUMO energy levels could be matched well with the donor‐PCzTh‐TVDCN. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Synthesis and characterization of organic–inorganic hybrid block copolymers containing a fully condensed ladder‐like polyphenylsilsesquioxane

A series of inorganic–organic hybrid block copolymers were synthesized via atom transfer radical polymerization using a fully condensed, ladder‐like structured polyphenylsilsesquioxane end‐functionalized macroinitiator. The inorganic portion, ladder‐like polyphenylsilsesquioxane, was synthesized in a one‐batch, base‐catalyzed system, whereas organic hard and soft monomers, styrene, and n‐butyl acrylate, were polymerized and copolymerized on the ends of the linear, inorganic backbone. Synthesized hybrid diblock, triblock, and random copolymers were characterized by ¹H NMR, ²⁹Si NMR, gel permeation chromatography, static light scattering, Fourier transform infrared spectroscopy, thermogravimetric analysis, and differential scanning calorimetry. Hybrid block copolymers were well‐defined with low polydispersity (<1.4) and exhibited enhanced thermal properties in the form of increased glass transition and degradation onset temperatures over their organic analogues.© 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

A tetrahedrally coordinated AgI and NiII complex with a two‐dimensional framework containing one‐dimensional helical chains

The title complex, poly[bis(μ₆‐pyridine‐2,6‐dicarboxylato N‐oxide)nickel(II)disilver(I)], [Ag₂Ni(C₇H₃NO₅)₂]_n or [Ag₂Ni(pydco)₂]_n (H₂pydco = pyridine‐2,6‐dicarboxylic acid N‐oxide), has a two‐dimensional sheet structure. The two carboxylate groups adopt two coordination modes. The Ni^II ion displays a distorted octahedral geometry, bonded to two carboxylate O atoms of two different pydco ligands and four O donors from another two ligands, i.e. two carboxylate O atoms and two N‐oxide O atoms. The Ag^I ion adopts a tetrahedral coordination, linked by three O atoms of three different carboxylate groups and an N‐oxide O atom.     

Synthesis,characterization, and curing kinetics of novel ladder‐like polysilsesquioxanes containing side‐chain maleimide groups

Two ladder‐like polysilsesquioxanes (LPS) containing side‐chain maleimide groups have been synthesized successfully by reacting N‐(4‐hydroxyphenyl)maleimide (HPM) with LPS containing 100 mol % of chloropropyl groups (Ladder A ) and 50 mol % of each methyl and chloropropyl group (Ladder B ). HPM was synthesized by reacting maleic anhydride with 4‐aminophenol, and the resulting amic acid was imidized using p‐toluenesulfonic acid as a catalyst (Scheme 1 ). The LPSs were characterized by Fourier transform infrared (FTIR), ¹H nuclear magnetic resonance (NMR), proton‐decoupled ¹³C NMR, ²⁹Si NMR, wide‐angle X‐ray diffraction (WAXD), differential scanning calorimetry (DSC), and thermogravimetric analysis (TGA). Characterization indicated that these polymers had ordered ladder‐like structures with possible defects. These polymers were soluble in common solvents at ambient temperature, which suggested that they were not crosslinked. Both the polymers and the HPM were cured, and their kinetics were followed by dynamic DSC. The Ozawa and Kissinger methods were used to calculate activation energies for curing. Curing increased the temperature at which both 5% weight loss and maximum rate of weight loss were observed. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 4036–4046, 2004     

A one‐dimensional chloride‐bridged PtII/PtIV mixed‐valence complex with a 4‐[(4‐hydroxyphenyl)diazenyl]benzenesulfonate counter‐ion

The title compound, catena‐poly[[[bis(ethylenediamine‐κ²N,N′)platinum(II)]‐ μ‐chlorido‐[bis(ethylenediamine)platinum(IV)]‐μ‐chlorido] tetrakis{4‐[(4‐hydroxyphenyl)diazenyl]benzenesulfonate} dihydrate], {[Pt^IIPt^IVCl₂(C₂H₈N₂)₄](HOC₆H₄N=NC₆H₄SO₃)₄·2H₂O}_n, has a linear chain structure composed of square‐planar [Pt(en)₂]²⁺ (en is ethylenediamine) and elongated octahedral trans‐[PtCl₂(en)₂]²⁺ cations stacked alternately, bridged by Cl atoms, along the b axis. The Pt atoms are located on an inversion centre, while the Cl atoms are disordered over two sites and form a zigzag ...Cl—Pt^IV—Cl...Pt^II... chain, with a Pt^IV—Cl bond length of 2.3140 (14) Å, an interatomic Pt^II...Cl distance of 3.5969 (15) Å and a Pt^IV—Cl...Pt^II angle of 170.66 (6)°. The structural parameter indicating the mixed‐valence state of the Pt atom, expressed by δ = (Pt^IV—Cl)/(Pt^II...Cl), is 0.643.     

Hydrothermal synthesis of the fist two‐dimensional folded layer formed by a cyano‐bridged one‐dimensional chain joined by Cu(I)?Cu(I) bonding

Two cyano‐bridged polymers, [Cu₃(CN)₃(phen)]_n ( 1 ) and [Cu(CN)(phen)]_n ( 2 ) (phen = 1,10‐phenphralonine), were synthesized by the hydrothermal reaction of Cu(NO₃)₂· 3H₂O, K₃[Fe(CN)₆] and phen and were characterized structurally by X‐ray, IR and ERSC methods. Compound 1 shows a two‐dimensional folded coordination network by Cu(I)? CN? Cu(I) and Cu(I)? Cu(I) interaction, while compound 2 exhibits an infinite helix chain by Cu(I)? CN linkages. Copyright © 2005 John Wiley & Sons, Ltd.     

A New Two‐dimensional Cyano‐bridged Chromium (HI)‐Nickel (II) Bimetallic Assembly with Stair‐like Layers

From the reaction of K₃[Cr(CN)₆] and [NiL](CIO₄)₂ (L= 1,8‐di(hydroxyethyl)‐l, 3, 6, 8, 10, 13‐hexaazacyclotetradecane), an infinite stair‐like layered assembly [NiL]₃ [Cr‐(CN)₆]₂‐6.5H₂O is obtained, in which each hexacyanochromate(III) ion connects three nickel(II) ions using three cis Of groups and the bridging cyanide ligands coordinate to the nickel ion in a trans fashion forming trans‐NiL(N°C)₂ moieties.     

Synthesis and characterization of a novel soluble reactive ladder‐like polysilsesquioxane with side‐chain 2‐(4‐chloromethyl phenyl) ethyl groups

A new kind of soluble structure‐ordered ladder‐like polysilsesquioxane with reactive side‐chain 2‐(4‐chloromethyl phenyl) ethyl groups ( L ) was first synthesized by stepwise coupling polymerization. The monomer, 2‐(4‐chloromethyl phenyl) ethyltrichlorosilane ( M ), was synthesized successfully by hydrosilylation reaction with dicyclopentadienylplatinum(II) chloride (Cp₂PtCl₂) ­catalyst. Monomer and polymer structures were characterized by FT‐IR, ¹H‐NMR, ¹³C‐NMR, ²⁹Si‐NMR, differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), vapor pressure osmometry (VPO) and X‐ray diffraction (XRD). This novel reactive ladder‐like polymer has promise potential applications as initiator for atom transfer radical polymerization, and as precursor for a variety of advanced functional polymers. Copyright © 2001 John Wiley & Sons, Ltd.     

A novel binuclear copper complex incorporating a nalidixic acid derivative displaying a one‐dimensional coordination polymeric structure

The identification of the antibacterial action of nalidixic acid (nx) was central to the development of the quinolone antibacterial compounds. The ability of the nx naphthyridyl ring to interact with and inhibit some proteins has encouraged the investigation of similar structures in the search for more active compounds with less adverse effects. The possibility of structural modification by attachment of other biologically active moieties to the naphthyridyl ring of nx allowed the development of new active antimicrobial molecules. Hydrazone derivatives of nx can be synthesized easily based on the condensation of the hydrazide derivative of nx with the desired aldehyde or ketone. Only a few complexes with nx hydrazone derivatives have been described but for none were the crystal structures elucidated. The synthesis of a new one‐dimensional Cu^II coordination polymer, namely catena‐poly[[copper(II)‐di‐μ‐chlorido‐copper(II)‐{μ‐1‐ethyl‐N′‐[(1H‐imidazol‐4‐yl)methylidene]‐7‐methyl‐4‐oxo‐1,4‐dihydro‐1,8‐naphthyridine‐3‐carbohydrazidato}‐[dimethanolcopper(II)]‐{μ‐1‐ethyl‐N′‐[(1H‐imidazol‐3‐yl)methylidene]‐7‐methyl‐4‐oxo‐1,4‐dihydro‐1,8‐naphthyridine‐3‐carbohydrazidato}] dichloride methanol tetrasolvate], {[Cu₃(C₁₆H₁₅N₆O₂)₂Cl₂(CH₃OH)₂]Cl₂·4CH₃OH}_n, with the (1H‐imidazol‐4‐yl)methylidene carbohydrazide derivative of nalidixic acid (denoted h4imi), is presented and its structure is compared to the density functional theory (DFT) optimized structure of free h4imi. The title structure presents an octahedral Cu^II ion on an inversion centre alternating along a polymer chain with a square‐pyramidal Cu^II ion, with the two Cu^II centres bridged by two chloride ligands. Hydrogen bonds involving chloride counter‐ions and methanol solvent molecules mediate the three‐dimensional packing of the polymer. Comparison of the geometrical results from the structure analysis with those derived from a DFT study of the free ligand reveal the differences that arise upon coordination.     

Quartic lattice interactions,soliton‐like excitations,and electron pairing in one‐dimensional anharmonic crystals

In this study, it is shown that two added, excess electrons with opposite spins in one‐dimensional crystal lattices with quartic anharmonicity may form a bisolectron, which is a localized bound state of the paired electrons to a soliton‐like lattice deformation. It is also shown that when the Coulomb repulsion is included, the wave function of the bisolectron has two maxima, and such a state is stable in lattices with strong enough electron (phonon/soliton)–lattice coupling. Furthermore, the energy of the bisolectron is shown to be lower than the energy of the state with two separate, independent electrons, as even with account of the Coulomb repulsion the bisolectron binding energy is positive. © 2011 Wiley Periodicals, Inc. Int J Quantum Chem, 2011