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Special Issue "Coordination Polymers"

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A special issue of Polymers (ISSN 2073-4360).

Deadline for manuscript submissions: closed (31 July 2011)

Special Issue Editor

Guest Editor
Prof. Dr. Katharina M. Fromm

Department of Chemistry, University of Fribourg, Chemin du Musée 9, CH-1700, Fribourg, Switzerland
Website | E-Mail
Interests: coordination polymers; ion conducting channel compounds; precursors for oxide materials; antimicrobial silver compounds; lithium ion battery electrode materials

Special Issue Information

Dear Colleagues,

Coordination polymers and metal-organic frameworks have attracted a lot of attention during the past 15 years of research. This is due to the fact that the combination of properties of organic ligands and metal ions allows to convey the final product properties, which would not exist in classical complexes or in each individual entity alone. Furthermore, the ability to tune the dimensionality of the final compound allows the control over materials' properties such as for example porosity or magnetism. From these properties derive a wide variety of applications, as for example gas storage or catalysis.

Prof. Dr. Katharina M. Fromm
Guest Editor

Published Papers (12 papers)

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Research

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Open AccessArticle Spiral Assembly of the 1D Chain Sheet of Fe(NCBH3)2(bpa)2·(biphenyl) (bpa = 1,2-bis(4-pyridyl)ethane) and its Stepwise Spin-Crossover Phenomenon
Polymers 2012, 4(1), 880-888; doi:10.3390/polym4010880
Received: 18 January 2012 / Revised: 13 February 2012 / Accepted: 2 March 2012 / Published: 7 March 2012
Cited by 1 | PDF Full-text (635 KB) | HTML Full-text | XML Full-text
Abstract
The assembled complex, Fe(NCBH3)2(bpa)2, enclathrating biphenyl has been synthesized, the skeleton of which is a 1D chain. Several 1D chains gather together to form 1D chain sheet. The 1D chain sheet is stacked spirally to form novel spiral assembly. The average Fe-N distances
[...] Read more.
The assembled complex, Fe(NCBH3)2(bpa)2, enclathrating biphenyl has been synthesized, the skeleton of which is a 1D chain. Several 1D chains gather together to form 1D chain sheet. The 1D chain sheet is stacked spirally to form novel spiral assembly. The average Fe-N distances were 2.020(2), 2.083(2), and 2.191(2) Å at 100, 175, and 298 K, respectively, reflecting spin-state change of the iron ion. The assembly showed a stepwise spin-crossover phenomenon. Full article
(This article belongs to the Special Issue Coordination Polymers)
Open AccessCommunication Design of Improved Metal-Organic Framework (MOF) H2 Adsorbents
Polymers 2011, 3(4), 2133-2141; doi:10.3390/polym3042133
Received: 5 November 2011 / Revised: 28 November 2011 / Accepted: 6 December 2011 / Published: 12 December 2011
Cited by 5 | PDF Full-text (632 KB) | HTML Full-text | XML Full-text | Supplementary Files
Abstract
We attempted synthesis of the hydrogen adsorption material suitable for the fuel cell vehicles (FCEVs). The designed and synthesized Cu2(3,5-Pyridinedicarboxylate)2 (=Cu2PDC2) metal complex showed an extremely high volumetric uptake density for a physisorption material, even though
[...] Read more.
We attempted synthesis of the hydrogen adsorption material suitable for the fuel cell vehicles (FCEVs). The designed and synthesized Cu2(3,5-Pyridinedicarboxylate)2 (=Cu2PDC2) metal complex showed an extremely high volumetric uptake density for a physisorption material, even though the specific surface area was only about 1,000 m2 g−1. Factors for high uptake properties are considered to be the increased adsorption sites per unit area, the increased adsorption energy, and the optimized design of pore shapes. High hydrogen uptake on volumetric basis is especially effective for FCEV because the tank volume is reduced. It is expected that property prediction using computational simulation and sophisticated analysis at the micro and nano levels will become an indispensable tool in the design of functional materials. Full article
(This article belongs to the Special Issue Coordination Polymers)
Open AccessArticle Synthesis and Characterization of Novel Copper(II) 2D Coordination Polymers from a Fluorinated Flexible Ligand with Remarkable Clathration Ability
Polymers 2011, 3(4), 1934-1943; doi:10.3390/polym3041934
Received: 25 September 2011 / Revised: 18 October 2011 / Accepted: 31 October 2011 / Published: 7 November 2011
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Abstract
Two-dimensional (2D) grid coordination polymers were prepared by the reaction of 1,4-bis(4-pyridylmethyl)tetrafluorobenzene (bpf) with Cu(NO3)2 in the presence of aromatic compounds. Crystal structures of {[Cu(bpf)2(NO3)2]·(biphenyl)2}n (1), {[Cu(bpf)2(NO
[...] Read more.
Two-dimensional (2D) grid coordination polymers were prepared by the reaction of 1,4-bis(4-pyridylmethyl)tetrafluorobenzene (bpf) with Cu(NO3)2 in the presence of aromatic compounds. Crystal structures of {[Cu(bpf)2(NO3)2]·(biphenyl)2}n (1), {[Cu(bpf)2(NO3)2]·(m-C6H4(OMe)2)2}n (2), {[Cu(bpf)2(NO3)2]·PhtBu}n (3) and {[Cu(bpf)2(NO3)(H2O)]NO3·(bpf)0.5}n (4) were determined. The grid networks were held together by C–H···O and C–H···F hydrogen bonds via the NO3 anions and the tetrafluorophenylene rings of bpf, respectively. Biphenyl, m-dimethoxybenzene, t-butylbenzene, and bpf molecules were clathrated in cyclic cavities of the grid networks through arene-perfluoroarene interactions. These coordination networks have remarkable clathration ability for aromatic compounds. Full article
(This article belongs to the Special Issue Coordination Polymers)
Open AccessArticle One-Dimensional Helical Homochiral Metal-Organic Framework Built from 2,2′-Dihydroxy-1,1′-binaphthyl-3,3′-dicarboxylic Acid
Polymers 2011, 3(4), 1866-1874; doi:10.3390/polym3041866
Received: 17 August 2011 / Revised: 19 September 2011 / Accepted: 31 October 2011 / Published: 1 November 2011
Cited by 1 | PDF Full-text (349 KB) | HTML Full-text | XML Full-text
Abstract
A homochiral metal-organic framework (MOF) based on enantiopure (R)-2,2′-dihydroxy-1,1′-binaphthyl-3,3′-dicarboxylic acid was synthesized. X-ray crystal diffraction studies revealed that the MOF adopts a one-dimensional infinite right-handed helical tubular structure along the a-axis, which serves as a host for the inclusion of
[...] Read more.
A homochiral metal-organic framework (MOF) based on enantiopure (R)-2,2′-dihydroxy-1,1′-binaphthyl-3,3′-dicarboxylic acid was synthesized. X-ray crystal diffraction studies revealed that the MOF adopts a one-dimensional infinite right-handed helical tubular structure along the a-axis, which serves as a host for the inclusion of guest dimethylformamide (DMF) molecules. Full article
(This article belongs to the Special Issue Coordination Polymers)
Figures

Open AccessArticle Crystal Engineering: Synthesis and Structural Analysis of Coordination Polymers with Wavelike Properties
Polymers 2011, 3(4), 1662-1672; doi:10.3390/polym3041662
Received: 17 August 2011 / Revised: 5 September 2011 / Accepted: 27 September 2011 / Published: 7 October 2011
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Abstract
Supramolecular coordination polymers with wavelike structures have been synthesized by self-assembly and their structures analyzed using the sine trigonometric function.Slow evaporation of a methylene chloride-methanol solution of a 1:1 molar mixture of [M(tmhd)2], where M = Co or Ni, and
[...] Read more.
Supramolecular coordination polymers with wavelike structures have been synthesized by self-assembly and their structures analyzed using the sine trigonometric function. Slow evaporation of a methylene chloride-methanol solution of a 1:1 molar mixture of [M(tmhd)2], where M = Co or Ni, and quinoxaline; a 1:2:1 molar mixture of [M(acac)2], where M = Co or Ni, 2,2,6,6-tetramethyl-3,5-heptadione and quinoxaline; or a 1:2:1 molar mixture of [Co(acac)2], dibenzoylmethane, and quinoxaline, yielded the crystalline coordination polymers. In the presence of the nitrogenous base, ligand scrambling occurs yielding the most insoluble product. The synthesis and structures of the following wavelike polymers are reported: trans-[Co(DBM)2(qox)]n·nH2O (2), trans-[Co(tmhd)2(qox)]n (3), trans-[Ni(tmhd)2(qox)]n (4), where DBM= dibenzoylmethanate, tmhd= 2,2,6,6-tetramethyl-3,5-heptadionate, and qox = quinoxaline. The wavelike structures are generated by intramolecular steric interactions and crystal packing forces between the chains. Some of the tert-butyl groups show a two-fold disorder. The sine function, φ = A sin 2πx/λ, where φ = distance (Ǻ) along the polymer backbone, λ = wavelength (Ǻ), A = amplitude (Ǻ), x = distance (Ǻ) along the polymer axis, provides a method to approximate and visualize the polymer structures. Full article
(This article belongs to the Special Issue Coordination Polymers)
Figures

Open AccessArticle Novel Countercation in MMX-Type Mixed-Valence Chain Compound: Coexistence of Neutral and Protonated Amino Substituents
Polymers 2011, 3(4), 1652-1661; doi:10.3390/polym3041652
Received: 2 August 2011 / Revised: 7 September 2011 / Accepted: 27 September 2011 / Published: 6 October 2011
Cited by 5 | PDF Full-text (499 KB) | HTML Full-text | XML Full-text
Abstract
The first MMX-type quasi-one-dimensional (Q1D) Pt chain complex (MMX chain) that contains a mono-protonated diamine as countercation, {o-(H3NC6H4NH2)}4[Pt2(pop)4I]·H2O (pop = P2H2O
[...] Read more.
The first MMX-type quasi-one-dimensional (Q1D) Pt chain complex (MMX chain) that contains a mono-protonated diamine as countercation, {o-(H3NC6H4NH2)}4[Pt2(pop)4I]·H2O (pop = P2H2O52–), was synthesized. According to the crystal structural analysis, –NH2 group was hydrogen-bonded to either lattice H2O molecule or –NH3+ group in addition to typical hydrogen bond between –NH3+ group and pop ligand. To control the partial deprotonation of the countercation will be an important method for achieving the high-conductive MMX-chain polymer by the hole doping. Full article
(This article belongs to the Special Issue Coordination Polymers)
Figures

Open AccessArticle Loading of Two Related Metal-Organic Frameworks (MOFs), [Cu2(bdc)2(dabco)] and [Cu2(ndc)2(dabco)], with Ferrocene
Polymers 2011, 3(3), 1565-1574; doi:10.3390/polym3031565
Received: 9 July 2011 / Revised: 30 August 2011 / Accepted: 20 September 2011 / Published: 21 September 2011
Cited by 3 | PDF Full-text (1082 KB) | HTML Full-text | XML Full-text
Abstract
We have studied the loading of two related, similar porous metal-organic frameworks (MOFs) [Cu2(bdc)2(dabco)] (1), and [Cu2(ndc)2(dabco)] (2) with ferrocene by exposing bulk powder samples to the corresponding vapor. On the
[...] Read more.
We have studied the loading of two related, similar porous metal-organic frameworks (MOFs) [Cu2(bdc)2(dabco)] (1), and [Cu2(ndc)2(dabco)] (2) with ferrocene by exposing bulk powder samples to the corresponding vapor. On the basis of powder X-ray diffraction data and molecular dynamics (MD) calculations we propose that each pore can store one ferrocene molecule. Despite the rather pronounced similarity of the two MOFs a quite different behavior is observed, for 1 loading with ferrocene leads to an anisotropic 1% contraction, whereas for 2 no deformation is observed. Mössbauer spectroscopy studies reveal that the Fe oxidation level remains unchanged during the process. Time dependent studies reveal that the diffusion constant governing the loading from the gas-phase for 1 is approximately three times larger than the value for 2. Full article
(This article belongs to the Special Issue Coordination Polymers)
Open AccessArticle A Molecular Antenna Coordination Polymer from Cadmium(II) and 4,4’-Bipyridine Featuring Three Distinct Polymer Strands in the Crystal
Polymers 2011, 3(3), 1458-1474; doi:10.3390/polym3031458
Received: 26 July 2011 / Revised: 18 August 2011 / Accepted: 31 August 2011 / Published: 5 September 2011
Cited by 5 | PDF Full-text (1478 KB) | HTML Full-text | XML Full-text
Abstract
Reaction of cadmium perchlorate and the prototypical linear bridging ligand 4,4’-bipyridine (4,4’-bipy) in an ethanol/water mixture affords the one-dimensional coordination polymer, [{Cd(m-4,4’-bipy)(4,4’-bipy)2(H2O)2}(ClO4)2 × 2 4,4’-bipy × 4.5 H2O]n(
[...] Read more.
Reaction of cadmium perchlorate and the prototypical linear bridging ligand 4,4’-bipyridine (4,4’-bipy) in an ethanol/water mixture affords the one-dimensional coordination polymer, [{Cd(m-4,4’-bipy)(4,4’-bipy)2(H2O)2}(ClO4)2 × 2 4,4’-bipy × 4.5 H2O]n (1). The Cd2+ ions adopt an octahedral coordination sphere and are joined into linear chains by 4,4’-bipy via two trans coordination sites. The remaining two trans sites in the equatorial plane carry terminally monodentate-bound 4,4’-bipy ligands, resulting in a molecular antenna arrangement. The two axial sites of each Cd2+ ion are occupied by aqua ligands. Compound 1 crystallizes in the non-centrosymmetric, monoclinic space group C2 with three similar, crystallographically independent, cationic coordination polymer strands in the unit cell, which essentially differ only in the conformations of the 4,4’-bipyridyl ligands. Consistent with the similarity of the local coordination environments of the three independent Cd atoms in the structure, 113Cd MAS NMR spectroscopy reveals a single resonance line at 89 ppm. Full article
(This article belongs to the Special Issue Coordination Polymers)
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Open AccessArticle Tunable Crystal-to-Crystal Phase Transition in a Cadmium Halide Chain Polymer
Polymers 2011, 3(3), 1151-1161; doi:10.3390/polym3031151
Received: 8 June 2011 / Revised: 11 July 2011 / Accepted: 21 July 2011 / Published: 25 July 2011
Cited by 9 | PDF Full-text (4103 KB) | HTML Full-text | XML Full-text
Abstract
The chain polymer [{Cd(μ-X)2py2}1] (X = Cl, Br; py = pyridine) undergoes a fully reversible phase transition between a monoclinic low-temperature and an orthorhombic high-temperature phase. The transformation can be directly monitored in single crystals and
[...] Read more.
The chain polymer [{Cd(μ-X)2py2}1] (X = Cl, Br; py = pyridine) undergoes a fully reversible phase transition between a monoclinic low-temperature and an orthorhombic high-temperature phase. The transformation can be directly monitored in single crystals and can be confirmed for the bulk by powder diffraction. The transition temperature can be adjusted by tuning the composition of the mixed-halide phase: Transition temperatures between 175 K up to the decomposition of the material at ca. 350 K are accessible. Elemental analysis, ion chromatography and site occupancy refinements from single-crystal X-ray diffraction agree with respect to the stoichiometric composition of the samples. Full article
(This article belongs to the Special Issue Coordination Polymers)
Open AccessCommunication Observation of Long-Range Vicinal Effect in Chiral Cu(II)-Cr(VI) or Cu(II)-W(VI) Bimetallic Coordination Polymers
Polymers 2011, 3(3), 1029-1035; doi:10.3390/polym3031029
Received: 13 May 2011 / Revised: 17 June 2011 / Accepted: 28 June 2011 / Published: 29 June 2011
PDF Full-text (391 KB) | HTML Full-text | XML Full-text
Abstract
We have prepared some diastereomers of [CuL2][M2O7] (L is 1,2-diaminocyclohexane and its derivatives; M = Cr and W) bimetallic coordination polymers and confirmed their structural similarity and inner electronic states by means of XRD and XAS, respectively.
[...] Read more.
We have prepared some diastereomers of [CuL2][M2O7] (L is 1,2-diaminocyclohexane and its derivatives; M = Cr and W) bimetallic coordination polymers and confirmed their structural similarity and inner electronic states by means of XRD and XAS, respectively. For the first time, we have successfully observed distant vicinal effect of which the chiral source is only chiral organic ligands of [CuL2]2+ moieties (acting as ligand complex), while probe bands for solid state CD spectra are charge transfer (CT) bands of [M2O7]2− moieties (achiral complex) with the d0 electronic configuration. The new concept (interpretation) of this observation will be important for supramolecular chirality of coordination polymers built by ligand complexes. Full article
(This article belongs to the Special Issue Coordination Polymers)

Review

Jump to: Research

Open AccessReview Coordination Polymers and Metal Organic Frameworks Derived from 1,2,4-Triazole Amino Acid Linkers
Polymers 2011, 3(4), 1750-1775; doi:10.3390/polym3041750
Received: 5 July 2011 / Revised: 20 September 2011 / Accepted: 7 October 2011 / Published: 11 October 2011
Cited by 27 | PDF Full-text (4018 KB) | HTML Full-text | XML Full-text
Abstract
The perceptible appearance of biomolecules as prospective building blocks in the architecture of coordination polymers (CPs) and metal-organic frameworks (MOFs) are redolent of their inclusion in the synthon/tecton library of reticular chemistry. In this frame, for the first time a synthetic strategy has
[...] Read more.
The perceptible appearance of biomolecules as prospective building blocks in the architecture of coordination polymers (CPs) and metal-organic frameworks (MOFs) are redolent of their inclusion in the synthon/tecton library of reticular chemistry. In this frame, for the first time a synthetic strategy has been established for amine derivatization in amino acids into 1,2,4-triazoles. A set of novel 1,2,4-triazole derivatized amino acids were introduced as superlative precursors in the design of 1D coordination polymers, 2D chiral helicates and 3D metal-organic frameworks. Applications associated with these compounds are diverse and include gas adsorption-porosity partitioning, soft sacrificial matrix for morphology and phase selective cadmium oxide synthesis, FeII spin crossover materials, zinc-b-lactamases inhibitors, logistics for generation of chiral/non-centrosymmetric networks; and thus led to a foundation of a new family of functional CPs and MOFs that are reviewed in this invited contribution. Full article
(This article belongs to the Special Issue Coordination Polymers)
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Open AccessReview An Excursion into the Intriguing World of Polymeric Tl(I) and Ag(I) Cyanoximates
Polymers 2011, 3(3), 1475-1511; doi:10.3390/polym3031475
Received: 30 June 2011 / Revised: 16 August 2011 / Accepted: 30 August 2011 / Published: 13 September 2011
Cited by 7 | PDF Full-text (1891 KB) | HTML Full-text | XML Full-text | Supplementary Files
Abstract
The reaction of hot (~95 °C) aqueous solutions of Tl2CO3 with solid HL (HL = NC-C(=N-OH)-R is a cyanoxime, and R is an electron-withdrawing group; 37 ligands are known up-to-date) leads to crystalline yellow/orange TlL. Similarly, the reaction between AgNO
[...] Read more.
The reaction of hot (~95 °C) aqueous solutions of Tl2CO3 with solid HL (HL = NC-C(=N-OH)-R is a cyanoxime, and R is an electron-withdrawing group; 37 ligands are known up-to-date) leads to crystalline yellow/orange TlL. Similarly, the reaction between AgNO3 and ML (M = K+, Na+; L = anion of the monodeprotonated cyanoxime) this time at room temperature in mixed ethanol/aqueous solutions leads to sparingly soluble, colored AgL in high-yield. All synthesized monovalent Tl and Ag complexes were characterized using a variety of spectroscopic methods and X-ray analysis, which revealed the formation of primarily 2D coordination polymers of different complexity. In all cases cyanoxime mono-anions act as bridging ligands. Thallium(I) cyanoximates adopt in most cases a double-stranded motif that is originated from centrosymmetric (TlL)2 dimers in which two Tl2O2 rhombs are fused into infinite “ladder-type” structure. There are very short (3.65–3.85 Å) intermetallic distances in (TlL)n, which are close to that (3.46 Å) in metallic thallium. This opens the possibility for the electrochemical or chemical generation of mixed valence Tl(I)/Tl(III) polymers that may exhibit electrical conductivity. Synthesized silver(I) compounds demonstrate a very significant (for multiple years!) stability towards visible light. There are three areas of potential practical applications of these unusual complexes: (1) battery-less detectors of UV-radiation, (2) non electrical sensors for gases of industrial importance, (3) antimicrobial additives to light-curable acrylate polymeric glues, fillers and adhesives used during introduction of indwelling medical devices. Chemical, structural, technological and biological aspects of application of Tl(I) and Ag(I) cyanoximes-based coordination polymers are reviewed. Full article
(This article belongs to the Special Issue Coordination Polymers)

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