Showing papers on "Coordination polymer published in 2014"
TL;DR: Two-probe and van der Pauw electrical measurements reveal bulk and surface conductivity values of 2 and 40 S·cm(-1), respectively, both records for MOFs and among the best for any coordination polymer.
Abstract: Reaction of 2,3,6,7,10,11-hexaaminotriphenylene with Ni2+ in aqueous NH3 solution under aerobic conditions produces Ni3(HITP)2 (HITP = 2,3,6,7,10,11-hexaiminotriphenylene), a new two-dimensional metal–organic framework (MOF). The new material can be isolated as a highly conductive black powder or dark blue-violet films. Two-probe and van der Pauw electrical measurements reveal bulk (pellet) and surface (film) conductivity values of 2 and 40 S·cm–1, respectively, both records for MOFs and among the best for any coordination polymer.
809 citations
TL;DR: The lanthanides are under the limelight when it comes to high technology as discussed by the authors, because of their remarkable and unmatched optical and magnetic properties, these elements are used in strategic application.
Abstract: Because of their remarkable and unmatched optical and magnetic properties, the lanthanides are under the limelight when it comes to high technology. These elements are used in strategic application...
223 citations
TL;DR: A lanthanide coordination polymer Tb0.957Eu0.043cpda was synthesized as a ratiometric and colorimetric luminescent thermometer to detect and visualize temperature over a wide range from cryogenic to room temperature (40-300 K).
187 citations
TL;DR: In this article, a new PCP called [La(BTN)DMF]·guest (PCP-1⊃guest), which has a large aromatic organic surface and a low binding energy for high CO2 separation from four-gas mixtures (CO2-N2-O2-CO) at ambient temperature, was proposed.
Abstract: Porous coordination polymers (PCPs), constructed from organic linkers and metal ions, can provide special pore environments for selective CO2 capture. Although many PCPs have been reported, a rational design for identifying PCPs that adsorb CO2 molecules with a low binding energy, high separation ability and high chemical stability remains a great challenge. Here, we propose and validate, experimentally and computationally, a new PCP, [La(BTN)DMF]·guest (PCP-1⊃guest), that has a large aromatic organic surface and a low binding energy for high CO2 separation from four-gas mixtures (CO2–N2–O2–CO) at ambient temperature. In addition, it shows good water and chemical stability; in particular, it is stable from pH = 2 to 12 at 100 °C, which is unprecedented for carboxylate-based PCPs.
177 citations
TL;DR: A flexible 3D Supramolecular framework with confined nanospaces that can accommodate different electron-donating aromatic amine guests with selective turn-on emission signaling is reported, which serves as a molecular recognition platform through an emission-readout process.
Abstract: Flexible and dynamic porous coordination polymers (PCPs) with well-defined nanospaces composed of chromophoric organic linkers provide a scaffold for encapsulation of versatile guest molecules through noncovalent interactions. PCPs thus provide a potential platform for molecular recognition. Herein, we report a flexible 3D supramolecular framework {[Zn(ndc)(o-phen)]⋅DMF}n (o-phen = 1,10-phenanthroline, ndc = 2,6-napthalenedicarboxylate) with confined nanospaces that can accommodate different electron-donating aromatic amine guests with selective turn-on emission signaling. This system serves as a molecular recognition platform through an emission-readout process. Such unprecedented tunable emission with different amines is attributed to its emissive charge-transfer (CT) complexation with o-phen linkers. In certain cases this CT emission is further amplified by energy transfer from the chromophoric linker unit ndc, as evidenced by single-crystal X-ray structural characterization.
166 citations
TL;DR: The crystal structure of a 1D Zn(II) coordination polymer fused with an organic polymer ligand made in–situ by a [2+2] cycloaddition reaction of a six-fold interpenetrated metal-organic framework is reported.
Abstract: Organic polymers are usually amorphous or possess very low crystallinity. The metal complexes of organic polymeric ligands are also difficult to crystallize by traditional methods because of their poor solubilities and their 3D structures can not be determined by single-crystal X-ray crystallography owing to a lack of single crystals. Herein, we report the crystal structure of a 1D ZnII coordination polymer fused with an organic polymer ligand made in situ by a [2+2] cycloaddition reaction of a six-fold interpenetrated metal–organic framework. It is also shown that this organic polymer ligand can be depolymerized in a single-crystal-to-single-crystal (SCSC) fashion by heating. This strategy could potentially be extended to make a range of monocrystalline metal organopolymeric complexes and metal–organic organopolymeric hybrid materials. Such monocrystalline metal complexes of organic polymers have hitherto been inaccessible for materials researchers.
127 citations
TL;DR: A carboxyl-containing coordination polymer catalyst was synthesized rapidly in an aqueous medium using microwave energy and characterized for its structure, morphology, acid base sites and heterogeneity using experimental and physicochemical techniques as discussed by the authors.
116 citations
TL;DR: In this work the logic gate is integrated into the therapeutic agent and this will be highly beneficial in future molecular computing.
Abstract: Fluorescence switching of guest molecules confined in coordination polymer nanoparticles (CPNs) generated from nucleotides and lanthanide ions are used to construct multiconfigurable logic gates. Moreover, the potential of the material as fluorescent probe with large Stokes shift is demonstrated for cellular imaging. In this work the logic gate is integrated into the therapeutic agent and this will be highly beneficial in future molecular computing.
108 citations
TL;DR: A new inorganic-organic hybrid solid, [Zn(dap)2 ][AlB5 O10 ], combining the structural features of 3D open-framework inorganic solids and 2D metal-organic coordination polymers has been synthesized under solvothermal conditions.
Abstract: A new inorganic–organic hybrid solid, [Zn(dap)2][AlB5O10], combining the structural features of 3D open-framework inorganic solids and 2D metal–organic coordination polymers has been synthesized under solvothermal conditions. The compound displays extensive luminescence and moderate second-harmonic-generation efficiency.
104 citations
TL;DR: A copper(i)/copper(ii)-salen coordination polymer prepared by solvothermal reactions shows prominent bimetallic catalytic activities towards three-component Strecker reactions and photodegradation of organic dyes under visible-light illumination.
102 citations
TL;DR: The state-of-the-art of coordination polymers using nucleobases as ligands can be found in this article, which collects the literature already published in a comprehensive way and attempts to provide perspectives for this research field.
TL;DR: A porous coordination polymer has been synthesized employing an organic ligand in which a stable free radical, isoindoline nitroxide, is incorporated and was verified to be an efficient, recyclable, and widely applicable catalyst for selective oxidation of various alcohols to the corresponding aldehydes or ketones.
Abstract: A porous coordination polymer (PCP) has been synthesized employing an organic ligand in which a stable free radical, isoindoline nitroxide, is incorporated. The crystalline PCP possesses one-dimensional channels decorated with the nitroxyl catalytic sites. When O2 gas or air was used as the oxidant, this PCP was verified to be an efficient, recyclable, and widely applicable catalyst for selective oxidation of various alcohols to the corresponding aldehydes or ketones.
TL;DR: A review of polyoxometalates-based coordination polymers with entangled structures can be found in this paper, where different concepts, such as interpenetration, polycatenation, polyrotaxane, poly pseudo-rotaxanes and self-penetrations, are employed to describe the various types of POM-based polymers.
TL;DR: Density of states calculations show a higher contribution from Ag(I) ions to the valence band in the photodimerized solid, supporting the increase in conductivity.
Abstract: Ag(I) is used to form a π-stacked metal–organic solid that exhibits remarkably high electrical conductivity. The solid undergoes a single-crystal-to-single-crystal [2+2] photodimerization to generate a 1D coordination polymer with over 40% higher conductivity. The Ag(I) complex represents the first example of an increase in conductivity resulting from a [2+2] photodimerization. Density of states calculations show a higher contribution from Ag(I) ions to the valence band in the photodimerized solid, supporting the increase in conductivity.
TL;DR: A strong synergism was discovered among three reaction (quasi)equilibria and three types of photochemical reactions (isomerization, dimerization, and polymerization) and a strong coupling and feedback mechanism among the photocenters moderated by the coordination backbone is indicated.
Abstract: We carried out photopolymerization by [2 + 2] dimerization of a photoreactive guest molecule in the channels of a photoreactive porous coordination polymer. The photoreactions of the guest and two host ligands were monitored by single-crystal X-ray crystallography, providing snapshots of the interplay between the reactive centers. By correlating the structures of these three photocenters, a strong synergism was discovered among three reaction (quasi)equilibria and three types of photochemical reactions (isomerization, dimerization, and polymerization). This result indicates a strong coupling and feedback mechanism among the photocenters moderated by the coordination backbone.
TL;DR: In this paper, a hydrophilic lanthanide/nucleotide coordination polymer constructed by spontaneous self-assembling of terbium ion (Tb 3+ ) and adenosine monophosphate (AMP) was used as a receptor platform for direct detection of anthrax biomarker (dipicolinic acid, DPA) in aqueous solution.
Abstract: The metal-organic coordination polymers as attractive functional nanomaterials have shown a promising potential in a variety of important applications. In this work, we employed a hydrophilic lanthanide/nucleotide coordination polymer constructed by spontaneous self-assembling of terbium ion (Tb 3+ ) and adenosine monophosphate (AMP) as a receptor platform for direct detection of anthrax biomarker (dipicolinic acid, DPA) in aqueous solution. Due to the coordination of DPA with Tb 3+ on the surface of the AMP/Tb, significant enhancement in the fluorescent intensity of the coordination polymer (AMP/Tb) was obtained. The enhanced fluorescence intensity of AMP/Tb displayed a good linear response to DPA concentrations in the range from 20 nM to 20 μM with a detection limit of 10 nM. As a kind of DPA sensor, the AMP/Tb also showed excellent selectivity. Compared with conventional receptor platforms based on molecular lanthanide compounds, the presented receptor platform has an advantage of allowing simple, direct analysis for DPA without requiring complicated preparation processes and any extra steps of surface modification. This presented straightforward strategy may be extended to the construction of other coordination polymer-based lanthanide receptor reagent and hence a wider application field of coordination polymer as fluorescent sensor is expected.
TL;DR: In this article, a 2D Co-based metal-organic coordination polymer (Co-MOCP) was used as an electrode material for the electrocatalytic oxidation of reduced glutathione (GSH).
TL;DR: An ordered-to-disordered structural transformation in a Cu(2+) coordination polymer generated highly mobile proton carriers in the structure and exhibited a conductivity greater than 10(-2) S cm(-1) at 130 °C.
TL;DR: Light-induced changes in the magnetization of the normally light-insensitive KCoCr shell exhibit a new property resulting from the synergy between the core and shell of a coordination polymer heterostructure, giving direct evidence that the photomagnetic response of the shell is magnetomechanical in origin.
Abstract: Particles of formula Rb0.24Co[Fe(CN)6]0.74@K0.10Co[Cr(CN)6]0.70·nH2O with a light-responsive rubidium cobalt hexacyanoferrate (RbCoFe) core and a magnetic potassium cobalt hexacyanochromate (KCoCr) shell have been prepared and exhibit light-induced changes in the magnetization of the normally light-insensitive KCoCr shell, a new property resulting from the synergy between the core and shell of a coordination polymer heterostructure. A single batch of 135 ± 12 nm RbCoFe particles are used as seeds to generate three different core@shell samples, with KCoCr shell thicknesses of approximately 11, 23 and 37 nm, to probe the influence of the shell thickness over the particles’ morphology and structural and magnetic properties. Synchrotron powder X-ray diffraction reveals that structural changes in the shell accompany the charge transfer induced spin transition (CTIST) of the core, giving direct evidence that the photomagnetic response of the shell is magnetomechanical in origin. The depth to which the KCoCr she...
TL;DR: In this article, the photoluminescence and oxygen-sensing properties of the porous Cu(I) triazolate framework [Cu(detz)] (MAF-2, Hdetz = 3,5-diethyl-1,2,4-trizole) are studied in detail, which shows high chemical stability in moisture and water, very long phosphorescent lifetime (116 μs) and large Stokes shift (14 562 cm−1), as well as considerable oxygen permeability (1.7 × 10−11 mol cm−
Abstract: Phosphorescent complexes of precious metal ions are widely studied as optical sensing materials for molecular oxygen. Combining the advantages of luminescent complexes and porous matrixes, porous coordination polymers show great potential for oxygen-sensing, although their sensitivity, requirement of precious metal, and device fabrication remain challenging issues. In this work, the photoluminescence and oxygen-sensing properties of the porous Cu(I) triazolate framework [Cu(detz)] (MAF-2, Hdetz = 3,5-diethyl-1,2,4-trizole) is studied in detail, which shows high chemical stability in moisture and water, very long phosphorescent lifetime (116 μs) and large Stokes shift (14 562 cm−1), as well as considerable oxygen permeability (1.7 × 10−11 mol cm−1 s−1 bar−1) at ambient conditions, giving rise to exceptionally high luminescence quenching efficiency of 99.7% at 1 bar O2 (I 0/I 100 = 356) with a perfectly linear Stern-Volmer plot (K SV = 356 bar−1, R 2 = 0.9998), fast response and good reversibility. Further, a counter-diffusion crystal-growth method was developed to fabricate MAF-2 thin films protected by silicone rubbers as the first example of soft membrane oxygen sensor based on coordination polymer or metal-organic framework, which exhibited extraordinary oxygen-sensing performance (limit of detection = 0.047 mbar) and outstanding mechanical property, as well as outstanding chemical stability even in an acidic atmosphere.
TL;DR: The magnetic studies and heat capacity measurements reveal that the two-dimensional Gd(III)-based coordination polymer of 2 has the higher magnetic density and exhibits a larger cryogenic magnetocaloric effect (MCE) than previously reported.
Abstract: Two new oxalate-bridged Gd(III) coordination polymers, namely, (choline)[Gd(C2O4)(H2O)3Cl]Cl·H2O (1) and [Gd(C2O4)(H2O)3Cl] (2), were first obtained ionothermally by using a deep eutectic solvent (DES). The magnetic studies and heat capacity measurements reveal that the two-dimensional Gd(III)-based coordination polymer of 2 has the higher magnetic density and exhibits a larger cryogenic magnetocaloric effect (MCE) (ΔSm = 48 J kg–1 K–1 for ΔH = 7 T at 2.2 K).
TL;DR: In this paper, two luminescent coordination polymers were constructed with a fluorescent ligand, and the emissions of these compounds could be effectively and selectively quenched by acetone, showing their potential as acetone sensors.
Abstract: Two luminescent coordination polymers were constructed with a fluorescent ligand. The emissions of these compounds could be effectively and selectively quenched by acetone, showing their potential as acetone sensors. The formation of a coordination polymer structure is proven to be responsible for their strong emission and sensing properties.
TL;DR: The compound was magnetically characterized, and the complementary magnetic study of a known and very similar compound, [Co(NCS)2(bpe)]n (bpe = 1,2-bis(4-pyridyl)-ethylene), was also undertaken, which showed a metamagnetic transition with a critical field HC ∼ 40 Oe and ∼ 400 Oe, respectively.
Abstract: Reaction of Co(NCS)2 with 1,2-bis(4-pyridyl)-ethane (bpa) leads to the formation of [Co(NCS)2(bpa)2]n, which, on heating, transforms into the new layered coordination polymer [Co(NCS)2(bpa)]n. This compound can also be prepared in solution, but because no reasonable single crystals are available, its crystal structure was determined from X-ray powder data from scratch. In the crystal structure of [Co(NCS)2(bpa)]n, the cobalt(II) cations are coordinated by two S-bonded and two N-bonded thiocyanato anions and two N atoms of the bpa co-ligands in a distorted octahedral geometry. The cobalt(II) cations are linked into chains by pairs of μ-1,3 bridging thiocyanato anions. These chains are further connected into layers by the 1,2-bis(4-pyridyl)-ethane ligand. The compound was magnetically characterized, and, for comparative purposes, the complementary magnetic study of a known and very similar compound, [Co(NCS)2(bpe)]n (bpe = 1,2-bis(4-pyridyl)-ethylene), was also undertaken. The compounds differ in their inte...
TL;DR: The abrupt and hysteretic two-step spin crossover in a new triazole-based 2-D Hofmann-type complex shows a record breaking 120 K intermediate plateau (IP) region stabilized by negative cooperative interactions.
TL;DR: In this paper, eight coordination polymers based on H4L1/H4L2 (5,5′-(1,4/1,3-phenylenebis(methoxy))diisophthalic acid) and 3/4-abpt (4-amino-3,5-bis(3/4)-pyridyl)-1,2,4-triazole) ligands were synthesized.
Abstract: Eight coordination polymers based on H4L1/H4L2 (5,5′-(1,4/1,3-phenylenebis(methoxy))diisophthalic acid) and 3/4-abpt (4-amino-3,5-bis(3/4-pyridyl)-1,2,4-triazole) ligands were synthesized: [Co4(L1)2(4-abpt)(H2O)10.5]n (1), {[Zn2(L1)(4-abpt)(H2O)3]·5H2O}n (2), {[Co(H2L1)(3-abpt)(H2O)2]·0.5H4L1}n (3), {[Co2(L1)(4-abpt)2]·4H2O}n (4), {[Zn2(L2)(4-abpt)(H2O)]·2.5H2O}n (5), {[Zn2(L2)(4-abpt)(H2O)]·3H2O}n (6), {[Co1.5(HL2)(3-abpt)(H2O)]·H2O}n (7), and {[Zn1.5(HL2)(3-abpt)(H2O)]·H2O}n (8). Their structures were characterized by EA, IR, powder X-ray diffraction, thermogravimetric analysis (TGA), and single crystal X-ray diffraction. Complex 1 exhibits a three-dimensional (3D) metal–organic framework (MOF) composed of an interesting tetranuclear Co4(μ2-H2O)3(μ2-COO)4 cluster and 76-membered ring. Complex 2 shows a two-dimensional (2D) sheetlike network assembled by a one-dimensional (1D) [Zn2(L1)(H2O)3]n ribbon and 4-abpt linker. Complex 3 is a 1D nanotube coordination polymer constructed from parallel Co2(H2L1)2 r...
TL;DR: A general solvothermal method is proposed for preparing carboxylate complexes in DMF solution without any basic additive.
Abstract: Seven coordination polymers, namely [Mn(4-cptpy)2]n (1), [Co(4-cptpy)2]n (2), [Mn3(4-cptpy)6(H2O)]n·2nH2O (3), [Co(4-cptpy)(HCOO)(H2O)]n·nDMF (4), [Zn2(4-Hcptpy)2Cl4]n·2nC2H5OH·nH2O (5), [Co4(3-cptpy)4(HCOO)4(H2O)2]n (6), and [Mn(3-cptpy)2]n (7) (4-Hcptpy = 4-(4-carboxyphenyl)-4,2′:6′,4′′-terpyridine; 3-Hcptpy = 4-(4-carboxyphenyl)-3,2′:6′,3′′-terpyridine), have been synthesized under hydro(solvo)thermal conditions and structurally characterized. A general solvothermal method is proposed for preparing carboxylate complexes in DMF solution without any basic additive. 1 and 2 possess isostructural 3D metal–organic frameworks containing nanosized cavities. 3 is a beautiful 2D coordination polymer assembled by flower-like Mn3(4-cptpy)6(H2O) subunits. 4 and 6 both display 2D polymeric networks constructed from 4/3-cptpy− ligands, in which the formate ligands originate from the hydrolysis of DMF. 5 is a 1D 21 helical chain polymer. 7 shows a 2D network with a (3.6) two-nodal kgd topology. 4/3-Hcptpy ligands display seven types of coordination modes. The zinc complex 5 emits strong violet luminescence. 1 and 2 are both thermally stable below 440 °C and exhibit antiferromagnetic interactions.
TL;DR: The results for this quasi-one dimensional Ising ferromagnet, having also some features of a cluster spin-glass, are compared with those of related compounds.
Abstract: Three new coordination compounds with the composition Co(NCS)2(4-(3-phenylpropyl)pyridine)4 (1), Co(NCS)2(4-(3-phenylpropyl)pyridine)4(H2O)2 (2) and [Co(NCS)2(4-(3-phenylpropyl)pyridine)2]n (3) were prepared and investigated. The crystal structures of compounds 1 and 2 consist of discrete complexes, in which the Co(II) cations are coordinated by only terminal N-bonded thiocyanato anions. In the crystal structure of 3 the Co(II) cations are linked into chains by pairs of μ-1,3-bridging thiocyanato anions. DTA-TG measurements on compound 1 show decomposition without the formation of 3 as an intermediate. In contrast, on heating compound 2 two water molecules are removed in the first step leading to the formation of compound 3 in the second step. Magnetic measurements on 3 reveal ferromagnetic interactions between Co(II) ions along chains with J = 29.5(1) K, and also ferromagnetic interactions between chains with zJ′ = 0.38(1) K. The ferromagnetic transition is observed at 3.3 K, which is confirmed by specific heat measurements. The temperature dependent ac susceptibility shows slow relaxations above and below 3.3 K. The results for this quasi-one dimensional Ising ferromagnet, having also some features of a cluster spin-glass, are compared with those of related compounds.
TL;DR: A trinuclear complex was synthesized by using a metalloligand [CuL] (H2L = N,N′-bis(salicylidene)-1,3-propanediamine or salpn) as mentioned in this paper, which is used as a new 3d-4f metallatecton for stepwise supramolecular oligomerization along with a simple diimine linker, 4,4′-bipyridine (bpy).
Abstract: A trinuclear complex [(CuL)2Tb(H2O)(NO3)3]·MeOH·H2O (1) is synthesized by using a metalloligand [CuL] (H2L = N,N′-bis(salicylidene)-1,3-propanediamine or salpn). This complex is used as a new 3d-4f metallatecton for stepwise supramolecular oligomerization along with a simple diimine linker, 4,4′-bipyridine (bpy). A ratio of metallatecton/linker = 2:1 is conducive for the formation of a dimer [{(CuL)2Tb(H2O)(NO3)3}2bpy]·2MeOH·4H2O (2), whereas a higher proportion of linker at a ratio of 1:1 gives rise to a zigzag one-dimensional coordination polymer {[(CuL)2Tb(NO3)3bpy]·MeOH·2H2O}∞ (3). The inherent conformational flexibility of the trinuclear (CuL)2Tb node which is folded (cisoid) for 1 and 2 (asymmetric TbO9 tricapped trigonal prism) and unfolded (transoid) for 3 (a C2-symmetric TbO10 tetradecahedron) seems to stabilize the crystal packing of these coordination-driven self-assemblies. The rapidly saturated magnetization at 1.8 K for 1 (11 μB) and 2 (22 μB) clearly indicates the presence of Tb–Cu ferromag...
TL;DR: In this article, a simple room temperature solution-based method for the preparation of highly porous coordination polymer films on the internal surface is reported, and the resulting metalorganic polymer hybrid (MOPH) maintains a high specific micropore surface area of 389 m2 g•1 and thermal stability above 250 °C in air.
Abstract: A simple room temperature solution‐based method for the preparation of highly porous
iron(III) benzenetricarboxylate coordination polymer films on the internal surface
of a macroporous polystyrene‐divinylbenzene‐methacrylic acid polymer is reported
The resulting metal‐organic polymer hybrid (MOPH) maintains a high specific micropore
surface area of 389 m2 g‐1 and thermal stability above 250 °C in air The MOPH preparation is readily adapted
to a capillary column, yielding a flow‐through separation device with excellent flow
permeability and modest back‐pressure The excellent separation capability of the
MOPH column is demonstrated by enriching phosphopeptides from mixtures of digested
proteins This approach to MOPH synthesis is easily implemented and likely adaptable
to a wide range of coordination polymers and metal‐organic frameworks
TL;DR: This study demonstrates that these different optical behaviors can be attributed to the presence of a PET (photoinduced electron transfer) mechanism that is only present in the amino-isophthalate-containing coordination polymers.
Abstract: The luminescent properties of two families of heteronuclear lanthanide-containing coordination polymers are compared. These families have general chemical formulas [Ln2–2xLn′2x(ip)3(H2O)9·6H2O]∞ and [Ln2–2xLn′2x(aip)2(H2O)10·(aip)·4H2O]∞ where H2ip and H2aip stand for isophthalic acid and 5-amino-isophthalic acid, respectively, and where Ln and Ln′ are one of the lanthanide ions between Sm3+ and Dy3+. Heteronuclear compounds that belong to each family are isostructural to the already reported homonuclear compounds [Gd2(ip)3(H2O)9·6H2O]∞ and [Eu2(aip)2(H2O)10·(aip)·4H2O]∞, respectively. These two crystal structures are very similar. However, despite similar chemical formulas, similar crystal structures, and similar hydration rates, these two families of compounds present very different luminescent properties that have thus been deeply investigated. This study demonstrates that these different optical behaviors can be attributed to the presence of a PET (photoinduced electron transfer) mechanism that is onl...