Showing papers on "Coordination polymer published in 2015"
TL;DR: Four-probe measurements show that the room temperature conductivity of this material can reach up to 1,580 S cm−1, which is the highest value ever reported for coordination polymers, and it displays ambipolar charge transport behaviour and extremely high electron and hole mobilities under field-effect modulation.
Abstract: Currently, studies on organic two-dimensional (2D) materials with special optic-electronic properties are attracting great research interest. However, 2D organic systems possessing promising electrical transport properties are still rare. Here a highly crystalline thin film of a copper coordination polymer, Cu-BHT (BHT = benzenehexathiol), is prepared via a liquid-liquid interface reaction between BHT/dichloromethane and copper(II) nitrate/H2O. The morphology and structure characterization reveal that this film is piled up by nanosheets of 2D lattice of [Cu-3(C6S6)](n), which is further verified by quantum simulation. Four-probe measurements show that the room temperature conductivity of this material can reach up to 1,580 S cm (-1), which is the highest value ever reported for coordination polymers. Meanwhile, it displays ambipolar charge transport behaviour and extremely high electron and hole mobilities (99 cm(2) V (-1) s (-1) for holes and 116 cm(2) V (-1) s (-1) for electrons) under field-effect modulation.
528 citations
TL;DR: In this article, a terpyridyl-end-capped four-arm poly(ethylene glycol) polymer was developed for light-emitting metallogels functionalized with lanthanide metal-ligand coordination complexes.
Abstract: We have developed model light-emitting metallogels functionalized with lanthanide metal-ligand coordination complexes via a terpyridyl-end-capped four-arm poly(ethylene glycol) polymer. The optical properties of these highly luminescent polymer networks are readily modulated over a wide spectrum, including white-light emission, simply by tuning of the lanthanide metal ion stoichiometry. Furthermore, the dynamic nature of the Ln-N coordination bonding leads to a broad variety of reversible stimuli-responsive properties (mechano-, vapo-, thermo-, and chemochromism) of both sol-gel systems and solid thin films. The versatile functional performance combined with the ease of assembly suggests that this lanthanide coordination polymer design approach offers a robust pathway for future engineering of multi-stimuli-responsive polymer materials.
345 citations
TL;DR: A new perovskite-like coordination polymer which undergoes a reversible ferroelastic phase transition is reported which may serve as a model compound for the development of sensitive thermoresponsive dielectric materials and may be key to understanding and modulating molecular/ionic dynamics of guest molecules in confined space.
Abstract: A new perovskite-like coordination polymer [(CH3)2NH2][Cd(N3)3] is reported which undergoes a reversible ferroelastic phase transition. This transition is due to varied modes of motion of the [(CH3)2NH2](+) guest accompanied by a synergistic deformation of the [Cd(N3)3](-) framework. The unusual two-staged switchable dielectric relaxation reveals the molecular dynamics of the polar cation guest, which are well controlled by the variable confined space of the host framework. As the material switches from the ferroelastic phase to the paraelastic phase, a remarkable increase of the rotational energy barrier is detected. As a result, upon heating at low temperature, this compound shows a notable change from a low to a high dielectric state in the ferroelastic phase. This thermoresponsive host-guest system may serve as a model compound for the development of sensitive thermoresponsive dielectric materials and may be key to understanding and modulating molecular/ionic dynamics of guest molecules in confined space.
177 citations
TL;DR: This work offers a new photoinduced post-synthetic method for the synthesis of multifunctional MOFs, which show luminescence sensing of Fe(3+) ions and dye adsorption properties.
Abstract: One coordination polymer [Zn2(L)2(bpe)2(H2O)2] (1) (L = 4,4′-((1,2-phenylenebis(methylene))bis(oxy))dibenzoic acid; bpe = (E)-1,2-di(pyridin-4-yl)ethene) was prepared and structurally determined. Compound 1 has a chain structure in which its pair of bpe ligands is arranged in a head-to-tail manner with their CC bonds being close enough for a [2 + 2] cycloaddition reaction. Upon exposure to UV light, compound 1 undergoes a single-crystal-to-single-crystal (SCSC) [2 + 2] photodimerization to generate one 2D coordination polymer [Zn(L)(rctt-tpcb)0.5(H2O)] (1a) (rctt (regio cis, trans, trans)-tpcb = tetrakis(4-pyridyl)cyclobutane). The tpcb ligands in the crystals of 1a show an intriguing in situ thermal isomerisation. The nanospheres of 1 can be obtained by recrystallization in DMSO/alcohol. The nanospheres of 1a can also be readily produced from the corresponding nanospheres of 1 by the photocyclodimerization method. Compared with those of 1a, the nanospheres of 1 display highly selective sensing of Fe3+ ions over mixed metal ions through fluorescence quenching. Moreover, the nanospheres of 1a can rapidly adsorb CR (congo red), MB (methylene blue) or RhB (rhodamine B) over MO (methyl orange) from aqueous solutions. This work offers a new photoinduced post-synthetic method for the synthesis of multifunctional MOFs, which show luminescence sensing of Fe3+ ions and dye adsorption properties.
161 citations
TL;DR: The reversible solid-to-liquid phase transition of crystalline CPs is reported, and it is found that the coordination bonds are not fully preserved in the liquid state but are re-formed in the glass state.
Abstract: The solid-to-liquid phase transition, a fundamental process commonly observed for various types of substances with significant potential for application, has been given little attention in the field of coordination polymers (CPs) despite the rich functionality of these compounds. In this article, we report the reversible solid-to-liquid phase transition of crystalline CPs. These CPs are composed of zinc ions, phosphate, and azoles, and a well-balanced composition, ionicity, and bond strength afford "melting" CPs. We examined the structure of one such melting framework in the liquid and glass states and found that the coordination bonds are not fully preserved in the liquid state but are re-formed in the glass state. As a demonstration, we fabricated, via phase transition, a thin film with an aligned crystal orientation and a monolith crystal of the CP.
157 citations
TL;DR: It is shown that a magnetic response to light can also be enforced in a nonphotomagnetic compound by applying mechanical stress, which is the first pressure-induced spin-crossover photomagnet.
Abstract: Photomagnetic compounds are usually achieved by assembling preorganized individual molecules into rationally designed molecular architectures via the bottom-up approach. Here we show that a magnetic response to light can also be enforced in a nonphotomagnetic compound by applying mechanical stress. The nonphotomagnetic cyano-bridged FeII–NbIV coordination polymer {[FeII(pyrazole)4]2[NbIV(CN)8]·4H2O}n (FeNb) has been subjected to high-pressure structural, magnetic and photomagnetic studies at low temperature, which revealed a wide spectrum of pressure-related functionalities including the light-induced magnetization. The multifunctionality of FeNb is compared with a simple structural and magnetic pressure response of its analog {[MnII(pyrazole)4]2[NbIV(CN)8]·4H2O}n (MnNb). The FeNb coordination polymer is the first pressure-induced spin-crossover photomagnet.
136 citations
TL;DR: In this article, an Ag(I)/tetraphosphine coordination polymer [Ag 4 (NO 3 ) 4 (dpppda)] n ( 1 ) has been shown to have good catalytic activity towards the photodegradation of nitrobenzene.
Abstract: Reaction of AgNO 3 with one tetraphosphine ligand, 1,4- N , N , N ′, N ′-tetra(diphenylphosphanylmethyl) benzene diamine (dpppda), gave rise to a Ag(I)/tetraphosphine coordination polymer [Ag 4 (NO 3 ) 4 (dpppda)] n ( 1 ). Compound 1 has a one-dimensional (1D) chain structure in which the chair-like [Ag 4 (NO 3 ) 4 ] cores are linked by the dpppda ligands using a Z-shaped μ - η 2 : η 2 side-by-side mode. Compound 1 exhibited good catalytic activity towards the photodegradation of nitrobenzene (NB), paranitrophenol (PNP) and 2,4-dinitrophenol (2,4-DNP) in aqueous solution under UV light irradiation. The kinetics and the mechanism of such catalytic photodegradation reactions were also investigated. The present work provided some new insight into the design and preparation of new coordination polymers as catalyst for high-performance photodegradation of toxic and persistent organic species existed in industrial wastewaters.
127 citations
TL;DR: In this article, a two-dimensional (2D) coordination Cd(II) polymer [Cd(ppvppa)(1,4-NDC)]n (1) (n = N-(pyridin-4-yl)vinyl)phenyl)pyrin-2-amine; 1, 4naphthalenedicarboxylic acid (1, 4-H2NDC) = 1.4-naphthyricarboxyl acid).
Abstract: A stable two-dimensional (2D) coordination Cd(II) polymer [Cd(ppvppa)(1,4-NDC)]n (1) (ppvppa = N-(pyridin-2-yl)-N-(4-(2-(pyridin-4-yl)vinyl)phenyl)pyridin-2-amine; 1,4-H2NDC = 1,4-naphthalenedicarboxylic acid) was prepared by the solvothermal reactions of Cd(NO3)2·4H2O with ppvppa and 1,4-H2NDC in H2O and MeCN at 150 °C. Compound 1 was characterized by elemental analysis, IR, powder X-ray diffraction (PXRD), and single crystal X-ray diffraction and thermogravimetric analysis (TGA). Compound 1 consists of dimeric [Cd2(μ-ppvppa)2] fragments linked by 1,4-NDC bridges to generate a 2D honeycomb network. Complex 1 strongly emits blue light in the solid state when excited at 419 nm at ambient temperature. This emission is selectively quenched by nitro aromatic compounds in water with good sensitivity. Compound 1 also displays recyclable detection of nitro aromatic compounds.
127 citations
TL;DR: This work represents the first case of a 2D Co(II)-based SIM composed of a monocomponent organic spacer and indicates that the spatially separated high-spin Co( II) ions act as single-ion magnets (SIMs).
Abstract: A novel two-dimensional (2D) coordination polymer, [Co(ppad)2]n (1), resulted from the assembly of CoII ions based on a versatile ligand termed N3-(3-pyridoyl)-3-pyridinecarboxamidrazone. Alternating/direct-current magnetic studies of compound 1 indicate that the spatially separated high-spin CoII ions act as single-ion magnets (SIMs). The present work represents the first case of a 2D CoII-based SIM composed of a monocomponent organic spacer.
126 citations
TL;DR: A new PCP, [(Cu4Cl)(BTBA)8·(CH3)2NH2)·(H2O)12]·xGuest (PCP-33⊃guest), which shows high potential for purification of natural gas, separation of C2H2/CO2 mixtures, and selective removal of C 2H2 from C2 H2/C2H4 mixtures at ambient temperature is demonstrated.
Abstract: Porous coordination polymers (PCPs), constructed by bridging the metals or clusters and organic linkers, can provide a functional pore environment for gas storage and separation. But the rational design for identifying PCPs with high efficiency and low energy cost remains a challenge. Here, we demonstrate a new PCP, [(Cu4Cl)(BTBA)8·(CH3)2NH2)·(H2O)12]·xGuest (PCP-33⊃guest), which shows high potential for purification of natural gas, separation of C2H2/CO2 mixtures, and selective removal of C2H2 from C2H2/C2H4 mixtures at ambient temperature. The lower binding energy of the framework toward these light hydrocarbons indicates the reduced net costs for material regeneration, and meanwhile, the good water and chemical stability of it, in particular at pH = 2 and 60 °C, shows high potential usage under some harsh conditions. In addition, the adsorption process and effective site for separation was unravelled by in situ infrared spectroscopy studies.
123 citations
TL;DR: In this article, the Ag(I)-doping synthetic strategy reported in this work may be applicable to other coordination polymer systems containing thiolate ligands for the preparation of various metal ion-doped multidimensional coordination polymers with new topological structures and better catalytic performances in the photodecomposition of azo dyes in industrial wastewater.
Abstract: Ambient temperature solid state reaction of a preformed compound {[Pb(Tab)2]2(PF6)4}n (1) (TabH = 4-(trimethylammonio)benzenethiol) with two equiv. of 1,2-bis(4-pyridyl)ethylene (bpe) quantitatively produces a unique two-dimensional coordination polymer {[Pb(Tab)2(bpe)]2(PF6)4}n (2). The Ag(I)-doped coordination polymer {[Pb(Tab)2(bpe)]2(PF6)4·1.64AgNO3}n (2a) is readily prepared by immersing 2 into AgNO3 aqueous solution. Compared with its two precursors 1 and 2, 2a exhibits greatly enhanced catalytic activity towards the photodegradation of a family of 12 azo dyes within a short period of time under UV light irradiation and excellent adaptability on the elimination of azo dyes in water. It is anticipated that the ‘Ag(I)-doping’ synthetic strategy reported in this work may be applicable to other coordination polymer systems containing thiolate ligands for the preparation of various metal ion-doped multidimensional coordination polymers with new topological structures and better catalytic performances in the photodecomposition of azo dyes in industrial wastewater.
TL;DR: Instant adsorption of Congo Red by a 1D coordination polymer leads to the formation of a unique dye composite 1·0.75CR·6H2O, which demonstrates a remarkably enhanced photocurrent response compared to that of its precursor.
TL;DR: A pentadentate chelate-bridging ligand possessing an inner N 2 O 3 coordination site with one amide, one imine, and two phenoxo functions, 2-hydroxy-N-(2-(((3-hydroxynaphthalen-2-yl)methylene)amino)ethyl)benzamide (H 3 L), was synthesised Reaction it with Mn(OAc) 2 ·4H 2 O yielded a novel zigzag penta-coordinated Mn(III) coordination polymer, [MnL
TL;DR: Rational design and synthesis of a new low molecular weight gelator (LMWG) having 9,10-diphenylanthracene core and terminal terpyridine is reported, which leads to yellow and white light emitting bimetallic gels.
TL;DR: A facile yet effective fluorescent method for sensing of Cu(2+) in rat brain using one kind of lanthanide coordination polymer nanoparticle, adenosine monophosphate (AMP) and terbium ion (Tb(3+)), i.e., AMP-Tb, as the sensing platform is reported.
Abstract: Copper ions (Cu2+) in the central nervous system play a crucial role in the physiological and pathological events, so simple, selective, and sensitive detection of cerebral Cu2+ is of great importance. In this work, we report a facile yet effective fluorescent method for sensing of Cu2+ in rat brain using one kind of lanthanide coordination polymer nanoparticle, adenosine monophosphate (AMP) and terbium ion (Tb3+), i.e., AMP-Tb, as the sensing platform. Initially, a cofactor ligand, 5-sulfosalicylic acid (SSA), as the sensitizer, was introduced into the nonluminescent AMP-Tb suspension, resulting in switching on the luminescence of AMP-Tb by the removal of coordinating water molecules and concomitant energy transfer from SSA to Tb3+. The subsequent addition of Cu2+ into the resulting SSA/AMP-Tb can strongly quench the fluorescence because the specific coordination interaction between SSA and Cu2+ rendered energy transfer from SSA to Tb3+ inefficient. The decrease ratio of the fluorescence intensities of S...
TL;DR: Amorphous three-dimensional (3D) nanoflake array-assembled porous 2D cobalt-oxalate coordination polymer thin sheets (CQU-Chen-OA-Co-1-1) were first synthesized by using a facile hydrothermal route under electro-magnetic stirring as mentioned in this paper.
Abstract: Amorphous three-dimensional (3D) nanoflake array-assembled porous 2D cobalt–oxalate coordination polymer thin sheets (CQU-Chen-OA-Co-1-1) were first synthesized by using a facile hydrothermal route under electro-magnetic stirring. The resulting material exhibited excellent pseudocapacitive performance with a high specific capacitance of 702.75 F g−1 at 1 A g−1 and remarkable cycling stability.
TL;DR: The self-assembled zinc(II) coordination polymers [Zn(L)(H2O)2]n (1), Zn3(L)2(formate)2 (4,4′-bipyridine)3]n·2n(DMF)·2 n(H2Os) (L = 5-acetamidoisophthalate) as mentioned in this paper have been synthesized and characterized by elemental microanalysis, infrared spectroscopy, thermogravimetric analysis, and X-ray single crystal x-ray
Abstract: The novel self-assembled zinc(II) coordination polymers [Zn(L)(H2O)2]n (1), [Zn(L)(H2O)2]n·n(formamide) (2), [Zn(L)(H2O)2]n·n(N-methylformamide) (3), [Zn(L)(H2O)(formamide)]n (4), and [Zn3(L)2(formate)2(4,4′-bipyridine)3]n·2n(DMF)·2n(H2O) (5) (L = 5-acetamidoisophthalate) have been synthesized and characterized by elemental microanalysis, infrared spectroscopy, thermogravimetric analysis, and X-ray single crystal X-ray diffraction. 1, 2, and 3 are one-dimensional (1D) coordination polymers that crystallize in monoclinic P21, monoclinic P21/m, and triclinic P1 systems, respectively, and are pseudo-polymorphic supramolecular isomers with 1 having a helical arrangement, and 2 and 3 exhibiting zigzag type structures containing different guest molecules. Compound 4 crystallizes in the triclinic P1 space group and is a 1D coordination polymer that exhibits fused 8-membered and 16-membered dimetallic rings. Compound 5 features a two-dimensional network type polymer with trimetallic cores. Compounds 1–5 expand ...
TL;DR: The time-dependent measurements for both compounds demonstrate their ability to retain conductivity up to 10 h, and compound 2 shows the highest proton conductivity among the carboxylate-based 1D CPs.
Abstract: We report the proton conduction properties of a 2D flexible MOF and a 1D coordination polymer having the molecular formulas {[Zn(C10H2O8)0.5(C10S2N2H8)]·5H2O]}n (1) and {[Zn(C10H2O8)0.5(C10S2N2H8)]·2H2O]}n (2), respectively. Compounds 1 and 2 show high conductivity values of 2.55 × 10–7 and 4.39 × 10–4 S cm–1 at 80 °C and 95% RH. The conductivity value of compound 1 is in the range of those for previously reported flexible MOFs, and compound 2 shows the highest proton conductivity among the carboxylate-based 1D CPs. The dimensionality and the internal hydrogen bonding connectivity play a vital role in the resultant conductivity. Variable-temperature experiments of both compounds at high humidity reveal that the conductivity values increase with increasing temperature, whereas the variable humidity studies signify the influence of relative humidity on high-temperature proton conductivity. The time-dependent measurements for both compounds demonstrate their ability to retain conductivity up to 10 h.
TL;DR: DSC and temperature dependent X-ray powder diffraction (XRPD) measurements prove that 3/II transforms into 3/I on heating, and the crystal structure of3/II was determined ab initio from XRPD data.
Abstract: Reaction of cobalt thiocyanate with 4-acetylpyridine leads to the formation of [Co(NCS)2(4-acetylpyridine)2]n (3/I). In its crystal structure the Co cations are connected by pairs of μ-1,3-bridging thiocyanato ligands into dimers that are further connected into layers by single anionic ligands. DTA-TG measurements of Co(NCS)2(4-acetyl-pyridine)4 (1) led to the formation of 3/I. In contrast, when the hydrate Co(NCS)2(4-acetyl-pyridine)2(H2O)2 (2) is decomposed, a mixture of 3/I and a thermodynamically metastable form 3/II is obtained. Further investigations reveal that thermal annealing of 2 leads to the formation of 3/II, that contains only traces of the stable form 3/I. DSC and temperature dependent X-ray powder diffraction (XRPD) measurements prove that 3/II transforms into 3/I on heating. The crystal structure of 3/II was determined ab initio from XRPD data. In its crystal structure the Co cations are linked by pairs of bridging thiocyanato anions into a 1D coordination polymer, and thus, 3/II is an is...
TL;DR: Two new coordination compounds with tetracopper(II) cores act as bioinspired precatalysts for mild homogeneous oxidation, by aqueous hydrogen peroxide at 50 °C in an acidic MeCN/H2O medium, of various cyclic and linear C5-C8 alkanes to the corresponding alcohols and ketones.
Abstract: Two new coordination compounds with tetracopper(II) cores, namely, a 1D coordination polymer, [Cu4(μ4-H2edte)(μ5-H2edte)(sal)2]n·10nH2O (1), and a discrete 0D tetramer, [Cu4(μ4-Hedte)2(Hpmal)2(H2O)]·7.5H2O (2), were easily self-assembled from aqueous solutions of copper(II) nitrate, N,N,N′,N′-tetrakis(2-hydroxyethyl)ethylenediamine (H4edte), salicylic acid (H2sal), or phenylmalonic acid (H2pma). The obtained compounds were characterized by IR and electron paramagnetic resonance spectroscopy, thermogravimetric and elemental analysis, and single-crystal X-ray diffraction. In addition to different dimensionalities, their structures reveal distinct single-open [Cu4(μ2-O)(μ3-O)3] (in 1) or double-open [Cu4(μ2-O)2(μ3-O)2] (in 2) cubane cores with 3M4-1 topology. In crystal structures, numerous crystallization water molecules are arranged into the intricate infinite 1D {(H2O)18}n water tapes (in 1) or discrete (H2O)9 clusters (in 2) that participate in multiple hydrogen-bonding interactions with the metal–organi...
TL;DR: In this article, a three-dimensional coordination polymer, [Eu3(bcbp)3(NO3)7(OH)2]n (1) (H2bcbp·2Cl = 1,1′-bis(4-carboxyphenyl)-(4,4′-bipyridinium) dichloride), was prepared by the solvothermal reaction of Eu( NO3)3·6H2O and H2bcBP·2CL in methanol, which was characterized by infrared spect
Abstract: A stable three-dimensional coordination polymer, [Eu3(bcbp)3(NO3)7(OH)2]n (1) (H2bcbp·2Cl = 1,1′-bis(4-carboxyphenyl)-(4,4′-bipyridinium) dichloride), was prepared by the solvothermal reaction of Eu(NO3)3·6H2O and H2bcbp·2Cl in methanol, which was characterized by infrared spectroscopy, single-crystal X-ray diffraction, powder X-ray diffraction, and thermogravimetric analyses. In the solid state, 1 consists of an unusual trinuclear Eu(III) unit (Eu3(CO2)6(NO3)7(OH), Eu3–SBU), which further connects to six neighboring ones through six bcbp ligands to form a three-dimensional network. As expected, 1 exhibits a strong red-light emission at ambient temperature. Due to the presence of the electron-deficient bipyridinium moiety in the conjugation, this emission is selectively quenched by electron-rich organic amine compounds with high sensitivity and exhibits a prominent visual color change.
TL;DR: In this article, a two-dimensional zinc-pamoate coordination polymer (Zn(PAM) en) was synthesized under hydrothermal conditions and the strong emission of 1 was quenched efficiently by adding trace amounts of 2,4,6-trinitrophenol (TNP).
Abstract: A luminescent two-dimensional zinc–pamoate coordination polymer, [Zn(PAM)(en)] ( 1 ) (PAM = 4,4′-methylenebis(3-hydroxy-2-naphthalenecarboxylate), en = 1,2-ethanediamine) has been synthesized under hydrothermal conditions. The strong emission of 1 was quenched efficiently by adding trace amounts of 2,4,6-trinitrophenol (TNP), even in the presence of other interfering analytes such as 4-nitrophenol, 2,6-dinitrotoluene, 2,4-dinitrotoluene, nitrobenzene, 1,3-dinitrobenzene, hydroquinone, dimethylbenzene and bromobenzene, which exhibited superior selectivity of 1 for the detection of TNP via a fluorescence quenching mechanism. Similarly, 1 also exhibited unique selectivity and sensitivity toward Cu 2+ compared to other metal cations such as Zn 2+ , Mn 2+ , Mg 2+ , K + , Na + , Ni 2+ , Co 2+ and Ca 2+ . This reveals compound 1 can be used as a dual luminescence sensor for the detection of TNP and Cu 2+ alternatively.
TL;DR: A one-dimensional cobalt(II) coordination polymer, [Co(btm)2(SCN)2·H2O]n [btm = bis(1H-1,2,4-triazol-1-yl)methane], was synthesized and magnetically characterized.
Abstract: A one-dimensional cobalt(II) coordination polymer, [Co(btm)2(SCN)2·H2O]n [btm = bis(1H-1,2,4-triazol-1-yl)methane], was synthesized and magnetically characterized. The isolated slightly distorted octahedral CoII ion displays field-induced slow relaxation with a big positive axial and a negative rhombic magnetic anisotropy (D = 93.9 cm–1 and E = −10.5 cm–1), and the anisotropy energy barrier is 45.4 K.
TL;DR: This work showed the potential perspective of Mx(C3N3S3)y (M = transitional metals) coordination polymers as a series of new materials for solar energy storage and conversion.
Abstract: Herein, we reported a octahedral Cd3(C3N3S3)2 coordination polymer as a new noble metal-free photocatalyst for robust photocatalytic H2O2 production from methanol/water solution. The coordination polymer can give an unprecedented H2O2 yield of ca. 110.0 mmol • L−1 • g−1 at pH = 2.8 under visible light illumination. The characterization results clearly revealed that the photocatalytic H2O2 production proceeds by a pathway of two-electron reduction of O2 on the catalyst surface. This work showed the potential perspective of Mx(C3N3S3)y (M = transitional metals) coordination polymers as a series of new materials for solar energy storage and conversion.
TL;DR: Density functional theory calculations on the special model of Cu-LCP support the occurrence of ferromagnetic interactions between the adjacent copper(II) ions.
Abstract: A copper-based layered coordination polymer ([Cu(hmt)(tfbdc)(H2O)]; hmt = hexamethylenetetramine, tfbdc = 2,3,5,6-tetrafluoroterephthalate; Cu-LCP) has been synthesized, and it has been structurally and magnetically characterized. The Cu-LCP shows ferromagnetic interactions between the adjacent copper(II) ions. Density functional theory calculations on the special model of Cu-LCP support the occurrence of ferromagnetic interactions. As an electrode material for supercapacitors, Cu-LCP exhibits a high specific capacitance of 1274 F g−1 at a current density of 1 A g−1 in 1 M LiOH electrolyte, and the capacitance retention is about 88% after 2000 cycles.
TL;DR: Interestingly, complex 1 can selectively capture cationic dye molecules from mixtures of dye molecules containing different charges in aqueous solutions and could serve as a good candidate material for the selective removal of cationIC dyes during the treatment of wastewater.
Abstract: A 1D anionic lanthanide coordination polymer {[(CH3)2NH2] [(H2abtc)2Ho(H2O)]}n (1) (H4abtc = 3,3′,5,5′-azobenzene-tetracarboxylic acid) has been synthesized under hydrothermal reaction conditions. The protonated [(CH3)2NH2]+ is generated from decomposed DMA during the reaction, and balances the negative charge of the framework. The as-obtained samples were characterized using single-crystal and powder X-ray diffraction and TGA. Interestingly, 1 can selectively capture cationic dye molecules from mixtures of dye molecules containing different charges in aqueous solutions. Furthermore, 1 exhibits a different adsorption efficiency toward different cationic dyes (crystal violet, rhodamine B, safranine T and methylene blue). Among the studied dyes, methylene blue has a higher adsorption efficiency in comparison to the others. Thus, complex 1 could serve as a good candidate material for the selective removal of cationic dyes during the treatment of wastewater.
TL;DR: In this paper, two new crystalline materials bearing distinct tricopper(II) cores were easily generated by the aqueous medium self-assembly method from copper (II) nitrate, bis(2-hydroxyethyl)amino-tris(hydroxymethyl)methane (H5bis-trIS) or triethanolamine (H3tea) aminoalcohol biobuffers and homophthalic acid (H2hpa).
Abstract: Two new crystalline materials [Cu3(μ2-H3bis-tris)2(μ2-Hhpa)2]·H2O (1) and [Cu3(μ2-H2tea)2(μ2-hpa)(μ3-hpa)]n (2) bearing distinct tricopper(II) cores were easily generated by the aqueous medium self-assembly method from copper(II) nitrate, bis(2-hydroxyethyl)amino-tris(hydroxymethyl)methane (H5bis-tris) or triethanolamine (H3tea) aminoalcohol biobuffers and homophthalic acid (H2hpa). The obtained products were characterised by IR, UV-vis and EPR spectroscopy, ESI-MS(±), thermogravimetric, elemental and single crystal X-ray diffraction analysis. Apart from possessing different dimensionality, the crystal structures of the discrete 0D trimer 1 and the zigzag 1D coordination polymer 2 show distinct symmetric [Cu3(μ-O)4(μ-COO)2] and asymmetric [Cu3(μ-O)3(μ-COO)2] tricopper(II) cores, respectively. An intense pattern of intermolecular O–H⋯O hydrogen bonds provides a 0D → 3D (1) or 1D → 2D (2) extension of the structures into intricate topologically unique H-bonded nets. After additional simplification, these were classified as a uninodal 6-connected 3D framework with the snk topology in 1 and a binodal 3,5-connected 2D layer with the 3,5L50 topology in 2. Variable-temperature magnetic susceptibility studies indicate a predominant ferromagnetic coupling [J = 39.1(1) and 29.5(1) cm−1 for 1 and 2, respectively] within the mixed-bridged tricopper(II) cores. Both compounds 1 and 2 were also applied as rather efficient bio-inspired pre-catalysts for the mild homogeneous oxidation, by aqueous H2O2 at 50 °C in acidic MeCN–H2O medium, of cyclic (cyclopentane, cyclohexane, cycloheptane and cyclooctane) and linear (n-pentane, n-hexane, n-heptane and n-octane) alkanes to the corresponding alcohols and ketones with overall yields up to 26% based on the alkane. The effects of different reaction parameters (type of pre-catalyst and acid promoter, reaction time and substrate scope) and various selectivity features were investigated and discussed, supporting a free-radical mechanism in the present alkane oxidations.
TL;DR: The 1D coordination polymer (CP) is formed when CuI reacts with SMe2 in n-heptane, whereas in acetonitrile (MeCN), the reaction forms exclusively the 2D CP [(Me2S)3{Cu4(μ-I)4}]n (2) containing "flower-basket" Cu4I4 units.
Abstract: The 1D coordination polymer (CP) [(Me2S)3{Cu2(μ-I)2}]n (1) is formed when CuI reacts with SMe2 in n-heptane, whereas in acetonitrile (MeCN), the reaction forms exclusively the 2D CP [(Me2S)3{Cu4(μ-I)4}]n (2) containing “flower-basket” Cu4I4 units. The reaction product of CuI with MeSEt is also solvent-dependent, where the 1D polymer [(MeSEt)2{Cu4(μ3-I)2(μ2-I)2}(MeCN)2]n (3) containing “stepped-cubane” Cu4I4 units is isolated in MeCN. In contrast, the reaction in n-heptane affords the 1D CP [(MeSEt)3{Cu4(μ3-I)4}]n (4) containing “closed-cubane” Cu4I4 clusters. The reaction of MeSPr with CuI provides the structurally related 1D CP [(MeSPr)3{Cu4(μ3-I)4}]n (5), for which the X-ray structure has been determined at 115, 155, 195, 235, and 275 K, addressing the evolution of the metric parameters. Similarly to 4 and the previously reported CP [(Et2S)3{Cu4(μ3-I)4}]n (Inorg. Chem. 2010, 49, 5834), the 1D chain is built upon closed cubanes Cu4(μ3-I)4 as secondary building units (SBUs) interconnected via μ-MeSPr liga...
TL;DR: Variable-temperature dc and ac magnetic susceptibility measurements of Co(dca)2(atz)2 show that the high-spin cobalt(ii) ions act as single ion magnets (SIMs).
Abstract: A novel two-dimensional coordination polymer of the formula [Co(dca)2(atz)2]n (1) resulted from assembling trans-bis(2-amino-1,3,5-triazine)cobalt(II) motifs by dicyanamide spacers. Variable-temperature dc and ac magnetic susceptibility measurements of 1 show that the high-spin cobalt(II) ions act as single ion magnets (SIMs).
TL;DR: A copper-containing coordination polymer (BIT-C) was synthesized and structurally analyzed by single-crystal X-ray diffraction as discussed by the authors, which has an outstanding catalytic activity for the conversion of atmospheric pressure CO2 and various epoxides to cyclic carbonates.