Coordination Polymers Research Articles

Processable Coordination Polymer Inks for Highly Conductive and Robust Coatings.

The unique properties and processability of conducting and semiconducting organic materials have fascinated scientists since their discovery. Of this broad class of materials, conductive coordination polymers are of immense recent interest due to their innate modularity and tunability. However, these materials are typically generated as powders and, in some cases, single crystals which significantly limits possible processing and many applications. Herein, we report a method that enables solution-phase processing of a previously reported highly conductive coordination polymer, NiTTFtt (TTFtt = tetrathiafulvalenetetrathiolate), into thin films and conductive textiles. Thin films of NiTTFtt show record-breaking conductivity for a coordination polymer and unusual physical behavior that sheds light on the transport mechanisms in this glassy metallic material. Textiles coated with NiTTFtt are conductive and durable to air, water, washing, acid, base, and mechanical cycles. The properties and processability of NiTTFtt reported here make it notable among coordination polymers and conducting organic materials more broadly.

Synthesis and characterization of a new coordination polymer of copper (II): Catalytic application for reductive degradation of dyes under dark

Synthesis and characterization of a new coordination polymer of copper (II): Catalytic application for reductive degradation of dyes under dark

Stoichiometry-Regulated Synthesis of Three Adenine-Based Coordination Polymers for Catalytic Excellence through the Synergistic Amalgamation of Coordinative Unsaturation and Lewis Basic Sites.

Nucleobase adenine is a promising candidate for synthesizing fascinating coordination polymers (CPs) due to the presence of five potential metal-ion binding centers. In recent years, CPs have emerged as promising Lewis acid-base centers containing heterogeneous catalysts for a wide range of organic transformations. However, the crucial role of stoichiometric regulations of the starting materials and their consequential impact on catalytic performance are rarely studied. Herein, we have synthesized three adenine (Ad)-based cadmium CPs with 5-nitro isophthalic acid (H2NIPA) by a mixed linker approach by tuning the substrate's stoichiometric proportion. The single-crystal X-ray diffraction analysis of the synthesized CPs, SSICG-11, [Cd(Ad)(NIPA)(H2O)]·H2O; SSICG-12, [Cd(Ad)2(NIPA)(H2O)]; and SSICG-13, [Cd4(Ad)(NIPA)3]·H2O·DMF, reveals that these three compounds exhibit distinct asymmetric units, each reflecting varying precursor proportions. Due to their high chemical stability and the presence of both Lewis acidic-basic sites, SSICG-11-13 were employed as heterogeneous catalysts for Hantzsch and Strecker reactions. However, SSICG-12 is more efficient due to its capacity to form an open metal sites (OMSs) and the presence of a higher number of adenine moieties. Overall, this study demonstrated the stoichiometrically controlled synthesis of adenine-based CPs and dissected their efficiency as a heterogeneous catalyst by correlating their structures and compositions.

Regulating a sql layered coordination polymer into a rare fsc open framework with naphthalenedisulphonic acid pillar for C2H2/CO2 separation

The removal of carbon dioxide (CO2) from acetylene (C2H2) represents a pivotal industrial process for the production of high-purity C2H2. Nevertheless, the separation of C2H2 and CO2 is challenging due to their highly similar molecular sizes and physical properties. In this work, we report a fine regulation of a sql layered coordination polymer (termed NTU-107) into a rare fsc open framework (termed NTU-108) with naphthalenedisulphonic acid pillar for selective C2H2 capture from CO2-contained mixtures. NTU-107 was prepared by the reaction of 4-(1H-imidazol-1-yl)benzoic acid (L1) ligand and Cu2+ ion, showing a layered framework with a pore size of 4.2 Å. After inserting 1,5-naphthalenedisulphonic acid between the layers, a new pillar-layered open framework (5.8 Å) with sulphonic acid functional sites was prepared. Single-component gas adsorption experiments and breakthrough experiments demonstrated that NTU-108 with accessible sulphonic acid sites exhibits a high C2H2 absorption capacity and dynamic C2H2/CO2 separation performance at room temperature.

Elucidation of the Transformation of Coordination Polymer Intermediates into 2D Metal-Organic Framework Films during Chemical Vapor Deposition.

Chemical vapor deposition (CVD) is a rising tool to synthesize metal-organic framework (MOF) films. Despite growing interest and usage, its mechanism is less known. Especially, the identification of intermediates is crucial for understanding the growth mechanism and further controlling their structures. In this paper, we investigated the growth mechanism of 2D MOF Cu3(C6O6)2 film by CVD. We identified a novel intermediate phase: an octahedral coordination polymer that transforms into an edge-on-oriented 2D MOF. In situ grazing-incidence wide-angle X-ray scattering, X-ray absorption near-edge structure, high-resolution transmission electron microscopy, and Raman spectroscopy studies confirmed that this transformation involves the removal of pillars, leading to the formation of a square-planar 2D MOF. With the identification of intermediates, our study deepens the understanding of MOF film formation by CVD, which lays a foundation to control the structure.

Close‐Packed One‐Dimensional Coordination Polymer Cathode with Fast Kinetics for Sodium‐Ion Batteries

AbstractSustainable sodium‐ion batteries (SIBs) have gained tremendous attention; however, the large‐sized Na+ poses serious challenges on the development of inorganic‐based cathodes. To overcome the issues, metal–organic electrode materials are appealing because they combine attractive characteristics of organic redox centers (e. g., flexibility, highly reversible redox properties, fast kinetics (regardless of size and charge of guest ions), structural/redox tunability, and resource abundance) with structural stability arising from metal‐ligand coordination. Herein, a one‐dimensional copper−benzoquinoid coordination polymer (CP), [CuL(Py)2]n, (LH4=1,4‐dicyano‐2,3,5,6‐tetrahydroxybenzene, Py=pyridine) is investigated as cathode for SIBs. As opposed to most CPs reported for SIBs which possess high porosity and surface area, this close‐packed CP can deliver discharge capacity as high as 277 mAh g−1 at 2C (~523 mA g−1), and at extremely high rates of 50C and 300C (~13 and 78 A g−1), reversible capacities of 131 and 74 mAh g−1 still can be delivered, respectively. The transport kinetics of Na+ in [CuL(Py)2]n is found to be even faster than that of Li+ despite the close‐packed structure. The mechanistic and kinetic studies have been performed. The findings gained in this work undoubtedly unravel a potential design strategy for high‐performance metal–organic electrode materials for emerging post‐Li‐ion batteries.

Durable Photosynthesis of Hydrogen Peroxide Using a Uranyl Coordination Polymer: Exciton Dissociation and Hydrogen Abstraction.

The photosynthesis of hydrogen peroxide (H2O2), involving water oxidation and oxygen reduction, is crucial for optimizing light utilization. Here, a previously synthesized one-dimensional chain-like semiconductive uranyl coordination polymer (NDC-UCP) was used for the efficient overall photosynthetic reaction of H2O2 and its photocatalytic mechanism was systematically investigated. The excellent stability of NDC-UCP enables continuous H2O2 production for up to 96 h. Its unique hydrogen extraction capability enhances the photocatalytic performance, achieving a H2O2 production rate of 283.80 μmol g-1 h-1. Two mechanisms for H2O2 generation were revealed: efficient electron-hole separation in NDC-UCP facilitates a two-step one-electron oxygen reduction and direct water oxidation, while hydrogen abstraction of UO22+ generates hydroxyl (·OH) and hydroperoxyl radicals (HO2·), enhancing H2O2 photosynthesis. This study highlights the potential of uranyl coordination polymers in H2O2 production and their synergistic exciton dissociation and hydrogen abstraction functionalities in photocatalytic redox reactions.

Zwitterionic 2‐Phosphaethene‐thiolates [(LC)P=CS(LC/P)]+ as PCS Building Blocks (LC = NHC, LP = PR3)

The zwitterionic compounds [(LC)P=CS(LC/P)]+ (3+, LC = NHC, LP = PR3), featuring cationic substituents at the phosphorus and carbon atoms, are synthesized as their triflate salts at a multi‐gram scale from the reaction of Lewis base adducts of CS2, namely LC/P–CS2 (4), with a combination of [(LCP)4][OTf]4 (1[OTf]4) and Ph3P. The feasibility of using 3+ as PCS building blocks is showcased in their reactions with representative electrophiles (MeOTf) and nucleophiles (MesMgBr, Ph3PCH2), leading to selective functionalization of the PCS core at the S‐ and P‐terminus, respectively. Additionally, it is reported that 3+ can function as ambident nucleophiles with AgOTf (2 equivalents), affording unprecedented linear coordination polymer [Ag2(OTf)3‐μ2:κP,κS–((LC)P=CS(PCy3))]+ (6b), where the PCS moiety acts as a bridging ligand in transition metal complexes for the first time. Reduction of 3+ facilitates the cleavage of the P‐ and C‐bound substituents leading to the formation of the [PCS]– anion. Moreover, cycloaddition reactions of 3+ with 1[OTf]4 are shown to selectively yield five‐ and eight‐membered polyphosphorus heterocycles. Preliminary results suggest the possibility of activating the C–S bond in [(LC)P=CS(LC)]+, resulting in the formation of [(LC)P=C(LC)–P(LC)][OTf]2, 12[OTf]2, which may serve as a synthon for the PCP unit in future studies.

Coordinatively Unsaturated Structurally Diverse Homophthalate-Based Cobalt(II) Coordination Polymers for Efficient Multicomponent Catalysis

Coordinatively Unsaturated Structurally Diverse Homophthalate-Based Cobalt(II) Coordination Polymers for Efficient Multicomponent Catalysis

Light-Emitting Coordination Polymers: Stimuli-Responsive Gels, PMMA-Based Composite Films, and UV-Shielding.

Lanthanide-based light-emitting coordination polymers (CPs) and CP gels (CPGs) have significance for applications in optical systems, image processing/multiplexing, and optical sensors. In this study, we report two new luminescent CPs (EuL-CP (1) and TbL-CP (2)) and CPGs (EuL-gel (5) and TbL-gel (6)) using lanthanide(III) ions (Ln(III) = Eu(III) and Tb(III)) and 4-(4-carboxyphenyl)-2,2:6,2-terpyridine ligand (L) capable of forming stable thermoreversible gels. Probable structures of EuL-CP (1) and TbL-CP (2) and the formations of EuL-gel (5) and TbL-gel (6) are proposed based on adequate computational studies. The CPGs are stimuli-responsive and could be utilized as invisible security inks for encryption. Further, poly(methyl methacrylate) (PMMA) polymer doped with respective CPs (0.75 wt %) is found to be suitable for forming composite films with UV-shielding properties.

Delivery of differentiation therapy into solid tumor cancer stem-like cells to prevent metastasis and recurrence

Abstract. The concept of differentiation therapy offers an attracting explanation for plenty of clinical observations, such as relapse and metastasis. Its hallmark success has been in the treatment of acute promyelocytic leukaemia, a condition that is now highly curable through the combination of retinoic acid (RA) and arsenic. Recently, the finding of cancer stem-like cells (CSCs) triggers more attentions due to its unique high tumourigenicity and chemoresistance., which reside in hypoxic tumor regions, and are characterized by high tumourigenicity and chemoresistance. Considerable efforts have been made to develop promising anti-CSC strategies, including blocking surface biomarkers and inhibiting self-renewal signaling pathways. In this study, we engineered a liposomal delivery strategy that enables the codelivery of RA and arsenate, aiming to differentiate and potentiate CSCs. The core of the liposome is formed through coordination polymerization between arsenate and Calcium, while the membraneincorporates RA and helper lipids. We evaluated their cytotoxicity against cultured CSCs and their potential to differentiate CSCs into less malignant phenotypes.

A Ni4O4-cubane-squarate coordination framework for molecular recognition

Molecular recognition is a fundamental function of natural systems that ensures biological activity. This is achieved through the sieving effect, host-guest interactions, or both in biological environments. Recent advancements in multifunctional proteins reveal a new dimension of functional organization that goes beyond single-function molecular recognition, emphasizing the need for artificial multifunctional materials in industrial applications. Herein, we have designed a porous Ni4O4-cubane squarate coordination polymer as an artificial molecular recognition host, drawing inspiration from the structural and functional features of natural enzymes. A comprehensive assessment of the material’s ability to distinguish target species under different operating conditions was carried out. The results confirm its sieving function through hexane isomers separation, host-guest interaction function via xenon/krypton separation, and dual presence of sieving and interaction through carbon dioxide/nitrogen separation. Additionally, the material demonstrates good stability and feasibility for large-scale production, indicating its practical potential. Our findings provide a bio-inspired multifunctional recognition material for chemical separations as proof-of-concept while offering solutions to advance artificial multifunctional materials adaptable to other applications beyond chemical separations.

Enhancing Near-Infrared Photothermal Performance by Molecular Aggregation Optimization in Semiconductive Coordination Polymers.

Near-infrared (NIR) photothermal conversion materials have recently received widespread attention due to their potential in diverse applications. However, highly efficient organic-based NIR photothermal agents remain limited. Developing strategies to enhance the efficiency of NIR photothermal materials and elucidating the relationship between the NIR photothermal performance and molecular aggregation are highly desired. Herein, we report two coordination polymers {[Cd2(ONDI)(ox)]·2/3(H2O)}n (1) and [Ba(ONDI)(H2O)2]n (2), in which the ONDI2- ligands assemble into different π-π stacking arrangements. Compound 1 exhibits H-aggregation, while compound 2 displays X-aggregation. The X-aggregation in compound 2 extends the optical absorption into the NIR region and enhances the absorption intensity. Consequently, compound 2 demonstrates a 1.8-fold increase in NIR photothermal efficiency (68.6%) compared to compound 1 (38.8%), attributed to more effective π-π interactions in X-aggregation. In addition, both compounds show semiconductive properties, with conductivities of 2.1 × 10-7 S/cm for compound 1 and 3.0 × 10-7 S/cm for compound 2 at 30 °C in a nitrogen atmosphere. These properties arise from the synergistic effects of "band-like" charge transport within crystals and "hopping" charge transport across grain boundaries. By integration of their NIR photothermal effects and semiconductive properties, compounds 1 and 2 show interesting NIR photoelectrical responses.

Fibrous Pb(II)‐Based Coordination Polymer Operable as a Photocatalyst and Electrocatalyst for High‐Rate, Selective CO2‐to‐Formate Conversion

AbstractA nonporous [Pb(tadt)]n (tadt = 1,3,4‐thiadiazole‐2,5‐dithiolate) coordination polymer, KGF‐9, with a 2D infinite (−Pb−S−)n structure has been previously reported as a precious‐metal‐free photocatalyst for selective CO2‐to‐formate conversion under visible light. In the present work, a microwave (MW)‐assisted solvothermal reaction is used to synthesize KGF‐9 with improved physicochemical properties and catalytic activity. Compared with KGF‐9 prepared by the previously reported methods, that prepared by the new synthesis route exhibited a greater specific surface area, greater crystallinity, and greater photoconductivity. These improved properties led to a drastic increase of the apparent quantum yield (AQY) for selective formate production, from 2.6 to 25% at 400 nm; this AQY represents a record‐high value among reported heterogeneous photocatalysts for CO2‐to‐formate conversion. Interestingly, the AQY for formate production is unchanged irrespective of the light intensity (0.04–14 mW cm−2), indicating little contribution of charge accumulation in the bulk during the reaction (i.e., indicating efficient charge transport to surface reactants). When composited with Ketjen Black, KGF‐9 enabled the electrochemical conversion of CO2 to formate in aqueous solution while maintaining a high selectivity. A high‐rate reduction of CO2 to formate with a total absolute current density of 200–300 mA cm−2 is achieved, with a Faradaic efficiency (FE) of >90%.

Engineering Trifluoromethyl Groups in Porous Coordination Polymers to Enhance Stability and Regulate Pore Window for Hexane Isomers Separation.

Effective separation of hexane (C6) isomers is critical for a variety of industrial applications but conventional distillation methods are energy-intensive. Adsorptive separations based on porous coordination polymers (PCPs) offer a promising alternative due to their exceptional porosity and tunable properties. However, there is still an urgent need to develop PCPs with high stability and separation performance. This study investigates how substituting a methyl (-CH3) group with a trifluoromethyl (-CF3) group can regulate pores and hydrophobicity in PCPs. This precise adjustment aims to enhance stability and improve the kinetic separation performance of hydrophobic C6 isomers by considering the size and hydrophobicity of the trifluoromethyl group. Two isostructural PCPs with pcu topology, PCP-CH3 and PCP-CF3, were synthesized to vary pore diameters and hydrophobicity based on the presence of -CH3 or -CF3 groups. PCP-CF3 showed greater stability in water compared to PCP-CH3. While PCP-CH3 had high adsorption capacities, it lacked selectivity, whereas PCP-CF3 demonstrated improved selectivity, particularly in excluding dibranched isomers. Dynamic column separation experiments revealed that PCP-CF3 could selectively adsorb linear and monobranched isomers over dibranched isomers at room temperature. These findings highlight the potential of fluorine-modified PCPs for efficient isomer separation and underscore the importance of stability improvement strategies.

Solvent and additive-controlled supramolecular isomerism in zinc coordination polymers

A new series of Zn(II) supramolecular isomers containing ditopic 1,3-di(pyridin-4-yl)urea (4bpu) ligand were synthesized and characterized by infrared analysis, elemental analysis and TGA as well as single-crystal X-ray diffraction analysis. Four solvent-induced pseudopolymorphic zinc (II) coordination polymers (CPs), namely, {[Zn(4bpu)(OAc)2](CH3OH)}n (1), {[Zn(4bpu)(OAc)2](C2H5OH)}n (2), {[Zn(4bpu)(OAc)2](HOCH2CH2OH)}n (3), and {[Zn(4bpu)(OAc)2](0.5H2O)}n (4), were prepared by the reaction of Zn(OAc)2.2H2O and 4bpu via self-assembly under varying solvent systems. Also, a pair of polymorphic coordination polymers namely, {[Zn(4bpu)(OAc)2](CH3OH)}n (1α) and {[Zn3(4bpu)3(OAc)6](CH3OH)2}n(1β), was prepared in the presence of different organic additives. Single-crystal X-ray diffraction confirmed that 1−4 and 1α display 1D polymeric zig-zag chains and 1β exhibits 1D triple-stranded ladders that were self-assembled through various supramolecular interactions. In addition, a series of dissolution-recrystallization structural transformations (DRST) were performed on these supramolecular isomers.

Reversible Single-Crystal to Single-Crystal Transformation and Associated Magnetism of a Cyanide-Bridged Chiral-Structured Magnet.

A chiral molecule-based magnet [MnII (S-pnH) (H2O)][MnIII(CN)6]·H2O (S-pn = S-1,2-diaminopropane), 1S·2H2O (P212121), has been obtained, which has a two-dimensional (2D) square network of cyanide-bridged MnII-MnIII ions. The crystallographic research on this coordination polymer indicates that it is robust enough to transform the single-crystal structure upon dehydration as well as rehydration. Meanwhile, the magnetic property changes are reversibly associated with the structural phase transitions. The complete reversibility upon dehydration/rehydration was demonstrated using in situ X-ray diffraction from the as-prepared 1S·2H2O to the dehydrated [MnII (S-pnH)][MnIII(CN)6], 1S, then rehydrated to [MnII (S-pnH) (H2O)][MnIII(CN)6]·H2O, 1S-HP, and dehydrated again to [MnII (S-pnH)][MnIII(CN)6], 1S-DeHP. Neither the space groups nor the crystal axes changed during the dehydration/rehydration process. The dehydration is considered to be associated with a change in the coordination of the S-pnH from one 2D layer to the neighboring one involving a proton transfer and is accompanied by new cyanide bridging of MnII and MnIII ions formed between the 2D sheet. Corresponding to the 2D to three-dimensional (3D) structural transition, the study of magnetic properties reveals that the Curie temperature of long-range magnetic ordering for 1S (TC = 45 K) is more than double that for 1S·2H2O (TC = 21 K).

In vivo Study of the Anti/Prooxidant Activity of a Metal-Organic Coordination Polymer Modified with Iron Oxides and Ascorbic Acid

Experiments on 39 male Wistar rats were performed. A metal-organic coordination polymer modified with iron oxide and ascorbic acid (composite) was administered intravenously to healthy rats at doses of 25 and 50 mg/kg. The anti/prooxidant activity of the composite was assessed 3 and 24 hours after administration. The composite in both doses was shown to have no significant effect on the homeostasis of prooxidants/antioxidants in the blood serum in healthy animals. In high doses, the composite enhances apoptosis of lymphocytes, which indicates its possible use as a catalyst for free radical processes for further use in biomedicine.

Photoinduced Self-assembly: An Alternative Strategy for the Construction of Coordination Oligomers and Polymers.

Self-assembled oligonuclear and polynuclear complexes have numerous functionalities and potential applications. Generally, such compounds have been constructed by thermal substitution reactions with bridging ligands. Herein, we report bottom-up and photochemical construction of functional coordination oligomers and polymers by photosubstitution-induced self-assembly. The photosubstitution reactions of a ruthenium precursor complex with bridging ligands having pyrazole moieties afford mono-, di-, tri-, tetra-, and pentanuclear ruthenium complexes, Ru1-Ru5, which have one-dimensional architectures. Intramolecular hydrogen bonding between each bridging ligand is a key to construct the molecular nanowires. All the complexes have been isolated and thoroughly characterized. The photochemically synthesized ruthenium complexes act as synthons for longer metal-complex-based nanowires with a length of the order of tens-of nanometers. The multinuclear complexes are generated by photoinduced self-assembly in the presence of a base, and they undergo photoinduced disassembly in the presence of acid.

Syntheses, Structures, and Photocatalytic and Sonocatalytic Degradations of Methyl Blue of Cu(II) and Mn(II) Coordination Polymers Based on Tri(triazole) and Dicarboxylate Ligands.

Cu(II) and Mn(II) coordination polymers [Cu(ttpa)(sub)]n (Cuttpa or 1) and {[Mn2(ttpa)2(nip)2(H2O)2]·3H2O}n (Mnttpa or 2) (ttpa = tris(4-(1,2,4-triazol-1-yl)phenyl)amine, H2sub = suberic acid, nip = 5-nitroisophthalicate) were hydrothermally prepared and the structures were characterized. Cuttpa exhibited a 2D (4,4) network based on [Cu2(COO)4] dimers with upper and lower dangled ttpa ligands and a 2D → 3D polythreaded network. Mnttpa showed a 2D (4,4) network with dangled uncoordinated triazole rings from ttpa ligands and nitro groups from nip2- ligands and a 2D → 3D polythreaded network. Eg data of Cuttpa and Mnttpa were 1.88 eV and 2.11 eV. Cuttpa and Mnttpa exhibited good catalytic activity for the decomposition of methyl blue (MB) under visible light and supersound irradiation. The decomposition mechanism using Cuttpa was explored. The holes (h+) and •OH hydroxyl radicals played the main roles, and the •O2- superoxide radicals played certain auxiliary roles in the decomposition of MB within the Cuttpa catalyst.