Organic Coordination Polymers Research Articles

Multifaceted properties of an engineered three-dimensional Zn(ii)–metal–organic coordination polymer: synthesis, crystal structure, efficient photocatalytic degradation of an organic dye and selective luminescent sensing

Luminescent sensing of volatile organic solvents (VOCs), anions, cations, etc., and photocatalysts for aromatic dyes are two of the many emerging applications for metal-organic frameworks and coordination polymers (MOFs/CPs).

Cadmium(II)-Organic Coordination Polymer Containing Carboxyl Groups: Solvothermal Synthesis, Structure, and Properties

Cadmium(II)-Organic Coordination Polymer Containing Carboxyl Groups: Solvothermal Synthesis, Structure, and Properties

A Terbium(III)-organic Coordination Polymer: Synthesis, Characterization and Its Luminescence

A Terbium(III)-organic Coordination Polymer: Synthesis, Characterization and Its Luminescence

A silver‐based coordination polymer with phenylacetylene ligands for efficient visible light photocatalysis

AbstractA type of organic coordination polymer photocatalyst (PhC2Ag) that can respond to visible light was synthesized. The PhC2Ag with nanorods structure has good hydrophobicity and was reported in eliminating organic pollutants for the first time. The characterization results indicate that PhC2Ag has photoexcited carrier separation ability with the band gap of 2.63 eV. Experimental results indicate that the dominant active species in the PhC2Ag photocatalytic system are the superoxide radical and hydroxyl radical. First‐principles theoretical calculations revealed that effective mass of photogenerated electrons is smaller and has better migration ability. This work provides support for the application of PhC2Ag and its subsequent modified materials in energy and environmental fields such as photocatalytic degradation, hydrogen evolution, and hydrogen peroxide production.

Low-Temperature Synthesis of Metal–Organic Coordination Polymers Based on Oxo-centered Iron Complexes: Magnetic and Adsorption Properties

Low-Temperature Synthesis of Metal–Organic Coordination Polymers Based on Oxo-centered Iron Complexes: Magnetic and Adsorption Properties

Low-Temperature Synthesis of Metal–Organic Coordination Polymers Based on Oxo-centered Iron Complexes: Magnetic and Adsorption Properties

Low-Temperature Synthesis of Metal–Organic Coordination Polymers Based on Oxo-centered Iron Complexes: Magnetic and Adsorption Properties

Superior oxygen electrocatalyst derived from metal organic coordination polymers by instantaneous nucleation and epitaxial growth for rechargeable Li-O2 battery

Superior oxygen electrocatalyst derived from metal organic coordination polymers by instantaneous nucleation and epitaxial growth for rechargeable Li-O2 battery

High proton conductivity modulated by active protons in 1D ultra-stable metal–organic coordination polymers: a new insight into the coordination interaction/ability of metal ions

One-dimensional metal–organic coordination polymers show high proton conductivities and excellent stabilities, mainly attributable to the coordination interactions/abilities of metal ions.

Fabrication of 5-R-isophthalic acid-modulated cadmium–organic coordination polymers and selectivity for the efficient detection of multiple analytes

A series of Cd-CPs were synthesized and structurally characterized. They displayed remarkable fluorescence behaviours, and could serve as outstanding candidates in the selective sensing of multiple analytes with a low limit of detection.

Advanced 1D Metal–Organic Coordination Polymer for Lithium-Ion Batteries: Designing, Synthesis, and Working Mechanism

Anthraquinone (AQ) and its derivatives have been attracting more attention as promising electrode materials for lithium storage because of their high specific capacity, structural diversity, and environmental friendliness. The dissolution and poor electrical conductivity of AQ, however, limit its practical application. Here, a novel metal-organic coordination polymer with a one-dimensional (1D) chain ([C14H6O4Cu]n denoted as Cu-DHAQ; DHAQ, 1,5-dihydroxyl anthraquinone) and its composite with graphene (Cu-DHAQ/G; G, graphene) are developed by the introduction of graphene and copper ion into DHAQ. The fabricated polymer with a 1D chain not only well inhibits the dissolution of DHAQ in organic electrolytes but also facilitates lithium-ion insertion/extraction on carbonyl groups and shortens the migration path of lithium ions. Furthermore, the addition of the conductive network of graphene provides fast transfer rates of electrons. As a result, Cu-DHAQ/G delivers a high discharge capacity, long cycle life, and excellent rate capability. The lithium storage mechanism shows lithium ion insertion/extraction on two carbonyl groups of Cu-DHAQ in the range of 1.6-2.0 V and the redox reaction of Cu+/Cu2+ between 2.8 and 3.0 V, and Cu2+ and Cu+ coexist in the Cu-DHAQ/G electrode during the charge/discharge process. This study provides meaningful guidance to develop metal-organic coordination polymer electrodes for high-performance Li-ion batteries.

Tunable Full‐Color Room Temperature Phosphorescence of Two Single‐Component Zinc(II)‐Based Coordination Polymers

AbstractTunable full‐color room temperature phosphorescence (RTP) is charming due to its potentials in multiple anticounterfeitings, all‐color displays, and multichannel biomarkers. However, it is a huge challenge to achieve excitation‐dependent continuously adjustable full‐color RTP from a single‐component compound. Herein, two Zn(II)‐based organic coordination polymers are reported, which are the first examples characterized by blue, cyan, green, yellow, orange, and red continuously tunable phosphorescence with decent quantum efficiencies in response to variation of excitation energy at ambient conditions. The unique photoluminescence behavior is induced by the selective formation and decay of multiple triplet excited states, i.e., ligand‐centered 3π–π*, 3(ligand‐to‐ligand charge transfer), 3(halogen‐to‐ligand charge transfer), etc., in the coordination network based on the varying excitations. The population and stabilization of the unusual triplet excitons of Zn(II)‐based organic coordination polymers benefit from heavy atom effect of Br− ions and the restriction of molecular motion by crystallization. Here an insight is contributed for the construction of full‐color RTP materials, and metal‐organic coordination polymers are endowed with fresh features for extensive applications.

A high-spintronic helix metal-organic chain as a high-output triboelectric nanogenerator material for self-powered anticorrosion

The development of novel and stable metal–organic coordination polymer triboelectric materials is of great significance for the application of micro/nano power sources in self-powered systems. Here we report the example of a high-spintronic helical metal–organic chain (ZUT-9) by using ionic ligand. ZUT-9 has good chemical stability, functional tunability and excellent triboelectric output performance, which is superior to traditional polymer materials. By adjusting the type of metal and increasing the number of spinons in the metal center, the triboelectric behavior can be effectively improved. The good output performance makes ZUT-9 effective in preventing metal corrosion in cathodic protection system. Combined with theoretical calculation and magnetic behavior characterization, the results show that increasing the number of spinon can be an effective way to significantly enhance the electron delocalization effect and promote frictional power generation behavior. This study provides an idea for the research of helical metal–organic chain materials and will promote their application in self-powered electrochemical cathodic protection.

Synthesis and the Crystal Structure of a New Chiral 1D Metal–Organic Coordination Polymer Based on L-Prolineamide-Substituted Diarylacetylenedicarboxylic Acid Derivative

The new homochiral 1D metal-organic coordination polymer [Cu2(EDPB)•H2O]n was synthesized starting from the original 3,3'-ethyne-1,2-diylbis[6-(L-prolylamino)benzoic acid] (H4EDPB). The unique crystal structure of the new compound was established by powder X-ray diffraction. The [Cu2(EDPB)•H2O]n system shows catalytic activity and enantioselectivity in a Henry reaction of p-nitrobenzaldehyde with nitromethane.

Ag-organic coordination polymers with multi-dimensional electron transfer channels for enhancing CO2 electroreduction

Although, electrons transfer plays an important role in achieving the electrocatalytic CO2 reduction reaction (CO2RR), it is scarce to regulate the electron transfer channels for enhancing the performance of CO2RR via rational design. Here, based on different solvothermal conditions, two metal–organic coordination polymers (MOCPs, Ag-MOCP-1 and Ag-MOCP-2) electrocatalyst for CO2RR were obtained by the same Ag ions and 5-phenyltetrazolium ligands. Single crystal X-ray diffraction showed Ag-MOCP-2 with intra-&inter-layer CH···π and π···π interactions, while Ag-MOCP-1 with intra-layer π···π interactions. The intra-&inter-layer π interactions in Ag-MOCP-2 makes it show multi-dimensional electron transfer channels, which enable Ag-MOCP-2 with higher electron conductivities and lower band gap than Ag-MOCP-1. And the Faradaic efficiency of CO for Ag-MOCP-2 with 78.3 % is higher than that for Ag-MOCP-1 with 69.1 % at −1.08 V vs RHE, and the maximum difference can reach 22 % at −1.48 V vs RHE. Based on the same central metal and organic ligands of the two MOCPs, we believe that multi-dimensional electron transfer channels make a predominant contribution for improving CO2RR performance in this work.

Solid-State Proton Conduction Driven by Coordinated Water Molecules in Metal–Organic Frameworks and Coordination Polymers

As efficient alternative renewable energy resources, proton-exchange membrane fuel cells (PEMFCs) have received immense attention where proton-conducting materials act as PEMs for efficient proton migration. The recent past has witnessed considerable progress in the use of metal–organic frameworks (MOFs) and coordination polymers (CPs) as solid-state proton conductors (SSPCs) due to their structural superiority and architectural diversity. In order to impart proton conductivity, a variety of intrinsic and extrinsic proton sources have been installed onto these frameworks; however, reports on proton conduction where metal-coordinated water molecules act as solely intrinsic proton sources by virtue of their enhanced acidity are largely unexplored. The key examples of proton conduction driven by coordinated water molecules discussed in this Perspective present some unique features of MOFs and CPs as SSPCs, displaying a wide range of proton conductivity. The scope of works with plausible design principles that are urgently required to be investigated is also highlighted.

Progressive Trends in Hybrid Material-Based Chemiresistive Sensors for Nitroaromatic Compounds.

In the last decades, development of hybrid materials, especially inorganic-organic materials, coordination polymers, conducting polymers, carbon materials, and many more, has produced breakthroughs in diverse applications. Various advance materials have been reported in the literature using metal organic frameworks (MOFs), which compensate for the limitations of sensors. Diverse combinations of HMs not only offer excellent features, but also give a ray of hope for unprecedented advances in materials in different research areas, such as sensing, energy storage, catalysis, non-linear optics, drug-delivery systems, gas storage, etc. Chemiresistor sensors are a core enabling sensor technology and have led to much progress in the field of material science. Here, we have reviewed the recent progress in chemiresistive sensors based on HMs for nitroaromatic compounds, which could be beneficial for researchers that explore this field further. We have put emphasis on sensing mechanisms and the performance of diverse HMs for nitroaromatic sensing applications including pesticides, pollutants, explosives, polycyclic aromatic hydrocarbons (PAHs) and persistent organic pollutants (POPs). In the end, we explored opportunities, challenges, and future perspectives in this emerging field.

Advancement and future challenges of metal–organic coordination polymers: A case study of optical sensor for the detection of the environmental contaminants

Fast industrialization, increasing population, rapid urbanization, and the greediness of creamy layer in the society without the issues of caring the sustainability of ecosystem are the main out of many reasons behind the environmental catastrophe. The ecological balance is disturbed with the noxious materials generated from the uncontrolled use of modern science and technology and also unscientific and unsystematic societal growths. To save the modern civilization, a fast‐track task is the monitoring of the toxic materials for the maintenance of sustainable ecological health and their utilization in a circular economy. Accordingly, optical methods are employed for the detection and estimation of environmental contaminants for immediate monitoring. The stability and structural tunability of the coordination polymeric (CPs) materials make them promising optical sensors for easy, low cost, reliable, selective, and sensitive detection of toxic ions/molecules. The crystallinity, thermal, mechanical, magnetic, and optical stability and flexibility of the CPs play a beneficial role for the accurate and stress‐free recognition of the toxicants. In this review, the recent developments as well as the outlook on the sensing of pollutants at a very low concentration level using CPs as selective and specific sensors by spectro‐fluorometric method are summarized. The progresses and challenges in the fabrication of hybrid materials and understanding their structure property correlations are described with an aim to motivate and facilitate the future researchers to perform research in the area.

PH-Regulated Terbium(III) Infinite Coordination Polymer Sensor Array for Pattern Discrimination of Quinolone Antibiotics

In this study, dual-ligand lanthanide metal–organic infinite coordination polymer (BDC-NH2-Tb-AMP ICPs) with dual fluorescence emission was constructed. Considering that quinolone antibiotics can sensitize Tb3+ luminescence, the diverse fluorescence responses for different antibiotics on Tb3+ at various pH’s are distinct due to their structures. Inspired by these facts, a fluorescent sensor array, in which the pH-regulated BDC-NH2-Tb-AMP ICPs acted as the sensing element, was proposed for the pattern recognition of five representative quinolone antibiotics using principal component analysis. Furthermore, the sensor array can realize the detection of environmental quinolone antibiotics in real samples, confirming its reliability and practicality in complex conditions. More broadly, by using the simple yet powerful strategy of pH regulation, the presented sensor array holds a great ability for efficiently distinguishing quinolone antibiotics, which provides an approach for point-of-care monitoring of residual antibiotics in the environmental field.

Cobalt-doped iron-based coordination polymer catalyst with unique shell-shaped agglomerate for enhancing the reaction activity of Kumada-coupling

Metal organic coordination polymers (MOCPs) with versatile structural topologies and flexible design of metal active sites have been considered as suitable heterogeneous catalysts to catalyze various coupling reaction. However, for Kumada-coupling reaction regarded as the most powerful strategy to synthesize biaryls constitute core structural units, rare relevant examples about coordination polymers as catalyst were reported. Herein, we prepared two-dimensional layered MOCP {[Fe (tda)(H2O)]n}via a facile solvothermal method, and investigated the corresponding catalytic activity of Kumada-coupling. Excitingly, the catalytic activity can be efficiently regulated via doping different divalent metal (Co/Mn/Ni) in [Fe (tda)(H2O)]n. Among them, cobalt-doped in [Fe (tda)(H2O)]n can be directly utilized to catalyze Kumada-coupling reaction with good to excellent yield, and reused three times without significant loss of catalytic activity.

Selective CO2-to-Formate Conversion Driven by Visible Light over a Precious-Metal-Free Nonporous Coordination Polymer

Metal–organic frameworks (MOFs) and coordination polymers (CPs) are potential candidates for high-performance photocatalysts because of their high tunability of electronic and structural properties. For example, MOFs and CPs having a high specific surface area (∼1000 m2 g–1) have been applied as visible-light-driven photocatalysts for CO2 reduction and water splitting. Herein, we show a unique CP possessing a metal–sulfur bond with Pb2+, an earth-abundant metal ion. Different from ordinary high-surface-area MOFs and CPs, this CP is nonporous and has just 0.7 m2 g–1 surface area. Nevertheless, owing to its capability of absorbing visible light up to ∼500 nm, it efficiently photocatalyzes CO2 reduction to formate (HCOO–) under visible-light irradiation with >99% selectivity and an apparent quantum yield of 2.6% at 400 nm, even without postmodification treatment such as cocatalyst loading. These values are the highest yet reported for a precious-metal-free single-component photocatalyst for the visible-light-driven reduction of CO2 to HCOO–. This work may thus shed light on the great potential of nonporous CPs as building units of photocatalytic CO2 conversion systems.