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Tailoring the Coordination Micro‐Environment in Nanotraps for Efficient Platinum/Palladium Separation

Abstract Recovering platinum group metals from secondary resources is crucial to meet the growing demand for high‐tech applications. Various techniques are explored, and adsorption using porous materials has emerged as a promising technology due to its efficient performance and environmental beingness. However, the challenge lies in effectively recovering and separating individual platinum group metals (PGMs) given their similar chemical properties. Herein, a breakthrough approach is presented by sophisticatedly tailoring the coordination micro‐environment in a series of aminopyridine‐based porous organic polymers, which enables the creation of platinum‐specific nanotraps for efficient separation of binary PGMs (platinum/palladium). The newly synthesized POP‐o2NH 2 ‐Py demonstrates record uptakes and selectivity toward platinum over palladium, with the amino groups adjacent to the pyridine moieties being vital in improving platinum binding performance. Further breakthrough experiments underline its remarkable ability to separate platinum and palladium. Spectroscopic analysis reveals that POP‐o2NH 2 ‐Py offers a more favorable coordination fashion to platinum ions compared to palladium ions owing to the greater interaction between N and Pt 4+ and stronger intramolecular hydrogen bonding between the amino groups and four coordinating chlorines at platinum. These findings underscore the importance of fine‐tuning the coordination micro‐environment of nanotraps through subtle modifications that can greatly enhance the selectivity toward the desired metal ions.

Chemistry↗

How Outer Coordination Sphere Modifications Can Impact Metal Structures in Proteins: A Crystallographic Evaluation

A challenging objective of de novo metalloprotein design is to control of the outer coordination spheres of an active site to fine tune metal properties. The well-defined three stranded coiled coils, TRI and CoilSer peptides, are used to address this question. Substitution of Cys for Leu yields a thiophilic site within the core. Metals such as Hg II , Pb II , and AsIII result in trigonal planar or trigonal pyramidal geometries; however, spectroscopic studies have shown that Cd II forms three-, four- or five-coordinate Cd II S 3 (OH 2 ) x (in which x=0–2) when the outer coordination spheres are perturbed. Unfortunately, there has been little crystallographic examination of these proteins to explain the observations. Here, the high-resolution X-ray structures of apo- and mercurated proteins are compared to explain the modifications that lead to metal coordination number and geometry variation. It reveals that Ala substitution for Leu opens a cavity above the Cys site allowing for water excess, facilitating Cd II S 3 (OH 2 ). Replacement of Cys by Pen restricts thiol rotation, causing a shift in the metal-binding plane, which displaces water, forming CdIIS 3 . Residue d-Leu, above the Cys site, reorients the side chain towards the Cys layer, diminishing the space for water accommodation yielding Cd II S 3 , whereas d-Leu below opens more space, allowing for equal Cd II S 3 (OH 2 ) and Cd II S 3 (OH 2 ) 2 . These studies provide insights into how to control desired metal geometries in metalloproteins by using coded and non-coded amino acids.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Bioinspired Activation of N 2 on Asymmetrical Coordinated Fe Grafted 1T MoS 2 at Room Temperature

Inspired by the nitrogen fixation process on MoFe nitrogenase, asymmetrical coordinated Fe grafted onto 1T MoS 2 were successfully synthesized. The unique electron -rich structure with asymmetrical coordination made the 1T Fe 0.1 Mo 0.9 S 2 layered material actively react with water and dinitrogen at room temperature and atmosphere pressure. Subsequently, ammonia can be produced with a yield of 800 pmol (NH 4 + ) g -1 (12.5% yield in mole). The activation, fixation and reduction of dinitrogen were confirmed by isotopically labeled experiments. The location and the specific coordination environment of grafted Fe in Fe-Mo-S were further determined by X-ray absorption spectroscopy analysis. Our work demonstrates that the nitrogen fixation and reduction for ammonia at room temperature without any chemical and electrochemical assistance is distinctly different from traditional bionic -inspired nitrogen fixation process. The mechanism of the activation and reduction of N 2 was further investigated by density functional theory calculation and Raman spectra. Compared with 1T MoS 2 , the enriched electron nature and asymmetrical coordination of Fe in Fe-Mo-S materials play a critical role in the bioinspired activation of N 2 at ambient condition.

1T MoS2↗

Developing a strategy for the national coordinated soil moisture monitoring network

Soil moisture is a critical land surface variable, affecting a wide variety of climatological, agricultural, and hydrological processes. Determining the current soil moisture status is possible via a variety of methods, including in situ monitoring, remote sensing, and numerical modeling. Although all of these approaches are rapidly evolving, there is no cohesive strategy or framework to integrate these diverse information sources to develop and disseminate coordinated national soil moisture products that will improve our ability to understand climate variability. The National Coordinated Soil Moisture Monitoring Network initiative has developed a national strategy for network coordination with NOAA's National Integrated Drought Information System. The strategy is currently in review within NOAA, and work is underway to implement the initial milestones of the strategy. This update reviews the goals and steps being taken to establish this national-scale coordination for soil moisture monitoring in the United States.

54 ENVIRONMENTAL SCIENCES↗

A fully distributed asynchronous approach for multi-area coordinated network-constrained unit commitment

This paper discusses a consensus-based alternating direction method of multipliers (ADMM) approach to solve the multi-area coordinated network-constrained unit commitment (NCUC) problem in a distributed manner. Due to political and technical difficulties, it is neither practical nor feasible to solve the multi-area coordination problem in a centralized fashion, which requires full access to all data of individual areas. In comparison, in the proposed fully-distributed approach, local NCUC problems of individual areas can be solved independently, and only limited information is exchanged among adjacent areas for facilitating multi-area coordination. Furthermore, as traditional ADMM can only guarantee convergence for convex problems, this paper discusses several strategies to mitigate oscillations, enhance convergence performance, and derive good-enough feasible solutions, including: (i) A tie-line power flow based area coordination strategy is designed to reduce the number of global consensus variables; (ii) Different penalty parameters \r{ho} are assigned to individual consensus variables and are updated via certain rules during the iterative procedure, which would reduce the impact of initial values of \r{ho} on convergence performance; (iii) Heuristic rules are adopted to fix certain unit commitment variables for avoiding oscillations during the iterative procedure; and (iv) An asynchronous distributed strategy is studied, which solves NCUC subproblems of small areas multiple times and exchanges information with adjacent areas more frequently within one complete run of slower NCUC subproblems of large areas. Numerical cases illustrate effectiveness of the proposed asynchronous fully-distributed NCUC approach, and investigate key factors that would affect its convergence performance.

24 POWER TRANSMISSION AND DISTRIBUTION↗

Lamellipodial wrinkles in fish keratocytes as markers of imperfect coordination between extension and retraction during cell migration

Highlights: • Migrating fish keratocytes display prominent lamellipodial wrinkles. • A numerical model shows that wrinkles can arise due to compressive stresses. • In the model, wrinkles only arise if the rear of the cell is transiently stuck. • Experimentally pinning the rear of the cell also induces wrinkles. • Wrinkles reflect imbalances between retraction and extension during migration. Cell migration involves the precise coordination between extension at the front of the cell and retraction at the rear. This coordination is particularly evident in fast moving cells such as fish keratocytes, where it leads to highly stable gliding motion, propelled at the front by broad, 0.1-0-2 μm thick lamellipodia. Transient uncoupling between extension and retraction can occur if the rear is temporarily stuck, which might eventually lead to cell shape instabilities. We have frequently observed in fish keratocytes the presence of lamellipodial radial wrinkles, detected by confocal, scanning electron and side-view microscopy as folds in the lamellipodium up to 2 μm in height. Using a linear finite elements analysis, we simulated the displacement of cells either with perfect coordination between extension and retraction or with the rear transiently stuck while the front continues extending, and we observed that in this last condition compression stresses arise in the lamellipodium which predict the formation of the observed pattern of lamellipodial wrinkles. In support of the numerical modeling findings, we observed that the transient halting of retraction at the rear using micromanipulation induced the formation of lamellipodial wrinkles in previously flat lamellipodia. The obtained results suggest that the conspicuous lamellipodial wrinkles observed in migrating fish keratocytes are the product of transient imbalances between front and rear displacements, and are therefore useful markers of the short scale dynamics of extension and retraction coordination during cell migration.

60 APPLIED LIFE SCIENCES↗

Thermoelastic-plastic flow equations in general coordinates

The equations governing the thermoelastic-plastic flow of isotropic solids in the Prandtl- Reuss and small anisotropy approximations in Cartesian coordinates are generalized to arbitrary coordinate systems. In applications the choice of coordinates is dictated by the symmetry of the solid flow. Here, the generally invariant equations are evaluated in spherical, cylindrical (including uniaxial), and both prolate and oblate spheroidal coordinates.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Crystal structures, fluorescent and magnetic properties of five new coordination polymers based on biphenyl-3,4 Prime ,5-tricarboxylic acid

Five new coordination polymers, {l_brace}[Cd{sub 3}(bpt){sub 2}(DMF){sub 2}]{center_dot}(H{sub 2}O){sub 2}{r_brace}{sub n} (1), [Cd(Hbpt)(bipy){sub 0.5}(H{sub 2}O)]{sub n} (2), [Cd{sub 2}(bpt)(phen){sub 2}Cl]{sub n} (3), {l_brace}[Cu{sub 2}(bpt)(phen)({mu}{sub 2}-OH)(H{sub 2}O)]{center_dot}(H{sub 2}O){sub 2}{r_brace}{sub n} (4) and {l_brace}[Mn{sub 5}(Hbpt){sub 4}(phen){sub 4}({mu}{sub 2}-OH){sub 2}(H{sub 2}O){sub 2}]{center_dot}(H{sub 2}O){sub 2}(CH{sub 3}CN){sub 2}{r_brace}{sub n} (5) have been prepared through hydro(solvo)thermal reactions of H{sub 3}bpt (H{sub 3}bpt=biphenyl-3,4 Prime ,5-tricarboxylic acid) with different pyridyl-containing auxiliary ligands (bipy=4,4 Prime -bipyridine and phen=1,10-phenanthroline). Compound 1 represents a 3D ladder-like framework composed of rod-shaped infinite chains. In 2, the bridging ligand bipy links binuclear cadmium ions to generate a 2D layer. Compound 3 features a 1D ladder structure and further linked by {pi}-{pi} stacking interaction to form a 3D supramolecular network. Compound 4 exhibits a binodal 3-connected net which features the Schlafli symbol of (4{center_dot}8{sup 2}). Compound 5 contains trimetallic cluster and binuclear unite which are further linked by Hbpt ligand to form a 2D layer. Moreover, photoluminescent properties of compounds 1-3 were studied in the solid state. Magnetic susceptibility measurements indicate that compound 4 exhibits ferromagnetic exchange interactions, whereas compound 5 displays antiferromagnetic exchange interactions. - Graphical abstract: Five new coordination polymers have been prepared through reactions of H{sub 3}bpt with different pyridyl-containing auxiliary ligands. The bpt exhibits four new kinds of coordination modes with 'V or Y shape'. Highlights: Black-Right-Pointing-Pointer 1 represents a unique (4{center_dot}8)-connected network with a Schlafli symbol (4{sup 6})(4{sup 12}{center_dot}6{sup 12}{center_dot}8{sup 4}). Black-Right-Pointing-Pointer Compound 4 shows ferromagnetic interaction between the dimeric Cu{sup 2+} units. Black-Right-Pointing-Pointer The bpt ligand exhibits four new kinds of coordination modes with 'V or Y shape'.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Homochiral coordination polymers constructed from aminocarboxylate derivates: Effect of bipyridine on the amidation reaction

Using aminocarboxylate derivates (S)-N-(4-cyanobenzoic)-glutamic acid (denoted as cbg, 1a) and (S)-N-(4-nitrobenzoic)-glutamic acid (denoted as nbg, 1b) as chiral ligands, five new homochiral coordination polymers formulated as [Cu(cbg)(H{sub 2}O){sub 2}]{sub n} (3), [Cu(cbop){sub 2}(4,4 Prime -bipy)(H{sub 2}O)]{sub n} (4) (cbop=(S)-N-(4-cyanobenzoic)-5-oxoproline, 4,4 Prime -bipy=4,4 Prime -bipyridine), {l_brace}[Cu(nbop){sub 2}(4,4 Prime -bipy)]{center_dot}4H{sub 2}O{r_brace}{sub n} (5) (nbop=(S)-N-(4-nitrobenzoic)-5-oxoproline), {l_brace}[Cd(nbop){sub 2}(4,4 Prime -bipy)]{center_dot}2H{sub 2}O{r_brace}{sub n} (6), and [Ni(nbop){sub 2}(4,4 Prime -bipy)(H{sub 2}O){sub 2}]{sub n} (7) have been hydrothermally synthesized and structurally characterized. Single-crystal X-ray diffraction study reveals that the original chirality of aminocarboxylate derivates is maintained in all these complexes. Complexes 3, 4, and 7 are one-dimensional infinite chain coordination polymers, while complexes 5 and 6 possess two-dimensional network structures. In situ cyclization of 1a and 1b was taken place in the formation of complexes 4-7, which may be due to the competition of 4,4 Prime -bipyridine with chiral ligands during the coordination process. Preliminary optical behavior investigation indicates that ligands 1a, 1b, and complexes 6, 7 are nonlinear optical active. - Graphical abstract: Using aminocarboxylate derivates as chiral ligands, five new homochiral coordination polymers possessing second harmonic generation activities have been hydrothermally synthesized. Highlights: Black-Right-Pointing-Pointer Two new chiral aminocarboxylate derivates were firstly synthesized. Black-Right-Pointing-Pointer Five new homochiral metal organic complexes were obtained hydrothermally based on these ligands. Black-Right-Pointing-Pointer Intramolecular amidation was taken place on the aminocarboxylate derivates during the formation of these complexes. Black-Right-Pointing-Pointer In situ amidation may be due to the impact of 4,4 Prime -bipyridine. Black-Right-Pointing-Pointer The homochiral complexes are nonlinear optical active.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Syntheses, structure and properties of three-dimensional pillared-layer Ag(I)-Ln(III) heterometallic coordination polymers based on mixed isonicotinate and hemimellitate ligands

Three pillared-layer 4d-4f Ag(I)-Ln(III) heterometallic coordination polymers (HCPs), formulated as [Ln{sub 2}Ag(hma){sub 2}(ina)(H{sub 2}O){sub 2}]{sub n} nH{sub 2}O [Ln=La(1), Pr(2), Nd(3); Hina=isonicotinic acid, H{sub 3}hma=hemimellitic acid], have been synthesized under hydrothermal conditions. Single-crystal and powder X-ray diffractions confirm that they are isostructural, which features a three-dimensional (3D) pillared-layer heterometallic structure built upon the strictly alternate arrangement of lanthanide-organic layers and [Ag(ina)] pillars. The layers and pillars are connected to each other by Ln-O and Ag-O coordination bonds. The photoluminescent property of the Nd derivative (3) has also been investigated. - Graphical abstract: Three pillared-layer 4d-4f Ag(I)-Ln(III) heterometallic coordination polymers have been synthesized and structurally characterized. Highlights: Black-Right-Pointing-Pointer Three 3D pillared-layer 4d-4f HCPs were synthesized by hydrothermal reactions. Black-Right-Pointing-Pointer The synergistic coordination strategy was employed. Black-Right-Pointing-Pointer It opens new perspective for the construction of structurally diversified 4d-4f HCPs.

36 MATERIALS SCIENCE↗

Three new Ag(I) coordination architectures based on mixed ligands: Syntheses, structures and photoluminescent properties

Three new silver (I) coordination complexes, [Ag{sub 2}(1,2-bdc)(phdat)]{sub n} (1), [Ag{sub 2}(NO{sub 2}-bdc)(phdat)]{sub n} (2), [Ag{sub 4}(nta){sub 3}(phdat)NO{sub 3}]{sub n} (3) (1,2-bdc=phthalic acid dianion, NO{sub 2}-bdc=5-nitro-1,3-benzenedicarboxylic acid dianion, nta=nicotinic acid anion, phdat=2,4-diamine-6-phenyl-1,3,5-triazine) have been hydrothermally synthesized by the reactions of silver nitrate and phdat with the homologous ligands 1,2-H{sub 2}bdc, NO{sub 2}-H{sub 2}bdc, and Hnta, respectively, and characterized by single-crystal X-ray diffractions, IR spectra, elemental analyses thermogravimetric analyses (TGA). The compound 1 exhibits a chiral 3D network with cbs/CrB self-dual topological net, which contains two kinds of single helical chains. For compound 2, the 3D network is comprised of two kinds of similar 2D sheets with the topological symbol of sql-type packed in AABBAA mode by Ag–N/O weakly contacts. And compound 3 has 2D double layer architecture, consisting of the 2D plane with hcb-type topological symbol connected by Ag–O weakly coordinations. The photoluminescent properties associated with the crystal structures of three compounds have also been measured. - Graphical abstract: Three new silver(I) coordination complexes 1–3 have been synthesized and characterized by single-crystal X-ray diffractions, IR spectra, elemental analyses, thermogravimetric analyses (TGA) and photoluminescent spectra. Highlights: ► The compound 1 exhibits a novel chiral 3D network with two kinds of single helical chains. ► 3D or 2D new Ag coordination complexes. ► The photoluminescent properties have been measured.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Tuning metal–carboxylate coordination in crystalline metal–organic frameworks through surfactant media

Although it has been widely demonstrated that surfactants can efficiently control the size, shape and surface properties of micro/nanocrystals of metal–organic frameworks (MOFs) due to the strong interactions between surfactants and crystal facets of MOFs, the use of surfactants as reaction media to grow MOF single crystals is unprecedented. In addition, compared with ionic liquids, surfactants are much cheaper and can have multifunctional properties such as acidic, basic, neutral, cationic, anionic, or even block. These factors strongly motivate us to develop a new synthetic strategy: growing crystalline MOFs in surfactants. In this report, eight new two-dimensional (2D) or three-dimensional (3D) MOFs have been successfully synthesized in an industrially-abundant and environmentally-friendly surfactant: polyethylene glycol-200 (PEG-200). Eight different coordination modes of carboxylates, ranging from monodentate η{sup 1} mode to tetra-donor coordination µ{sub 3}-η{sup 1}:η{sup 2}:η{sup 1} mode, have been founded in our research. The magnetic properties of Co-based MOFs were investigated and MOF NTU-Z6b showed a phase transition with a Curie temperature (T{sub c}) at 5 K. Our strategy of growing crystalline MOFs in surfactant could offer exciting opportunities for preparing novel MOFs with diverse structures and interesting properties. - Graphical abstract: Surfactants have been used as reaction media to grow MOF single crystals for the first time. Eight new two-dimensional or three-dimensional MOFs were successfully synthesized in surfactant polyethylene glycol-200 (PEG-200). Coordination modes of carboxylates up to eight were founded. Our strategy of growing crystalline MOFs in surfactant could offer exciting opportunities for preparing novel MOFs with diverse structures and interesting properties. Display Omitted - Highlights: • Surfactant-thermal synthesis of crystalline metal–organic frameworks. • Eight new 2-D or 3-D metal–organic frameworks. • Eight different metal–carboxylate coordination modes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Syntheses and structures of three heterometallic coordination polymers derived from 4-pyridin-3-yl-benzoic acid

Three lanthanide–transition-metal coordination polymers, namely, [Er{sub 2}L{sub 6}(H{sub 2}O)][Cu{sub 2}I{sub 2}] (1), [ErL{sub 3}][CuI] (2), and [Dy{sub 2}L{sub 6}(BPDC){sub 0.5}(H{sub 2}O){sub 4}][Cu{sub 3}I{sub 2}] (3) (HL=4-pyridin-3-yl-benzoic acid, H{sub 2}BPDC=4,4′-biphenyldicarboxylic acid) have been made by reacting Ln{sub 2}O{sub 3} and CuI with HL at different temperatures under hydrothermal conditions. All the complexes are characterized by elemental analysis, IR spectroscopy, thermogravimetric analysis, powder X-ray diffraction, and single-crystal X-ray diffraction, respectively. 1–3 all construct from dimeric (Ln{sub 2}) and (Cu{sub 2}) units and exhibit two types of the structural features: 1 is a two-dimensional layer, 2–3 are three-dimensional frameworks. Interestingly, the in situ formation of the BPDC ligand is found in the structure of 3. The distinct architectures of these complexes indicated that the reaction temperature plays an important role in the formation of higher dimensional coordination polymers. - Graphical abstract: By hydrothermal reaction of lanthanide oxide, copper halide, and 4-pyridin-3-yl-benzoic ligand at different temperatures, a series of 1-D to 3-D 3d–4f coordination polymers, namely [ErL{sub 3}(H{sub 2}O){sub 2}][CuI], [Er{sub 2}L{sub 6}(H{sub 2}O)][Cu{sub 2}I{sub 2}], [ErL{sub 3}][CuI], and [Dy{sub 2}L{sub 6}(BPDC){sub 0.5}(H{sub 2}O){sub 4}][Cu{sub 3}I{sub 2}], have been made, respectively. - Highlights: • Three novel heterometallic coordination polymers derived from 4-pyridin-3-yl-benzoic acid have been hydrothermally synthesized. • Mixed dinuclear motifs of (Ln{sub 2}) and (Cu{sub 2}) serve as secondary building units to generate 2-D layer and 3-D frameworks. • It is proved that higher temperature is apt to permit construction of high dimensional architectures.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Two new pyridine-2,3-dicarboxylate coordination polymers prepared from zerovalent metal precursor: Syntheses, luminescent and magnetic properties

Two new K{sup +}/Cu(II) and Zn(II) coordination polymers with pyridine-2,3-dicarboxylate (pydc), (K{sub 2}[Cu(μ-pydc){sub 2}]·3H{sub 2}O){sub n} (1) and ([Zn(µ-pydc)(H{sub 2}O)(4-mim)]·H{sub 2}O){sub n} (2) (4-mim=4-methylimidazole) have been synthesized from zerovalent metal and characterized by IR, EPR spectroscopy, thermal analysis and single crystal X-ray diffraction techniques. In the sandwiched 3D anionic framework of 1, pydc ligands exhibit hexadentate coordination; tridentate coordination bond with Cu(II) and tridentate ionic interaction with K{sup +} ions. (K{sub 2}[Cu(μ-pydc){sub 2}]·3H{sub 2}O){sub n} shows a rare topology consists of three dimensional (3,4,5)-connected network with the point symbol of (4{sup 2}.6){sub 2}(4{sup 2}.8{sup 4})(4{sup 3}.6.8{sup 6}){sub 2}. The distorted square pyramidal geometry of 2 is completed with an nitrogen atom from 4-mim and aqua ligand to form a 1D polynuclear structure. The hydrogen bonds link the 1D chains into 3D architecture. The temperature dependent magnetic property of complex 1 has been studied. Complex 2 exhibits unusual yellow luminescence in the solid state at room temperature. - Graphical abstract: Two new K{sup +}/Cu(II) and Zn(II) coordination polymers with pyridine-2,3-dicarboxylate (pydc), (K{sub 2}[Cu(μ-pydc){sub 2}]·3H{sub 2}O){sub n} (1) and ([Zn(µ-pydc)(H{sub 2}O)(4-mim)]·H{sub 2}O){sub n} (2) (4-mim=4-methylimidazole) have been synthesized from zerovalent metal and characterized by IR, EPR spectroscopy, thermal analysis and single crystal X-ray diffraction techniques. The water soluble (K{sub 2}[Cu(μ-pydc){sub 2}]·3H{sub 2}O){sub n} shows three dimensional a rare 3,4,5-connected network with the point symbol of (4{sup 2}.6){sub 2}(4{sup 2}.8{sup 4})(4{sup 3}.6.8{sup 6}){sub 2}. The temperature dependent magnetic property of complex 1 has been studied. Complex 2 exhibits unusual yellow luminescence in the solid state at room temperature. Display Omitted - Highlights: • Water-soluble (K{sub 2}[Cu(μ-pydc){sub 2}]·3H{sub 2}O){sub n} has synthesized. • Zerovalent metal precursors are utilized. • The temperature dependent magnetic properties have been studied.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Cu{sup II} coordination polymers based on 5-methoxyisophthalate and flexible N-donor ligands: Structures and magnetic properties

Three Cu{sup II} coordination polymers, ([Cu{sub 2}(CH{sub 3}O-ip){sub 2}(bmib)]){sub n} (1), ([Cu{sub 2}(CH{sub 3}O-ip){sub 2}(bmib){sub 2}]){sub n} (2) and ([Cu(CH{sub 3}O-ip)(bbip)]∙2H{sub 2}O){sub n} (3) (CH{sub 3}O-H{sub 2}ip is 5-methoxyisophthalic acid, bmib is 1,4-bis(2-methylimidazol-1-yl)butane and bbip is 1,3-bis(1H-benzimidazolyl)propane), have been synthesized by hydrothermal methods. Complexes 1–3 were structurally characterized by elemental analysis, infrared (IR) spectra and X-ray single-crystal diffraction. Complex 1 shows a 3D six-connected self-penetrating network based on paddlewheel secondary building units. Complex 2 has a 3-fold interpenetrating 3D diamond framework. Complex 3 possesses a 1D tube-like chain. Thermo-gravimetric and magnetic properties of 1–3 were also investigated. - Graphical abstract: Structures and magnetic properties of copper(II) coordination polymers constructed from 5-methoxyisophthalate linker and two flexible N-donor ancillary ligands. Three copper(II) coordination polymers with 5-methoxyisophthalate and two related flexible N-donor ancillary ligands have been synthesized and structurally characterized. Moreover, thermal behaviors and magnetic properties of these complexes have also been investigated. - Highlights: • Three Cu(II) coordination polymers were synthesized. • The conformations of N-donor ligands and pH value have an effect on the final structures. • The magnetic properties of 1–3 have been investigated.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Mixed ligand coordination polymers with flexible bis-imidazole linker and angular sulfonyldibenzoate: Crystal structure, photoluminescence and photocatalytic activity

Four ternary coordination polymers (CPs) namely, ([Ni(SDB)(BITMB)(H{sub 2}O)]·H{sub 2}O){sub n} (CP1), ([Cd(SDB)(BITMB) (H{sub 2}O)]·(THF)(H{sub 2}O)){sub n} (CP2), ([Zn{sub 2}(SDB){sub 2}(BITMB)]·(THF){sub 2}){sub n} (CP3) and ([Co{sub 2}(SDB){sub 2}(BITMB)]·(Dioxane){sub 3}){sub n} (CP4) composed of angular dicarboxylate SDB (4,4'-sulfonyldibenzoate) and N-donor BITMB (1,3-bis(imidazol-1-ylmethyl)-2,4,6-trimethyl benzene) have been synthesized by solvothermal reactions and characterized by single crystal X-ray diffraction and other physico-chemical techniques. CP1 possesses one-dimensional ribbon type metal–organic motifs glued together by H-bonds and π⋯π interactions, whereas CP2–CP4, exhibit non-interpenetrated sql networks supported by weak supramolecular interactions. Structural diversity of these CPs can be attributed to the coordination geometry adopted by the metal nodes, versatile coordination modes of SDB and conformational flexibility of BITMB. Solid state luminescence properties of CP1–CP4 were explored. Photocatalytic performance of all CPs for the decomposition of metanil yellow by dilute hydrogen peroxide in the presence of visible light was also investigated. 25–83% dye removal from aqueous solutions in the presence of CP1–CP4 was observed. - Graphical abstract: Four new ternary transition metal CPs have been hydrothermally prepared and their structural aspects as well as photocatalytic activity for decolourization of metanil yellow (MY) dye have been investigated. - Highlights: • Four ternary coordination polymers containing Ni, Cd, Zn and Co center are prepared. • Crystal structure and thermal stability of all four CPs has been described. • PL and diffuse reflectance spectra of synthesized CPs have also been examined. • Band gap values suggest semiconducting behavior of prepared CPs. • Photocatalytic activity of CPs for oxidative degradation of metanil yellow is studied.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Mercury coordination polymers with flexible ethane-1,2-diyl-bis-(pyridyl-3-carboxylate): Synthesis, structures, thermal and luminescent properties

The reaction of the flexible ligand, ethane-1,2-diyl-bis-(pyridyl-3-carboxylate), (L) with HgI{sub 2} and HgBr{sub 2} salts under the same experimental conditions leads to the formation of two coordination polymers with different motifs: ([Hg(L)(Br{sub 2})]){sub n}(1) and ([Hg(L)(I{sub 2})]){sub n}(2). In both compounds, the ligand, (L) acts in a μ2-N:N′-bidentate fashion to link HgBr{sub 2} and HgI{sub 2} units to form a linear and helical chain motif, along [1 0 0] for (1) and [0 0 1] for (2). The ethylene moiety of (L) has gauche and trans conformation in compounds (1) and (2), respectively. The flexible conformation of L produces differences in the optical and crystal properties of the two compounds. - Graphical abstract: This work demonstrates how the HgX{sub 2} units are coordinates by bi-dentate ligand forming polymeric coordination complexes by self-assembly of both chemical units.- Highlights: • News 1-D d{sup 10} transition metal coordination polymers. • The photoluminescent properties have been measured. • The thermal properties have been measured.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Effects of isomorphous substitution of a coordination polymer on the properties and its application in electrochemical sensing

This work concerns the isomorphous substitution of coordination polymers (CPs) and its effect on the optical and electrochemical properties. The application of CPs in electrochemical sensing was studied as well. Isomorphous coordination polymers, [Co{sub x}Zn{sub 1−x}tyr]{sub n} (tyr=L-tyrosine), where x (0–1) was controlled by the Co/Zn ratios of raw materials, were successfully synthesized via a hydrothermal method, as proved by XRD and EDS results. Their UV–vis DRS and fluorescence spectra change gradually along with the composition. Cyclic voltammograms of modified electrodes, [Co{sub x}Zn{sub 1−x}tyr]{sub n}/GCE, show that as more and more Zn replaced Co, the current signal decreases greatly and the potential shifts negatively. Much attention was paid to [Cotyr]{sub n} due to its highest sensitivity. Refreshable modified carbon paste electrode, [Cotyr]{sub n}-CPE, was used to determine nitrite, and showed pretty good performance as evidenced by chronoamperometry. The response was made very fast within mere 5 s. The linear detection range was from 5.00×10{sup −5} to 3.45×10{sup −3} M, with sensitivity of 263.4 mA mol{sup −1} L cm{sup −2}. The detection limit was found to be 2.00×10{sup −5} M. The sensor also showed good antiinterference and reproducibility. - Graphical abstract: Evolution of the optical and electrochemical properties of isomorphic coordination polymers [Co{sub x}Zn{sub 1−x}tyr]{sub n} along with the changing of x was studied. The CP also showed perfect performance in the electrochemical determination of nitrite. - Highlights: • Isomorphous substitution of coordination polymers (CPs). • Substitution-caused evolution of optical and electrochemical properties of CPs. • Application of CPs in electrochemical sensing, an incipient area. • Perfect performance of CPs in electrochemical determination of nitrite.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗