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[Display omitted] • New Zn(II) carboxylate complex containing 2-aminopyridine ligand was synthesized and structurally characterized. • FT-IR, UV–visible, fluorescence spectroscopy; single crystal XRD studies were performed. • DNA binding ability of the complex was assessed using absorption and emission spectral studies. • Sensing ability of the complex towards nitroaromatic compounds were explored by fluorescence quenching measurements. • Selective sensing of picric acid in presence of other nitroaromatics explored. • Theoretical studies (DFT) carried out to ascertain complex's preferential binding towards nitroaromatics, especially picric acid revealing involvement of π-stacking and spodium bonding interactions. A mononuclear zinc(II) carboxylate complex containing 4-hydroxybenzoic acid and N -donor 2-aminopyridine was synthesized in aqueous methanol and comprehensively characterized by elemental, spectroscopic, and single-crystal X-ray diffraction analyses. The complex crystallized in monoclinic space group P 2 1 / c having a distorted square pyramidal structure. Spectral and X-ray diffraction analyses confirm the molecular composition of the complex. The complex has shown strong fluorescence emission, acts as a selective and sensitive chemosensor for nitroaromatics. The complex is able to selectively detect picric acid in the presence of other nitroaromatics. Density Functional Theory (DFT) calculations further elucidate the complex's preferential binding towards nitroaromatics, revealing the involvement of π-stacking and spodium bonding interactions. This work not only expands the understanding of zinc(II) carboxylate complexes in supramolecular chemistry but also highlights their promising applications in environmental monitoring and biological studies due to their significant fluorescence quenching in the presence of nitroaromatics and moderate DNA binding affinity. [ABSTRACT FROM AUTHOR]

Neutral and cationic copper(II) semicarbazone complexes with perfluoroalkyl carboxylates as ligands or counter anions, respectively, were synthesized. The lipophilicity and cytotoxicity of these compounds were determined. The cationic complexes with perfluoroalkyl carboxylate anions are more cytotoxic towards MOLT-4 cells compared to their nitrate analogue. [Display omitted] • Eight novel copper(II) semicarbazone perfluoroalkyl carboxylates were synthesized. • Lipophilicity and cytotoxicity of these compounds were determined. • Lipophilic anions enhance cytotoxicity of cationic copper semicarbazone complexes. • Facile deprotonation of hydrazonic nitrogen of coordinated semicarbazone by acetate. A series of (2,4-dihydroxybenzaldehyde dibenzyl semicarbazone) perfluoroalkyl carboxylato copper(II) complexes, [CF 3 (CF 2) n CO 2 (LH)Cu] (LH 2 = 2,4-dihydroxybenzaldehyde dibenzyl semicarbazone; n = 0, 2, 4, 6; 1–4), and (2,4-dihydroxybenzaldehyde dibenzyl semicarbazone) pyridine copper(II) perfluoroalkyl carboxylates, [(LH)(py)Cu]+[CF 3 (CF 2) n CO 2 ]− (5–8) were synthesized. The lipophilicity of these compounds was determined by reverse-phase thin layer chromatography and correlated with their cytotoxicity towards MOLT-4 human leukaemia cells. Cytotoxicity is more strongly correlated with lipophilicity for the non-ionic compounds (1–4) than for the ionic compounds (5–8). Compounds 5–8 (IC 50 2.8–3.8 μM) are generally more cytotoxic than compounds 1–4 (IC 50 3.6–8.4 μM). They also exhibit slightly higher cytotoxicity than the parent anticancer compound [(LH)(py)Cu]+[NO 3 ]− (IC 50 4.15 μM), suggesting that it is possible to enhance the cytotoxicity of [(LH)(py)Cu]+[NO 3 ]− by replacing nitrate with anions of higher lipophilicity. Attempts to synthesize the non-fluorinated analogue [(LH)(py)Cu]+[CH 3 CO 2 ]− resulted in the formation of the deprotonated complex [L(py)Cu], whose structure was confirmed by X-ray crystallography. The structural parameters indicate that the deprotonation site is the hydrazonic nitrogen of the semicarbazone ligand. [ABSTRACT FROM AUTHOR]

[Display omitted] • Assembling of 2-D hydrogen bonded sheets in lithium complexes. • Chlorine-π interactions in assembling of cesium coordination polymer. • 1-D linear barium coordination polymer. • 1-D cadmium coordination polymer with ion-pairs. Two new lithium complexes and three coordination polymers with cesium, barium, and cadmium having deprotonated diclofenac acid (HDFA) ligand are reported. All these non-ionic complexes or the coordination polymers were characterized by single crystal X-ray diffraction, IR and thermal studies. The lithium-diclofenac complexes, [Li(DFA)(H 2 O) 3 ] and [Li(DFA)(H 2 O) 2 (DMF)] were respectively obtained from reaction carried out in aqueous ethanol or dimethylformamide as solvent. Each formed hydrogen bonded 2D-sheets, which were further assembled into 3D-layers by involving edge-on Cl-π interactions. The respective average particle sizes determined by dynamic light scattering of the respective lithium complexes were 648.3 nm and 588.8 nm. The average particle size of the tri-aquated complex dissolved in water was decreased upon addition of dimethylformamide. The cesium coordination polymer [Cs(DFA)(μ-H 2 O) 2 ] n had two-dimensional sheets formed through dative bonds. The hydrophobic parts of the sheets were projecting outward and two alternative sheets were inter-linked by edge-on chlorine-π interactions (3.391 Å) to provide 3-D supramolecular layered structure. One dimensional barium coordination polymer [Ba(DFA) 2 (H 2 O) 4 ] n and a cadmium coordination polymer [{Cd(DMF) 4 }2+{Cd(DFA) 4 }2− ] n having linear-chain structure were reported. The linear chain of the cadmium coordination polymer was comprised of the coordinatively linked assembly of complex cation [Cd(DMF) 4 ]2+ with anion [Cd(DFA) 4 ]2− located at alternative positions by side-on carboxylate bridges. [ABSTRACT FROM AUTHOR]

Six new organotin(IV) carboxylates have been synthesized and characterized. The molecular structures show the formation of mononuclear, dinuclear and tetranuclear compounds. All compounds showed significant antibacterial activities against E. coli XL-1 Blue cells. [Display omitted] • Six new organotin(IV) carboxylates have been synthesized. • All compounds were characterized by FT-IR spectroscopy, elemental analysis, 1H, 13C{1H} and 119Sn{1H} NMR spectroscopy. • The solid-state molecular structures of all compounds have been elucidated by single crystal X-ray diffraction analyses. • Compound 1 shows a ladder-type structure consisting of four tin centres. Compounds 2 – 3 and 5 – 6 are mononuclear and contain one tin atom in each compound. Interestingly, compound 4 exhibits a hydroxide bridged dinuclear structure. • All compounds were evaluated for their antibacterial activities against E. coli XL-1 Blue cells. Six new imine-functionalized organotin(IV) carboxylates viz. {[(n -Bu) 2 Sn(L1)] 2 O]} 2 (1), [(t -Bu) 2 Sn(L1) 2 ] (2), [Ph 3 Sn(L1)] (3), [(t -Bu) 4 Sn 2 (OH) 2 (L2) 2 ] (4), [Ph 3 Sn(L2)] (5) and [(t -Bu) 2 Sn(L3) 2 ] (6) have been synthesized and characterized by FT-IR spectroscopy, elemental analysis, 1H, 13C{1H} and 119Sn{1H} NMR spectroscopy. The solid-state molecular structures of all compounds have been elucidated by single-crystal X-ray diffraction analyses. Compound 1 shows a ladder-type structure consisting of four tin atoms. Compounds 2 – 3 and 5 – 6 are mononuclear and contain only one tin atom in each compound. Interestingly, compound 4 exhibits a hydroxide-bridged dinuclear structure. All compounds were evaluated for their antibacterial activities against E. coli XL-1 Blue cells, and compound 1 showed maximum activity amongst all compounds. [ABSTRACT FROM AUTHOR]

Synthesis and characterization of supramolecular self-assembly dicopper carboxylates metallogels. Metallogelations triggered by pi-pin stacking, hydrogen bonding and non-cavalent interactions. Catecholase activity of the newly synthesized metallogels was explored. [Display omitted] • Synthesis and characterization of supramolecular self-assembly dicopper(II) carboxylates metallogels. • The structure of the bimetallic metallogel was established by single crystal X-ray crystallography. • Catecholase activity of the newly synthesized metallogels was explored. • The reaction follows the Michaelis-Menten enzymatic reaction kinetics, K cat value for this reaction is 165 h−1. A new bimetallic metallogel was synthesized and characterized by various spectroscopic techniques. The morphology of BMG has been explained with the help of scanning electron microscopy. The rheological investigation helps to examine the supramolecular BMG metallogel. It was found that the G′ value was significantly larger compare to G′′ value, which confirmed the gel nature of the material. Single X-ray diffraction studies verified the existence of pi-pi stacking, non-covalent interactions, and other short molecule interactions necessary for the formation of metallogel. Furthermore, copper-based metallogel BMG can be utilized as a catalyst for aerobic oxidation of 3,5-di- tert -butylcatechol (3,5-DTBC) to 3,5-di- tert -butyl benzoquinone (3,5-DTBQ). The kinetic parameters were obtained by plotting rate vs. substrate concentration of BMG based on Michaelis–Menten approach of enzymatic kinetics. To the best of our knowledge, only few metallogel materials were reported for bioinspired catalysis like catechol oxidation. [ABSTRACT FROM AUTHOR]

[Display omitted] • 13C NMR chemical shifts are very important in identifying the chemical surroundings of carbon nuclei in a molecule. • The electronic and steric environment of the ligand has a significant impact on the chemical shift of the carbonyl carbon (C O) in the carboxylate ligand. • The type of the ligand and the degree of its interaction with the tin atom may be determined from the chemical shift of the carbonyl carbon in a carboxylate ligand. • The intensity of the connection between the tin atom and the carboxylate ligand may be determined for butyltin carboxylates by measuring the coupling constant between the carbonyl carbon and the nearby carbon atoms in the ligand. This review article describes the findings of research on the 13C NMR spectra of di- and tri-butyltin carboxylates. The purpose of this review is to shed light on the experimental values of 13C NMR chemical shifts, as well as their importance in identifying the chemical surroundings of carbon nuclei. The study aims to gain a deeper understanding of how carbon nuclei interact with their electronic surroundings and how substituents attached can influence these interactions. The information presented in this review highlights the crucial role played by 13C NMR chemical shifts in establishing the structure of carbon frameworks, making it an indispensable tool for the structure elucidation. [ABSTRACT FROM AUTHOR]

Application of two new Cd(II)-based coordination polymers as dual sensor for sulfamethazine antibiotic and ferric ion. [Display omitted] • Two Cd(II) based coordination polymers (CPs) derived from 1,1′-biphenyl-2,3,3′,5′-tetracarboxylic acid (H 4 L) as the main ligand. • 2,2′-bipyridyl and 1,10-phenanthroline (phen) as co-ligands have also been used. • These CPs have been physico-chemically characterized. • Both CPs used as luminescent sensor for sensitive and selective detection of sulfamethazine antibiotic. • Additionally, these CPs also displayed selective sensing for Fe3+ ions. The precise combination of basic functionality and luminescence property can deliver multifunctional coordination polymers (CPs) with multifarious applications such as sensitive and selective detection of antibiotics and metal ions sensing. Herein, two new Cd(II)-based CPs having formula [Cd 2 (L)(bpy) 2 (H 2 O) 2 ·4H 2 O] (1) and [Cd 2 (L)(phen)(H 2 O)] (2) have been synthesized and characterized using mixed ligand strategy by solvothermal reaction of Cd(II) salts using 1,1′-biphenyl-2,3,3′,5′-tetracarboxylic acid (H 4 L) as the main ligand and 2,2′-bipyridyl (bpy) as co-ligand for CP 1 and 1,10-phenanthroline (phen) as co-ligand for CP 2. The CP 1 possesses (4,4)-connected sql topology, while CP 2 displays 2D bilayer network composed of ring-like Cd 2 (OCO) 6 subunits. The sensing studies indicated that both 1 and 2 can behave as luminescent sensor for sensitive and selective detection of sulfamethazine antibiotic with remarkable quenching and low limit of detection. Additionally, both CPs also displayed selective sensing for Fe3+ ions. The possible alleviation in the luminescence intensities of 1 and 2 in presence of antibiotic have been addressed using theoretical calculations which indicated that charge transfer as well as the weak interaction between antibiotic and CP may be responsible for the decline in the emission intensity. [ABSTRACT FROM AUTHOR]

A new 3D MOF was synthesized and characterized and its photocatalytic properties to photo-degrade the methyl violet were explored. • Title MOF shows 3D framework with a rare (4,6,6)-connected topology. • The materials display good photocatalytic property. • The plausible mechanism of the photocatalytic activities have been proposed. A new metal-organic framework of [Mn 4 (L) 2 (4,4′-bipy) 2 (H 2 O) 4 ]·(H 2 O)(4,4′-bipy)] (1) has been synthesized using a symmetrical tetracarboxylate 5-[bis(4-carboxybenzyl)-amino]isophthalic acid (H 4 L) and 4,4′-bipyridine (4,4′-bipy) coligands. The single crystal X-ray diffraction study indicates that in 1 , the Mn(II) centers are bridged by L4− and 4,4′-bipy ligands to furnish a 3D framework with a rare (4,6,6)-connected (4.53.62) 2 (42.54.66.72.8}{57.66.82} topology. 1 exhibits related lower photocatalytic activity for degradation of organic dye methyl violet (MV) under UV light and offers good stability after performing photocatalysis. A mechanism for the photcatalytic property of MOF is proposed, which is based on the results of density of states (DOS) and partial DOS calculations. [ABSTRACT FROM AUTHOR]

Graphical abstract The reaction CdCl 2 ·2.5H 2 O with pivalic acid in presence of aq. NaOH at RT afforded a discrete complex 1 while the reaction of Cd(OAc) 2 ·2H 2 O with pivalic acid under the aforementioned condition afforded a novel trinuclear heterobimetallic 1D-CP, 2. Highlights • A discrete mononuclear complex 1 and a trinuclear heterobimetallic 1D-CP 2 were isolated. • The composition of 1 and 2 was verified by analytical, thermal, spectroscopic studies and X-ray diffraction. • Complexes 1 and 2 represent the first of their kinds to be structurally characterised. Abstract The reaction of CdCl 2 ·2.5H 2 O with two equiv of aq. NaOH followed by treatment of the resulting solution with two equiv of pivalic acid gave [Cd(κ2-OC(O) t Bu) 2 (H 2 O) 2 ] (1) in 83% yield while the aforementioned reaction with Cd(OAc) 2 ·2H 2 O as Cd2+ source afforded a trinuclear heterobimetallic 1D-CP, {Na 2 [Cd(μ 5 -κ3:κ3-OAc)(μ 3 -κ2:κ3-OC(O) t Bu)(μ 3 -κ1:κ2-OC(O) t Bu) 2 ]·2 t BuC(O)OH} ∞ (2) in 90% yield. Complexes 1 and 2 were characterized by elemental analyses, IR spectroscopy, solution 1H and 13C {1H} NMR spectroscopy and solid state CP-MAS 13C{1H} NMR spectroscopy, TG-DTA analyses and single crystal X-ray diffraction. The phase purity of 2 was also verified by powder X-ray diffraction. Complex 1 represents the first structurally characterised discrete mononuclear cadmium(II) carboxylate complex which is known to contain a pair of chelating carboxylate ligand, while 2 represents the first structurally characterized trinuclear heterobimetallic 1D-CP formed through aggregation via covalent coordinate bond. [ABSTRACT FROM AUTHOR]

Graphical abstract Highlights • Two new Ln(III) complexes have been synthesized. • Two Ln(III) complexes are characterized by single crystal X-ray diffraction. • Compounds 1 – 2 are dinuclear and contain [Ln 2 (μ 2 -O 2 CFc) 4 ] cores. Abstract Two new lanthanum complexes, [La 2 (μ 2 -OOCFc) 4 (DTBbpy) 2 (NO 3) 2 ] (1 ·2CH 3 CN) and [La 2 (μ 2 -OOCFc) 4 (μ-HOOCFc) 2 (DTBbpy) 2 (HOCH 3) 2 ](ClO 4) 2 (2 ·2CH 3 OH); (Fc = ferrocene and DTBbpy = 4, 4′-di-tert butyl bipyridyl) were prepared and characterized by single crystal X-ray diffraction. The reaction of sodium ferrocene carboxylate (FcCOONa) with La(NO 3)·6H 2 O (1:1) in methanol at 80 °C followed by the addition of 4, 4′-di-tert-butyl bipyridyl (DTBbpy) resulted in the formation of (1). The use of La(ClO 4) 3 ·6H 2 O as a precursor under identical synthetic condition yielded (2). In 1 and 2 , the La atoms are bridged by four FcCOO- ligands forming the [La 2 (μ 2 -OOCFc) 4 ] core (La...La = 4.0357(4) Å in 1 and 4.3789(3) Å in 2). The coordination number of the La atoms is 9 for 1 and 8 for 2. [ABSTRACT FROM AUTHOR]

Graphical abstract Highlights • Hpytzipa and H 4 dtzpda were synthesized. • Zn(II) compounds based on them were prepared. • The NPs of the two compounds show cytotoxicity towards HeLa cells. Abstract Two new coordination compounds, [Zn(pytzipa) 2 (H 2 O) 4 ]·2H 2 O (1) and [Zn 2 (dtzpda)(H 2 O) 5 ]·3H 2 O (2) have been synthesized by solvothermal reactions of Zn(NO 3) 2 ·6H 2 O with Hpytzipa or H 4 dtzpda, respectively (Hpytzipa = 5-(3-pyridyl)tetrazole-2-isoproponaic acid, H 4 dtzpda = 3,3-di(1 H -tetrazol-5-yl)pentanedioic acid). The X-ray diffraction results reveal that compound 1 is a linear chain in which pytzipa acts as a bidentate ligand to bridge adjacent Zn2+ ions by the nitrogen atom of the pyridine ring and the oxygen atom of the carboxylate group. In compound 2 , dtzpda4− acts as a hepta-dentate ligand to bridge adjacent Zn2+ ions by the nitrogen atoms of the tetrazole rings and the oxygen atoms of the carboxylate in a chelating mode. Furthermore, nanoparticles (NPs) of the two compounds were prepared by co-precipitation with PEG -5000 (poly(ethyleneglycol -5000)). Both two NPs show considerable cytotoxicity towards HeLa cells but Hpytzipa and H 4 dtzpda are non-toxic in nature. The results show that coordination Zn(II) with Hpytzipa or H 4 dtzpda can improve the toxicity of the NPs significantly and the NPs of the compounds are potential candidates for treatment of cancer cells. [ABSTRACT FROM AUTHOR]

Graphical abstract Hydrothermal reaction of cadmium nitrate, 2,5-thiophenedicarboxylic acid and highly conformationally flexible dipyridylamide ligands resulted in a series of nitrobenzene-detecting coordination polymers with 1D chain, 2D layer, and 3D self-penetrated topologies. Highlights • Cadmium coordination polymers with rigid 2,5-thiophenedicarboxylate ligand. • Five different highly conformationally flexible dipyridylamide coligands. • 1D chain, 2D layer, and 3D self-penetrated topologies were observed. • All materials act as "turn-off" sensors for the detection of nitrobenzene. Abstract Hydrothermal reaction of cadmium nitrate, 2,5-thiophenedicarboxylic acid (H 2 tdc) and one of the conformationally flexible dipyridylamide ligands N , N ′-(heptane-1,7-diyl)dinicotinamide (hedn), N , N ′-(hexane-1,6-diyl)diisonicotinamide (hdin), N , N ′-(hexane-1,6-diyl)dinicotinamide (hdn), N , N ′-(propane-1,3-diyl)dinicotinamide (pdn), N , N ′-(propane-1,3-diyl)diisonicotinamide (pdin) produced five new coordination polymers which were structurally characterized by single-crystal X-ray diffraction. {[Cd(tdc)(hedn)(H 2 O)]·3H 2 O} n (1) manifests looped (4,4) grid motifs with two-fold parallel interpenetration. {[Cd(tdc)(hdin)(H 2 O)]·H 2 O} n (2) shows stacked (4,4) grid motifs. {[Cd 2 (tdc) 2 (hdn)(H 2 O) 4 ]·H 2 O} n (3) exhibits herringbone (6,3) grid motifs. In contrast to the 2D topologies seen in 1 – 3 , {[Cd 2 (tdc) 2 (pdn)(H 2 O) 2 ]·4H 2 O} n (4) displays a 3D self-penetrated net with 6482 nbo topology and [Cd(tdc)(pdin)] n (5) shows a 1D ribbon structure constructed from staple-conformation pdin ligands and {Cd 2 O 2 } dimer-containing [Cd(tdc)] n chains. Thermal decomposition and nitrobenzene detection properties of these five new materials are discussed. [ABSTRACT FROM AUTHOR]

Graphical abstract Ternary metal-NSAID prodrugs: M(II)-diclofenac (M = Fe, Co, Zn) complexes of tris(2-pyridylmethyl)amine display "two-in-one activity" by exhibiting anti-proliferative and anti-inflammatory activities. Highlights • Three M(II)-diclofenac complexes (M = Fe, Co and Zn) of a tripodal nitrogen ligand were isolated. • The Zn(II) complex revealed a five-coordinate metal center with monodentate diclofenac. • All the complexes are stable in solution under cell culture conditions. • The complexes exhibit both anti-proliferative and anti-inflammatory activities. Abstract To develop metallodrugs exhibiting anti-proliferative and anti-inflammatory activities, anti-proliferative supporting ligand and co-ligand NSAID were combined in ternary metal complexes. Three ternary complexes with the general formula [(TPA)MII(diclofenac)]+ (TPA = tris(2-pyridylmethyl)amine, M = iron, cobalt and zinc) have been isolated and characterized. The crystal structure of the zinc(II)-diclofenac complex reveals a five-coordinate metal center, in which diclofenac coordinates in monodentate mode through one carboxylate oxygen. The iron(II) and zinc(II) complexes exhibit anti-proliferative effect on MDA-MB-231 human breast cancer cells with the IC 50 value of 9.45 μM and 9.00 μM, respectively. On the contrary, the cobalt(II) complex shows less cytotoxicity due to its tendency toward oxidative degradation under aerobic conditions. The complexes display anti-inflammatory activity through inhibition of COX-pathways. [ABSTRACT FROM AUTHOR]

Graphical abstracts Calixarenes and coordination polymers: a promising union for future MOFs. Abstract 25,27-bis(methoxycarboxylic acid)-26,28-dihydroxycalix[4]arene (calixH2), so call here calix[4]arene dimethoxycarboxylic acid, was investigated for its ability to build metal–organic frameworks. When reacted with zinc or manganese chloride in DMF and deprotonated with trimethylamine it gives Zn (1) and Mn (2) coordination compounds. These crystallize in the triclinic P -1 space group and are isostructural as shown by X-ray diffraction on single crystals. The crystal structures evidence the coordination of calix[4]arenedimethoxycarboxylic acid through the carboxylate groups. This makes a 1D coordination polymer running along the c axis direction in which [MII 2 (calix) 2 (H 2 O) 3 (DMF) 2 ] (M = Zn or Mn) neutral units are connected. Last step refinements of the crystal structure reveal a lot of residual electron density which was ascribed to uncoordinated disordered water and DMF molecules. This was treated with the SQUEEZE routine of the program PLATON from which the solvent accessible voids per unit cell volume was calculated to be 24.5% for compound 1 (Zn) and 24.9% for compound 2 (Mn). Complementary differential thermal analyses (DTA) combined with thermogravimety analysis (TGA) and mass spectrometry (MS) are in agreement with large amount of incorporated and non-coordinated water and DMF molecules. Adsorption isotherms of N 2 measured for compound 1 do not show any significant porosity. The temperature dependence of the magnetic susceptibility (χ) of compound 2 evidences antiferromagnetic interactions and was best fitted with a weak antiferromagnetic exchange coupling between the manganese(II) ions J = − 1.5 cm−1 and small antiferromagnetic inter-dinuclear interactions zJ = − 1.2 cm−1 (g = 2.02). [ABSTRACT FROM AUTHOR]

Graphical abstract Critical role of carboxylate bridging was examined for carboxylate coordination assisted aggregation in [Cu 4 (µ 4 –O)(µ–L1) 2 (µ 1,3 –O 2 CCH 3) 4 ]·H 2 O (2a) and [Cu 4 (µ 4 –O)(µ–L1) 2 (µ 1,3 –O 2 CC 2 H 5) 4 ]·H 2 O (2b) avoiding ligand imine arm hydrolysis. Highlights • New ligand HL1 has been examined for synthesis of CuII coordination aggregates. • Use of carboxylates give rise to µ 4 –oxido bridged [Cu 4 ] complexes 2a and 2b. • Partial ligand arm hydrolysis observed in absence of any carboxylates. • The Cu 2 based building blocks present in MeOH solution showed catecholase activity. • DNA binding ability of the synthesized complexes was checked. Abstract The dinuclear copper(II) complex [Cu 2 (µ–L2NH) 2 (OH 2) 2 ](ClO 4) 4 (1) was obtained following one imine side arm hydrolysis of HL1 (2,6-bis-[{3-(diethylamino)propylimino}methyl]-4-methylphenol). Introduction of carboxylates inhibited the hydrolysis and resulted in two tetranuclear copper(II) complexes [Cu 4 (µ 4 –O)(µ–L1) 2 (µ 1,3 –O 2 CCH 3) 4 ]·H 2 O (2a) and [Cu 4 (µ 4 –O)(µ–L1) 2 (µ 1,3 –O 2 CC 2 H 5) 4 ]·H 2 O (2b). Use of perchlorate and carboxylate salts of copper(II) for the reactions under study with HL1 has directed these reactions. Perchlorate anions in presence of H 2 O molecules, as hydrolytic nucleophiles, triggered imine arm hydrolysis and bridging carboxylate anions allowed transformation of copper(II) bound H 2 O molecule to μ 4 -oxido central nucleating group via hydroxido-bridge. The complexes were obtained from simultaneous chelation and bridging by the hydrolyzed and as used ligand anions L2NH− and HL1− respectively. These complexes have been characterized in the solid state by X-ray crystallography and FT-IR spectroscopy. Solution phase stability of Cu 2 -based fragments was studied by UV–vis absorption spectroscopy. Solution properties have been examined for substrate binding in catechol oxidase activity and binding affinity for biomacromolecules like DNA and Human Serum Albumin. [ABSTRACT FROM AUTHOR]

Graphical abstract Carboxylate-bridged Mn(II) magnetic chains are linked into 3D networks with different structures; the carboxylate bridges and µ 2 -O carboxylate bridges all mediate antiferromagnetic couplings. Highlights • Four 3D Mn(II) coordination polymers have been synthesized by the solvothermal reaction. • They contain diverse carboxylate-bridged magnetic chain. • Carboxylate bridges mediate antiferromagnetic coupling between Mn(II) ions. Abstract Four new three-dimensional Mn(II) coordination polymers with two isomeric ligands, 5-(3-nitro-4-carboxylphenyl)isophthalic acid (H 3 L 1) and 5-(2-nitro-4-carboxylphenyl)isophthalic acid (H 3 L 2), have been prepared and structurally and magnetically characterized. They are of the formula [Mn(HL 1)(CH 3 CN)] (1), [Mn(L 2)]·H 2 O·H 3 O (2), [Mn 3 (L 2) 2 (DMF) 2 ]·H 2 O (3), [Mn 4 (HL 2) 4 (H 2 O) 5 ]·2H 2 O (4). Compounds 1 – 3 contain diverse alternating magnetic chain's sequences in which the chains are linked by the organic spacers into 3D structures. In 1 , the two double [(μ-O carboxylate) 2 and (μ- syn - anti -COO) 2 ] bridges with apparently different structural parameters alternate in the − ABAB − sequence. While in 2 , the two sets of double μ- syn - anti -carboxylate bridges with slightly different structural parameters also alternate in the -ABAB- sequence. In 3 , the double (μ- syn - anti -COO) 2 bridges and (μ-O DMF)(μ- syn - anti -COO)(μ 3 -COO) triple bridges alternate in the -ABB- sequence. Compound 4 contains two sets of independent motifs: one is 1D chain based on three different double (μ- syn - anti -COO) 2 bridges alternate in the -ABC- sequences; the other is 1D tape-like motifs with three different single μ- syn - anti -COO bridges. Two sets of motifs in 4 are alternately linked together by the organic backbones into a complicated 3D structure. Compounds 1 , 2 and 4 exhibit weak antiferromagnetic couplings. A magnetostructural survey indicates that the antiferromagnetic coupling through the (μ- syn - anti -COO) 2 bridges decreases as the Mn⋯Mn distances increases and the magnitude of antiferromagnetic coupling mainly depends on the Mn O Mn angle for the double (μ 2 -O carboxylate) 2 bridges. [ABSTRACT FROM AUTHOR]

Graphical abstract Highlights • The reaction between Cu(pic) 2 ·6H 2 O (pic = picrate anion) and tryptophan (trp) in aqueous solution. • Mononuclear Cu(II) complex Cu(l -trp) 2 (H 2 O) 4 ](pic) 2 ·4H 2 O. • An unusual tryptophan coordination to Cu(II) via carboxylate monodentate binding in trans -fashion. Abstract Herein, we report the synthesis, spectroscopy, crystal structure and theoretical studies of a new Cu(II) complex with formula [Cu(l -trp) 2 (H 2 O) 4 ](pic) 2 ·4H 2 O (1), which exhibits an unusual tryptophan coordination to copper(II) via carboxylate monodentate binding. The complex has been prepared using the mixed ligand approach. Single crystal X-ray diffraction structural analysis of 1 revealed that, in the complex, the Cu(II) site shows a distorted octahedral geometry, and the tryptophan (trp) ligand is coordinated through the carboxylate group in a monodentate fashion. The picric acid (pic) co-ligand, which is present in the anionic form, resides outside the coordination sphere forming a charge-separated complex. Density Functional Theory (DFT; including time-dependent DFT) has been employed to calculate the equilibrium geometry of the complex as isolated species in dimethylsulfoxide (DMSO) solution, and also its electronic spectrum, which was used to understand details of the experimentally obtained ultraviolet-visible (UV-Vis) spectrum. The structural analysis was complemented by additional spectroscopic studies [infrared (IR) and electron paramagnetic resonance (EPR) spectroscopies], and the thermal stability of the complex evaluated by thermogravimetric analysis (TGA). [ABSTRACT FROM AUTHOR]

Graphical abstract Highlights • Synthesis and structure of [AgO 2 CCR 2 OC(O)OMe] and [AgO 2 CCR 2 OC(O)OMe(PPh 3) 2 ] • The thermal decomposition of these complexes is studied by TG, DSC, TG–MS. • Their use for Cu joining is reported. Abstract The synthesis of [AgO 2 CCR 2 OC(O)OMe] (6 , R = H; 7 , R = Me) by treatment of HO 2 CCR 2 OC(O)OMe (4 , R = H; 5 , R = Me) with [AgNO 3 ] in presence of NEt 3 is reported. The reaction of 6 and 7 with 2 equiv of PPh 3 gave [AgO 2 CCR 2 OC(O)OMe(PPh 3) 2 ] (8 , R = H; 9 , R = Me). The thermal behavior of 6 and 7 was studied by TG, DSC and TG-MS of which the latter evinced decarboxylation as initial decomposition step followed by Ag C, C C and C O bond cleavages giving silver. For copper-to-copper joining, 6 and 7 were processed to spreadable pastes by mixing them with ethylene glycol (EG) or diethylene glycol (DEG). On contact of 7 -EG with Cu sheets [Cu 2 (O 2 CCMe 2 OC(O)OMe) 4 ·2H 2 O] (12) was formed. Therefore, only 6 -EG and 6 -DEG were used for pressureless joining of Cu at 250 °C. Thru addition of Ag µm-particles a tensile shear strength of 19 MPa was achieved, showing a significant higher value as received with commercially Ag nanopastes. The solid state structure of 5 , 8 , 9 and 12 was determined by single crystal X-ray structure analysis, showing [3+1] (P 2 O + O) (8), distorted tetrahedral (9) or octahedral (12) coordination spheres at the metal ion. [ABSTRACT FROM AUTHOR]

Graphical abstract Abstract The mixed-ligand binuclear complexes [Co 2 (BIBP)(2,6-PDC) 2 (H 2 O) 4 ] (1), [Ni 2 (BIBP)(2,6-PDC) 2 (H 2 O) 4 ] (2), and the coordination polymers 1D-{[Zn(BIBP)(2,6-PDC)]·4.5H 2 O} n (3), 2D-[Ni 2 (BIBP)(2,5-PDC) 2 (H 2 O) 4 ] n (4), and 3D-{[Ni 2 (BIBP) 3 (2,3-PDC) 2 ]·3.75H 2 O} n (5) were synthesized in good yields, characterized by IR, thermogravimetry and single X-ray diffraction method (BIBP = 4,4′-bis(1-imidazolyl)biphenyl, 2,6-PDC = 2,6-pyridinedicarboxylate, 2,3-PDC = 2,3-pyridinedicarboxylate, 2,5-PDC = 2,5-pyridinedicarboxylate). Compounds 1 and 2 are binuclear complexes, compound 3 is a 1D polymer, 4 has a 2D laminated structure, and 5 represent a 3D framework. A common motif in the structures, independent of their dimensionality is the bridging action of the neutral BIBP ligand between two metal ions and a metal chelating coordination of the dianionic PDC ligand through the pyridine nitrogen atom and the carboxylate group in 2-position. The comparative single crystal X-ray structure investigations reveal the fine-tuning influence of the carboxylic group positions in the pyridinedicarboxylate (PDC) ligands and the metal nature on the final structure topology and dimensionality. Compounds 1 and 2 are isostructural and represent Co(II) and Ni(II) isomorphs, where the metal ions coordinate two water molecules and the 2,6-PDC ligand in ONO chelate mode, while the bidentate BIBP ligand link the metal ions into a dinuclear complex. In 3 the 2,6-PDC ligand coordinates to the zinc atom in the same ONO chelate mode and two bridging BIBP ligands give a coordination number of five and extend the structure to a 1D polymer with an enantiopure triple-stranded helix motif in a case of spontaneous resolution in the chiral tetragonal space group P 4 3 22. In 4 the 2,5-PDC ligand realises its chelate-bridging function and together with the bridging BIBP ligand form 2D layers with the Ni(II) atoms with hcb (honeycomb or 6,3) topology. In 5 the chelate-bridging 2,3-PDC and BIBP ligands form (4,4)-layers which are interlinked by additional BIBP pillars to a 3D network with two-fold interpenetration of symmetry-related networks. [ABSTRACT FROM AUTHOR]

Graphical abstract Morphologies of Cu 3 (BTC) 2 (H2O) 3 ·10H 2 O (1) and Cu 2 (OH)(BTC)(H 2 O)·2H 2 O (2) compound. Highlights • 2 phases of CuBTC were synthesized by changing the one-pot synthesis method. • Both phases have different characteristic and adsorption capacity against MB dye. • The SEM images of [Cu 2 (OH)(BTC)(H 2 O)] n ·2 n H 2 O (2) that never been reported. Abstract Synthesis of metal organic framework (MOF), copper benzene-1,3,5-tricarboxylate was carried out at room temperature using water as solvent. Experimental results show that microporous Cu 3 (BTC) 2 (H 2 O) 3 ·10H 2 O (1) or Cu 2 (OH)(BTC)(H 2 O)·2H 2 O (2) (BTC = benzene-1,3,5-tricarboxylate) were formed depending on the rate of formation of MOF’s in similar synthesis systems. The octahedral shape Cu 3 (BTC) 2 (H 2 O) 3 ·10H 2 O (1) was formed when the crystallization occurred slowly while Cu 2 (OH)(BTC)(H 2 O)·2H 2 O (2) which was produced when the crystallization occurred quickly has an extended rod shape feature. The samples were characterised under infrared spectroscopy, powder X-ray diffraction, scanning electron microscopy, thermogravimetric analysis and N 2 adsorption desorption using the BET method. The Cu 3 (BTC) 2 (H 2 O) 3 ·10H 2 O (1) shows a greater characteristic in terms of crystallinity, specific surface area, specific pore volume and adsorption capacity against methylene blue (MB) dye compared to Cu 2 (OH)(BTC)(H 2 O)·2H 2 O (2). [ABSTRACT FROM AUTHOR]

Graphical abstract Four complexes based on two tetracarboxylate-functionalized resorcin[4]arenes have been synthesized. The luminescence sensing abilities of 1 – 3 for detecting nitrobenzene and Cr 2 O 7 2− were also investigated. Highlights • Four complexes base on two novel resorcin[4]arenes have been synthesized. • 1 – 3 could be applied as fluorescence sensors for nitrobenzene and Cr 2 O 7 2− anion. • 2 and 3 exhibit similar high sensitivity on detecting Cr 2 O 7 2− anion. Abstract Four new coordination complexes, namely, [NH 2 (CH 3) 2 ] 2 [Cd(L1)(DMF) 2 ] (1), [Zn(L1) 0.5 (phen)]·H 2 O (2), [Zn 2 (L2)(Phen) 2 (H 2 O) 2 ] (3) and [NH 2 (CH 3) 2 ][Zn 2 (L1)(Cl)(DMF)(H 2 O)]·2H 2 O (4) have been synthesized (H 4 L1 = 2,8,14,20-tetra-phenyl-4,12,16,24-tetra-oxyallylene-6,10,18,22-tetra-carboxymethoxy-resorcin[4]arene, H 4 L2 = 2,8,14,20-tetra-ethyl-6,12,18,24-tetra-oxyallylene-4,10,16, 22-carboxymethoxy-resorcin[4]arene and phen = 1,10-phenathroline). Complex 1 shows an infinite chain. Complexes 2 and 3 exhibit similar ribbon structures. The ribbons in 2 are extended by C-H⋯ π interactions to create a supramolecular layer. While in 3 , the ribbons are further connected via H-bonds and π - π interactions to yield a supramolecular double-layer. Complex 4 reveals a 3D framework with 4-connected (4284) 2 (427282) 2 topology. Solid state luminescent properties for all complexes were investigated. The temperature dependence fluorescence of 2 and 3 were studied. Luminescence sensing abilities of 1 – 3 for detected nitrobenzene and Cr 2 O 7 2− in aqueous were also investigated. [ABSTRACT FROM AUTHOR]

Graphical abstract Highlights • Hydrothermal synthesis of new MOF, [Co(2,5-Pydc)(H 2 O) 2 ].H 2 O. • Co2+ attains distorted octahedral geometry with 2,5-Pydc and H 2 O. • Versatile supramolecular 3D architecture is developed. • Unsaturated metal centres of Co2+ upon activation acted as Lewis acidic sites. • Worthy catalyst for contemporary organic synthesis. Abstract A cobalt based MOF, [Co(2,5-Pydc)(H 2 O) 2 ].H 2 O (CoPy) was hydrothermally synthesized by employing 2,5-Pyridinedicarboxylic acid (2,5-Pydc) as organic strut; and its characteristics were characterized by single crystal XRD, FT-IR, TGA and fluorescent measurements. The single crystal XRD studies reveals that the compound crystallized in orthorhombic crystal system of space group P212121 with lattice parameters a = 7.3253(1) Å b = 9.3906(1) Å c = 13.8054(2) Å. In CoPy , the central metal atom (Co2+) adopts a six coordination geometry by using the carboxylate oxygen atoms and nitrogen atom of pyridine ring of 2,5-Pydc. The compound is linked with 2,5-Pydc ligand in all three directions through hydrogen bonding and π-π stacking interactions, which further develops a supramolecular 3-dimensional assembled network. The CoPy exhibited impressive catalytic activity in the synthesis of seven tetrahydrobiphenylene-1,3-dicarbonitrile derivatives via an one-pot, three-component reaction between aromatic aldehyde, malononitrile and 3-methyl-cyclohexanon in ethanol giving excellent yields (91–96%) in 20-35 min reaction time. The Lewis acidic sites of CoPy, by Co2+ open metal sites probably ensure its catalytic performance. The eco-friendly protocol and recyclability of CoPy, with no noticeable leaching of metal ion, undoubtedly makes it an ideal catalyst. [ABSTRACT FROM AUTHOR]

Two isostructural lanthanide-based metal - organic frameworks, {[Ln(C 16 H 12 N 2 O 4 )(CHO 2 )(OH 2 )·2(C 5 H 11 NO)]} n , Ln = Yb ( 1 ) and Tm ( 2 ), and a cadmium(II) coordination polymer,{[Cd 2 (C 16 H 12 N 2 O 4 )(NO 3 )·4(C 3 H 7 NO)]} n, were synthesized by the combination of the respective metal nitrate and 2,2′-diamino- trans 4,4′-stilbenedicarboxylate (C 16 H 12 N 2 O 4 ) under solvothermal conditions [C 5 H 11 NO = diethylformamide and C 3 H 7 NO = dimethylformamide]. Their structures were determined by X-ray single crystal analysis, X-ray powder diffraction, Fourier transformed infrared spectroscopy, elemental analysis, thermogravimetric analysis and solid state photoluminescence spectroscopy. Both lanthanide structures are infinite three-dimensional non-penetrating networks with extremely large diamond shape accessible channels of cross-sectional dimensions [30 Å x 12 Å] and with the amino-functional groups projecting into the channels. The cadmium-based structure is a one-dimensional coordination polymer with both the carboxylate and the amino groups coordinating the cadmium atoms, which resulted in a large increase in the rigidity of the ligand. Ligand-based fluorescence was exhibited by all three networks, with the cadmium based structure showing the highest intensity and longest fluorescence radiative lifetime. [ABSTRACT FROM AUTHOR]

Anti-microbial effect is produced when the ligand (L) S-ethyl- l -cysteine sulfoxide (Ethiin) makes coordination complex with metal ‘M’ (M = Cu, Co, Ni), while, ethiin did not show any antimicrobial effect. The synthesized complexes have 1:2 metal to ligand ratio (ML 2 ). The spectro-chemical analysis revealed that the ligand coordinates with the metals through oxygens of the carboxylate and sulfoxide groups resulting in octahedral geometry around the central metal atom. Techniques like 1 H NMR, thermal analysis, mass spectrometry, UV-Vis spectroscopy, XAFS, FTIR, EPR and magnetic moments were used to elucidate the structure of the ligand and the metal complexes. The expected reasons for the creation of anti-microbial effect are, either the disturbance of the ionic environment within the microbial cytoplasm when the complex enters into it or interaction of the complex with the DNA. [ABSTRACT FROM AUTHOR]

In order to investigate the new drug candidates for healthy and risk free treatment of parasitic diseases like leishmaniasis, a series of new bioactive pentavalent antimonials ( LS-1 to LS-8 ) of the type [SbR 3 (OOCR′) 2 ] (R =  C 6 H 5 , (C 6 H 4 )CH 3 and R′ =  (C 6 H 4 )NO 2 , (C 6 H 4 )Br, CH(C 6 H 5 ) 2 , CH 2 CH(C 3 H 7 )NHSO 2 C 6 H 5 ) were synthesized. All the antimonials have been characterized using melting points, elemental analysis, and multinuclear ( 1 H and 13 C) NMR spectroscopy. In addition two compounds ( LS-3 and LS-5 ) were also studied by X-ray crystallography and showed trigonal–bipyramidal geometry around antimony. The leishmanicidal activity was assessed against the Leishmania tropica promastigote parasite. It was observed that IC 50 of the antimonials was many fold superior as compared with the standard antimonial drug used. Antibacterial assay along with docking study proved that the synthesized compounds are highly effective against various human pathogens. [ABSTRACT FROM AUTHOR]

Two new zinc(II) complexes [Zn 2 (ac) 3 (hmt) 2 (OH)]·H 2 O ( 1 ) and [{Zn 5 (Obz) 8 (H 2 O) 2 (μ 3 -OH) 2 }(μ 2 -hmt){Zn 2 (Obz) 4 }·6H 2 O] n ( 2 ) have been synthesized using two different carboxylate salts (acetate (ac) for 1 and benzoate (Obz) for 2 ) and hexamethylenetetramine (hmt). Both the complexes have been structurally characterized by X-ray crystallography. Their identities have also been established by elemental analysis and IR spectral studies. Complex 1 is a dimer in which two zinc atoms contain equivalent four-coordinate tetrahedral environments. On the other hand, complex 2 is a 1D zig-zag coordination polymer containing alternative zinc pentamers and zinc dimers separated by bridging μ 2 -hmts. The centrosymmetric pentamer unit contains three independent zinc atoms, one being four-coordinate with a tetrahedral environment and other two being six-coordinate with octahedral geometries whereas the centrosymmetric dimer unit contains two five-coordinate Zn atoms with square pyramidal geometries. H-bonding interactions play a key role in stabilizing the observed structures. In complex 1 , the water molecule is held within the dimer and in 2 , a rare water hexamer is encapsulated in the supramolecular assembly by hydrogen bonds. The DFT calculations reveal that inter- and outer-cluster H-bond stabilization energies of water hexamer are −29.99 and −15.93 kcal/mol respectively. Lower stabilization energy from the ideal hexamer of chair conformer is attributed to the deformation of H-atoms as well as longer hydrogen bonded O⋯O distances. Additionally, the extra stability due to outer-cluster H-bonds is responsible for significant deformation from ideal chair conformer of hexamer cluster. [ABSTRACT FROM AUTHOR]

Three new 2D lanthanide-organic networks, {[Sm 2 ( µ 4 -cpta)( µ 5 -cpta)(H 2 O) 3 ]·3H 2 O} n ( 1 ) and [Ln( µ 3 -cpta)(phen)(H 2 O) 2 ] n (Ln = Tb ( 2 ) and Sm ( 3 )), were successfully synthesized via hydrothermal reactions using Ln(NO 3 ) 3 ·6H 2 O, a flexible ether-bridged tricarboxylic acid H 3 cpta (2-(2-carboxyphenoxy)terephthalic acid) as a principal building block, and phen (1,10-phenanthroline) as an optional supporting ligand. All products were obtained as air and thermally stable microcrystalline solids and fully characterized by standard solid-state techniques, including elemental analysis, TGA, IR spectroscopy, powder and single-crystal X-ray diffraction. Compound 1 possesses an intricate 2D layer structure with the 4,5L51 topology, which is driven by the µ 4 - and µ 5 -cpta 3− and Sm(III) nodes. Compounds 2 and 3 are isostructural and disclose a different 2D metal-organic network with the fes topology, which is assembled from the µ 3 -cpta 3− and Ln(III) nodes. Luminescence properties of 2 and derived M n + @ 2 suspensions were investigated, disclosing a possible use of this compound as a notable luminescence sensor for the detection of Fe 3+ cations in aqueous medium. [ABSTRACT FROM AUTHOR]

A series of isomorphous random bimetallic Ni II -Mn II compounds with N -methylpyridinium-4-carboxylate (4-mpc) and azide, have been synthesized and characterized. They are of formula [Ni II x Mn II 1−x (N 3 ) 2 (4-mpc)] ( 1 − 6 ), ( x = 1 ( 1 ), 0.86 ( 2 ), 0.83 ( 3 ), 0.71 ( 4 ), 0.56 ( 5 ), 0.47 ( 6 )). Compounds 1 – 6 consist of one-dimensional uniform chains with [( μ -EO-N 3 ) 2 ( μ -COO)] triple bridges (EO = end-on). Magnetic measurements reveal that compounds 1 – 6 behave as antiferromagnets with a gradual ferromagnetic-to-antiferromagnetic evolution by the incorporating of isotropic Mn II ions into Ni II chain. The Ni II -rich compounds 1 – 3 exhibit field-induced metamagnetism. And the T N of the heterometallic compounds exhibit a composition-dependence of the content of Ni II . [ABSTRACT FROM AUTHOR]

Three new polymeric tridimensional compounds with the composition [M 3 (seb) 3 (phen) 2 ] n , where M = Co(II), Ni(II) and Mn(II), seb = (OOC–C 8 H 16 –COO), phen = C 12 H 8 N 2 were synthetized and characterized by physical and physico-chemical methods. The X-ray study revealed that the compounds structure consist of trinuclear units joined through carboxylate groups of the sebacate ligand molecules. Magnetic succeptibility data showed antiferromagnetic interactions in the Mn3 and Ni3 cores and ferromagnetic behavior for Co3 moiety. [Display omitted] Three new polymeric tridimensional compounds with the composition [M 3 (seb) 3 (phen) 2 ] n , where M = Co(II), Ni(II) and Mn(II), seb = (OOC–C 8 H 16 –COO)2-, phen = C 12 H 8 N 2 were synthesized and characterized by physical and physico-chemical methods. The X-ray study revealed that the structures of all three coordination polymers consist of the trinuclear cores joined through sebacate dianions. The thermoanalytical study showed that coordination polymers are stable up to 250 °C and further heating results in the framework decomposition. Magnetic susceptibility data showed antiferromagnetic interactions in the Mn 3 and Ni 3 cores and ferromagnetic behavior for Co 3 moiety. [ABSTRACT FROM AUTHOR]

[Display omitted] • A series of Zn(II) and Cd(II) carboxylate complexes have been synthesized and characterized. • Free hydroxyl functional groups in the complexes facilitate intra- and inter-hydrogen bonding. • Bulky isopropyl groups and auxiliary ligands help in modulating nuclearity of complexes. Five dinuclear Zn and Cd carboxylate complexes, [Zn(L)(µ -L)(im)·2H 2 O] 2 (1), [Zn(L)(µ -L)(meim).MeOH] 2 (2), [Zn(L)(µ -L)(dmp)] 2 (3), [Cd(L)(µ -L)(im)·2H 2 O] 2 (4) and [Zn(L)(µ -L)(dmp)] 2 (5) (HL = 3,5-diisopropyl-4-hydroxybenzoic acid, im = imidazole, meim = N- methylimidazole, dmp = 3,5-dimethylpyrazole) have been synthesized by reacting M(OAc) 2 ·2H 2 O (M = Zn and Cd) with a disubstituted aromatic carboxylic acid and various five-membered aromatic cyclic amines in methanol at ambient temperature. All complexes have been characterized by elemental analysis and FT-IR, Mass, UV–Vis, fluorescence, 1H and 13C NMR spectroscopic methods. The molecular structures and bulk purity of the compounds have been established by single-crystal and powder X-ray diffraction studies. In these complexes, the carboxylate groups exhibit terminal, chelating, chelate-bridging modes of coordination. The H-atom of dmp forms an intramolecular hydrogen bond with the carboxylate-O of the nearest ligand. The structures of the binuclear products obtained in the present study have been dictated by coordination mode of the carboxylate (chelate vs brdging) and size of the metal ion (Zn vs Cd). Presence of peripheral free hydroxyl functional groups facilitate intra- and inter-hydrogen bonding in the solid state structure. The luminescent properties of 1–5 have also been studied, exhibiting ligand-centred emission around 315 nm. [ABSTRACT FROM AUTHOR]

The synthesis, crystal structures and luminescence of a novel family of lanthanide polymer complexes with general formula [Ln 2 (Hmidp) 3 (H 2 O) 3 ](ClO 4 ) 3 ·6H 2 O (Ln = Nd, Sm, Eu, Gd, Dy, Ho, Tm; H 2 midp = N-methyliminodipropionic acid) are reported. The compounds were obtained by direct reaction of H 2 midp and lanthanide(III) perchlorate in aqueous solution. The choice of the conditions of synthesis were selected from speciation studies. The structure of the polymer complexes contains bimetallic cationic units [Ln 2 (Hmidp) 3 (H 2 O) 3 ] 3+ in which one of the Ln ions is eight-coordinated and the other nine-coordinated, linked by carboxylate bridges. This is expanded to a 2D network through carboxylate linkers. The solid state luminescence of the Eu complex was observed and an average lifetime value of 0.5 ms was verified for the red emitting 5 D 0 excited state. [ABSTRACT FROM AUTHOR]

Three coordination polymers based on m-phenylenediacrylic acid (H 2 mpda) with manganese(II) and cobalt(II), [Mn(Hmpda) 2 (H 2 O) 2 ] n ( 1 ), Co(Hmpda) 2 (H 2 O) 2 ] n ( 2 ), [Co(mpda)(H 2 O) 2 ] ( 3 ) were synthesized by the hydrothermal methods and their structures and magnetic properties were fully characterized. Compounds 1 and 2 are isomorphous coordination compounds in which carboxylate-bridged square-grid 2D sheets are separated by bilayers of Hmpda − . While compound 3 is composed of 1D coordination chains based on binuclear units with double carboxylate bridges. Magnetic investigations on the compounds have been carried out and revealed weak antiferromagnetic exchange mediated through the carboxylate bridges. [ABSTRACT FROM AUTHOR]

Hydrothermal reaction of cadmium nitrate, 1,3-adamantanedicarboxylic acid (adcH 2 ), and a hydrogen-bonding capable dipyridylamide ligand afforded five crystalline coordination polymers whose dimensionality depends on the dipyridylamide length and nitrogen donor disposition. The five new phases were structurally characterized via single-crystal X-ray diffraction. [Cd(adc)(4-pmina)] n ( 1 , 4-pmina = 4-pyridylmethylisonicotinamide) displays a (4,4) grid topology with [Cd(adc)] n chains pillared by the dipodal dipyridylamide ligands. {[Cd(adc)(4-pmna)(H 2 O)]·4H 2 O} n ( 2 , 4-pmna = 4-pyridylmethylnicotinamide) displays a similar layered topology, but with octameric water molecule clusters residing in the interlamellar regions. {[Cd(adc)(3-pna)(H 2 O)]·6H 2 O} n ( 3 , 3-pna = 3-pyridylnicotinamide) possesses 1-D ribbon submotifs due to the syn-conformation and shorter tether length of the dipyridylamide ligands. Compound 3 entrains intriguing “infinite” water molecule tapes comprised of 4- and 5-membered rings. {[Cd 2 (adc) 2 (3-pina) 2 ]·H 2 O} n ( 4 , 3-pina = 3-pyridylisonicotinamide) manifests a 4-connected 3D 6 5 8 cds topology. The minor coordination polymer chain product {[Cd(adc)(3-pyram) 2 (H 2 O)]·2H 2 O} n ( 5 ) was isolated along with 4 (3-pyram = 3-pyridylamine). Luminescent behavior in 1 – 4 is attributed to intra-ligand molecular orbital transitions. The new phases were also surveyed for the ability to detect nitrobenzene in ethanol suspension. Thermal decomposition behavior is also discussed herein. [ABSTRACT FROM AUTHOR]

A green-emitting iridium(III) complex Ir(dfppy) 2 (cbphen) (dfppy = 2-(4′,6′-difluoro-phenyl)pyridine, cbphen = 4-carboxylate-phenanthroline) was synthesized and fully characterized. The single crystal data confirm its Ir(C^N) 2 (N^N) structure with the carboxylate group on phenanthroline stretching freely which could be able to combine with europium(III) ion. The complex was reacted with EuCl 3 ·6H 2 O and Eu(TTA) 3 ·2H 2 O to provide bimetallic complexes. Through photophysical studies, characteristic emission from Eu III ion was obtained, and meanwhile the green emission from iridium(III) center was almost quenched completely, suggesting this iridium(III) complex is a good sensitizer for Eu III ions. It is well worth noticing that by introducing the iridium(III) complex as a chromophore, the excitation wavelength of Eu III ion has been extended to the visible range (470 nm). Besides, due to the efficient energy transfer, the quantum yield of Ir 3 -Eu was nearly equal to that of Eu(TTA) 3 ·2H 2 O. [ABSTRACT FROM AUTHOR]

Two lanthanide–organic coordination polymers incorporating both substituted imdazole dicarboxylate and benzene monocarboxylate auxiliary ligand, namely, {[Gd 2 (μ 3- OH)(pimda)(imba) (H 2 pimda) H 2 O]·2H 2 O} n ( 1 ) and {[Tb 2 ((μ 3- OH)(pimda)(imba) (H 2 pimda) H 2 O]·2H 2 O} n ( 2 ) (H 3 pimda = 2-propyl-1H-imidazole-4,5-dicarboxylic acid and H 2 imba = 4-(1H-imidazole-1-ly) benzoic acid) have been obtained under the hydrothermal conditions, and have been structurally characterized by elemental analysis, IR spectrum and single X-ray diffraction. The polymers are isostructural, both crystallizing in the triclinic system, with space group of p -1 . They display one dimensional (1-D) double-stranded ribbon chains based on hydroxyl-bridged [Ln 4 pimda 2 ] tetranuclear unit as second building block, which are interlinked forming 2-D corrugated layer. The extensive hydrogen bondings further extend these 2-D lamellar networks into 3-D supramolecular architecture. The emission spectrum of polymer 1 exhibits ligand-to-ligand charge-transfer (LLCT) transition luminescence; polymer 2 shows characteristic f-f transition luminescence, which can be considered as a fluorescent molecular sensor for zinc(II) ions in environment. Variable-temperature magnetic susceptibility measurement reveals that multi-bridging fashion of carboxylic group in 1 results in depopulation of the stark levels for a single Gd(III) ion and/or possible antiferromagntic interactions between adjacent Gd(III) cations within the carboxylato bridged binuclear unit. [ABSTRACT FROM AUTHOR]

Four coordination polymers of different transition metal ions with a new zwitterionic tricarboxylate ligand, 1-(3,5-dicarboxylatophenyl)-4-carboxylatopyridinium (L 2− ) were synthesized, and characterized. They are formulated as [Cu 3 L 2 (OH) 2 ] ( 1 ), [M(L)(H 2 O)] [M = Mn ( 2 ) and Cd ( 3 )] and [Zn(L)(H 2 O)]·2H 2 O ( 4 ). Compound 1 exhibits a 3D coordination framework containing carboxylate- and hydroxo-bridged chains. Compounds 2 and 3 are isomorphic and both contain 2D coordination layers based on carboxylate-bridged dinuclear units (Mn or Cd). Compound 4 shows a different 2D coordination layer, and extensive hydrogen bonding and π-π stacking interactions lead to a 3D architecture with 1D channels, in which square tetraaqua clusters are captured through hydrogen bonds. The compound undergoes a structural transformation upon dehydration and the structure can be switched back through reabsorbing water. Magnetic studies demonstrated that the mixed μ -OH and μ -1,3-carboxylate bridges in 1 mediate ferromagnetic exchange owing to orbital countercomplementarity. The carboxylate bridges in 2 mediate weak antiferromagnetic interactions. Compounds 3 and 4 show the fluorescence characteristic of the ligand. [ABSTRACT FROM AUTHOR]

Hydrothermal reaction of a metal nitrate, an adamantane-based dicarboxylic acid, and a long-spanning dipyridyl ligand produced six coordination polymers that were structurally characterized by single-crystal X-ray diffraction. [Ni 2 (adc) 2 (μ-H 2 O)(4-bpfh) 2 ] n ( 1 , adc = 1,3-adamantanedicarboxylate, 4-bpfh = bis(4-pyridylformyl)homopiperazine) displays 1D coordination polymer ribbons based on [Ni 2 (OCO) 2 (μ-H 2 O)] dimeric units. {[Ni(adc)(4-bpfp) 2 (H 2 O) 2 ]·H 2 O} n ( 2 , 4-bpfp = bis(4-pyridylformyl)piperazine) shows a simple stacked (4,4) layer structure. {[Ni 2 (adc) 2 (3-bpmp) 2 (H 2 O) 2 ]·15H 2 O} n ( 3 , 3-bpmp = bis(3-pyridylmethyl)piperazine) also possesses stacked (4,4) grids, but with two different types of infinite water tapes in the interlamellar regions. {[Ni 2 (adc) 2 (4-bpmp) 2 (H 2 O) 2 ]·3H 2 O} n ( 4 , 4-bpmp = bis(4-pyridylmethyl)piperazine) again exhibits (4,4) layers, but with two-fold 2D + 2D → 2D parallel interpenetration. [Co(adc)(4-bpmp)] n ( 5 ) displays carboxylate bridged {Co 2 (OCO) 2 } cluster units pillared by adc and 4-bpmp ligands into an 8-connected 4 24 6 4 bcu topology. Use of the longer 1,3-adamantanediacetate (ada) ligand afforded {[Ni 2 (ada) 2 (4-bpmp) 2 (H 2 O)]·2H 2 O} n ( 6 ), which possesses dinuclear {Ni 2 (OCO) 2 (μ-H 2 O)} cluster units linked into [Ni 2 (ada) 2 (H 2 O)] ribbons, further connected by 4-bpmp ligands into a rare 6-connected self-penetrated 4 8 6 7 msw net. Variable temperature magnetic studies were undertaken in cases where dimeric units were evident; antiferromagnetic coupling was observed for 1 and 5 , while ferromagnetic coupling with low temperature spin canting was observed for 6 . Thermal properties of all new materials were also investigated. [ABSTRACT FROM AUTHOR]

By reacting 2- and 3-aminobenzoic acids (HL 1 and HL 2 , respectively), as well as 2-, 3- and 4-{(E)-2-[4-(dimethylamino)phenyl]diazenyl}benzoic acids (HL 3 , HL 4 and HL 5 , in this order) with a n -butyltin(IV) source [ n BuSn(O)OH or n Bu 2 SnO], the drum-type butylstannoxane complexes of general composition [ n Bu 6 Sn 6 O 6 (L n ) 6 ] [L n = L 1 ( 1 ), L 2 ( 2 ) and L 3 ( 3 )] and the ladder-type compounds [ n Bu 8 Sn 4 O 2 (L n ) 4 ] [L n = L 3 ( 5 ), L 4 ( 6 ) and L 5 ( 7 )] were obtained and fully characterized. By reacting 1 with 2-{(E)-[4-(dimethylamino)benzylidene]amino}benzoic acid (HL 6 ), a co-crystal ( 4 ) was achieved which comprises the metal complex aggregate found in 1 and the neutral HL 6 molecule. The solution properties of the compounds were assessed from 1 H and 13 C NMR studies and, for the metal complexes, also from 119 Sn NMR. The molecular structures of 1 , 2 , 4 – 7 were confirmed by single-crystal X-ray diffraction. Compounds 1 – 3 and the complex moiety of 4 display hexameric Sn 6 O 6 clusters with drum-like structures, but 5 – 7 reveal Sn 4 O 2 cores with ladder-type structural motifs. Besides the observed relationship between the ligand N-functional group and obtained (drum- or ladder-type) assemblies, the relative position of the carboxylate group in the ligand itself influences its coplanarity. [ABSTRACT FROM AUTHOR]

The reaction of some saturated and unsaturated aliphatic copper(II) monocarboxylates, Cu(RCOO) 2 [R = C 6 H 5 CH 2 (phenylacetate, Phac), CH 2 CHCH 2 (vinylacetate, Vnac), C 6 H 5 CH CH (3- trans -phenylacrylate, Phacr), C 6 H 5 (CH 2 ) 2 (3-phenylpropionate, Phpr), c -C 6 H 11 ( ciclo –hexylcarboxylate, c -Hexc), CH 3 (CH 2 ) 10 (laurate, Lau), CH 3 (CH 2 ) 12 (myristate, Myr), (CH 3 ) 3 C (pivalate, Piv)] with pyrazole (Hpz) and water in protic solvents, yielded trinuclear triangular derivatives based on the [Cu 3 ( μ 3 -OH)( μ -pz) 3 ] fragment whose double positive charge is balanced by two coordinated carboxylate ions, actually [Cu 3 ( μ 3 -OH)( μ -pz) 3 (Phac) 2 ], 1 , [Cu 3 ( μ 3 -OH)( μ -pz) 3 (Vnac) 2 (Hpz)], 2 , [Cu 3 ( μ 3 -OH)( μ -pz) 3 (Phacr) 2 ], 3 , [{Cu 3 ( μ 3 -OH)( μ -pz) 3 (Phpr) 2 (Hpz)}{Cu 3 ( μ 3 -OH)( μ -pz) 3 (Phpr) 2 (Hpz)(H 2 O)}]· x H 2 O· y MeOH, 4 , [Cu 3 ( μ 3 -OH)( μ -pz) 3 ( c -Hexc) 2 ], 5 , [Cu 3 ( μ 3 -OH)( μ -pz) 3 (Lau) 2 ], 6 , [Cu 3 ( μ 3 -OH)( μ -pz) 3 (Myr) 2 ], 7 , [Cu 3 ( μ 3 -OH)( μ -pz) 3 (Piv) 2 (HPz)(HPiv) 2 ], 8 . This behavior is consistent with some previously observed features and evidences that the basicity of carboxylate ions is the key for the deprotonation of Hpz and water, leading to the formation of pz − and OH − ions, which are determinant for the self-assembly of the trinuclear triangular species. Single crystal XRD determinations evidenced that in compounds 1 , 2 and 5 the trinuclear moieties further self-assemble generating monodimensional coordination polymers or, in one case (compound 4 ), a dodecanuclear discrete assembly. [ABSTRACT FROM AUTHOR]

Two coordination polymers, namely [Zn 3 (PBDC) 3 (4,4′-bipy)] n ( 1 ) and [Co(PBDC)(4,4′-bipy) 0.5 ] n ( 2 ) have been prepared via hydrothermal reactions of metal(II) nitrates with 1,4-bis(4-phenoxy)benzenedicarboxylic acid (H 2 PBDC) and 4,4′-bipyridine. Both complexes were characterized by elemental analyses, FT-IR, thermogravimetric analysis (TGA), powder X-ray diffraction and single-crystal X-ray diffraction. Structure analyses reveal that complex 1 possesses a (3,4,6)-connected 3D topology with point symbol of {4·9 2 } 2 {4 2 ·6 8 ·8·9 2 ·10 2 }{9 5 ·10}, while complex 2 has a 3D 4-fold interpenetrating framework with point symbol of {4 12 ·6 3 }. In addition, the luminescent property of complex 1 and magnetic property of complex 2 were also studied. [ABSTRACT FROM AUTHOR]

A series of rare-earth metal carboxylates M(RCOO) 3 (M = La ( 1 ), Eu ( 2 ), Gd ( 3 ), Tb ( 4 ), Er ( 5 ); R = 3,5-di- tert -butyl-4-hydroxyphenyl) was synthesized and characterized by elemental analysis, NMR, IR spectroscopy and MALDI-TOF spectroscopy. The photoluminescent (PL) properties of 1 – 5 were investigated. The electron transfer reactions were examined in CUPRAC-test. The radical scavenging activity of the complexes was measured spectrophotometrically using a DPPH-test. The EC 50 values for complexes are varied from 32 to 57 μM while the EC 50 for RCOOH is 79 μM. The inhibition of lipoxygenase (LOX-1B) in the presence of compounds was evaluated. It was found that complexes are weak inhibitors, while RCOOH is inactive. The lanthanum complex was found to be the most efficient inhibitor of lipoxygenase. Thus, the lanthanide carboxylates with 2,6-di- tert -butylphenol moiety could be used as potential antioxidants and luminescent materials. [ABSTRACT FROM AUTHOR]

The mixed-ligand coordination polymers {[Zn(BIX) 2.5 ](NO 3 ) 2 ·5.5H 2 O} n ( 1 ), {[Co(BIX)(HBTC)](BIX) 0.5 ·H 2 O} n ( 4 ), [Ni(BIX) 2 (BDC)(H 2 O)] n ( 5 ), [Zn(BIX)(PDC)] n ( 6 ), [Ni(BIX)(PDC)(H 2 O)] n ( 7 ) and [Zn(BIX) 0.5 (HIDC)] n ( 8 ) were synthesized, structurally characterized and compared to the known coordination polymers {[Co(BIX) 3 ](NO 3 ) 2 ·4H 2 O} n ( 2 ) and {[Zn 2 (BIX)(BTC)(OH)]·H 2 O} n ( 3 ) to determine the mutual influence of an anionic carboxyl ligand and a neutral N-donor ligand (BIX = 1,4-bis((1H-imidazol-1-yl)methyl)-benzene; H 3 BTC = 1,2,3-benzene-tricarboxylic acid; H 2 BDC = 1,3-benzene-dicarboxylic acid (isophthalic acid); H 2 PDC = 3,4-pyridine-dicarboxylic acid; H 3 IDC = 4,5-imidazole-dicarboxylic acid). Compound 1 is a 1D ladder-like structure with two bridging and one terminal (dangling) BIX ligand. Neighboring ladders mutually entangle with the dangling BIX ligand being threaded through {Zn 4 (BIX) 4 } openings from adjacent strands. Compound 2 shows a 3D pcu -network with octahedrally coordinated cobalt ions bridged by three crystallographically different inversion-symmetric BIX ligands. The overall structure motifs in the mixed-ligand compounds are 1D metal-carboxylate chain-structures, bridged by neutral BIX ligands to form either 1D ladder-like strands ( 4 ), 2D networks ( 3 , 5 with square lattice, 4,4 or sql topology, 7 , 8 with honeycomb, 6,3 or hcb topology) or 3D frameworks ( 6 with diamond, 6,6 or dia topology). Noteworthy, compound 4 forms a 1D tubular structure of stacked {Co 2 (BIX) 2 } metallacycles that are threaded with uncoordinated BIX ligands like a rotaxane. A tetrahedral asymmetric Zn atom is formed in the crystals of 6 with spontaneous resolution as only one Zn configuration assembles into the 3D chiral framework of each single crystal. [ABSTRACT FROM AUTHOR]

A synthetic route to linear pairs of dirhodium tetracarboxylate ‘paddlewheel’ dimers bridged by Ru(II) complexes of tridentate ‘terpyridine-like’ ligands is presented. Three dimer-of-dimer assemblies were synthesized as well as two monomer-of-dimer assemblies. A bis(4′-(4-carboxyphenyl)-terpyridine)Ru(II) complex spanning two dirhodium dimers displays a 26 Å separation between the dimers in its X-ray crystal structure. Increased electronic interaction is found for the dimer of dimers without the phenyl groups using bis(4′-(4-carboxy)-terpyridine)Ru(II) as the bridging complex. The addition of one or two of the dirhodium dimers to the Ru photosensitizer leads to an increase in the molar absorptivity in an additive fashion. In the emission profile, the dirhodium tetracarboxylates act as energy transfer traps as the Ru based 3 MLCT (MLCT = metal-to-ligand charge-transfer) excited state is efficiently quenched by energy transfer from the Ru core to the dirhodium periphery, both at room temperature and low (77 K) temperature. [ABSTRACT FROM AUTHOR]

[Display omitted] • New heterometallic Cu(II)–Mn(II)/Co(II) complexes have been synthesized. • All the complexes have been structurally characterized. • Antiferromagnetic coupling between metal centres have been found in the complexes. • The Cu(II)–Mn(II) complexes exhibit only catecholase-like activity. • Heterometal can play a crucial role in catalytic activity. Three new heterometallic complexes [(CuL1) 2 Mn(o -(NO 2)C 6 H 4 CO 2) 2 ] (1), and{[(CuL2) 2 Mn(o -(NO 2)C 6 H 4 CO 2) 2 ]·2CH 3 CN } (2) and {[(CuL2) 2 Co(o -(NO 2)C 6 H 4 CO 2) 2 ]·2H 2 O} (3) have been synthesized using [CuL1]/[CuL2] as metalloligands (where H 2 L1 = N,N ′-bis(2-hydroxynaphthyl-methylidene)-1,3-propanediamine, H 2 L2 = N,N ́-bis(methyl2-hydroxynaphthyl-methylidene)-1,3-propanediamine). Structural characterization of complexes (1 – 3) show that contains linear trinuclear architecture, where the terminal [CuL1]/[CuL2] units are coordinated to the central MnII (for 1 and 2)/CoII (for 3) through double phenoxido bridge along with a syn - syn bridging carboxylate anion. Complexes 1 and 2 exhibit biomimetic catecholase-like activity with the turn over numbers (k cat) of 164 and 140 h−1, respectively. The mass spectral study suggest the most probable mechanism of this biomimetic oxidase reaction whereas, cyclic voltammetry measurements indicate that CuII is reducible to CuI during catalysis. Variable temperature (2–300 K) magnetic susceptibility measurements reveal that all complexes (1 – 3) possess an overall antiferromagnetic coupling between CuII and the hetero metal ions with J values of –7.027(2), –7.076(1) and –2.2(1) cm−1, respectively. [ABSTRACT FROM AUTHOR]

[Display omitted] • The current mini-review is mainly focussed on proton conductivities of metal carboxylates, phosphonates, sulphonates and other related MOFs as membranes for PEMFCs. • The mechanism for proton conduction is explained by two approaches like Grotthuss and Vehicle mechanisms with illustrations. • In order to apply MOFs in commercial applications of the PEMFCs, some of the practical issues like temperature range of operation, robustness, flooding of the interface, ease of fabrication, flooding of electrodes by condensed water, fuel crossover etc. has to be addressed. As eco-friendly energy, the proton exchange membrane fuel cells (PEMFCs) utilize H 2 and O 2 as energy sources wherein the water is the only by-product. As a result, they are the suitable candidates for replacement of combustion engines. Various materials such as hydrocarbon polymers, nafions, CNTs, graphene ionic liquids, etc., have been used as conducting membranes to efficiently transport and transfer charges such as protons across the electrode interfaces. However, many of these materials show mechanical instability at high temperatures and exhibit conductance dependent on relative humidity. They also foul quickly. All these drawbacks reduce the conductivity of the PEMs-constituted layer and lead to the poor output voltage of the fuel cells. The most promising materials to be used as part of the electrode interfaces for fuel cells are Metal Organic Frameworks (MOFs). They have good structural diversity and variability in dimensions/coordination, mechanical and thermal stability and have high surface area, adsorption, catalytic property, luminescence, magnetic properties, etc. MOFs have a high proton conductivity. Due to their structural diversity and variable coordination modes, many MOFs have been identified for their proton conductivity. In this current mini-review, we give a summary report on proton conductivities of metal carboxylates, phosphonates, sulphonates and other related MOFs as membranes for polymer membrane exchange fuel cells (PEMFCs). Charge transport and transfer in these MOF membranes have been established to occur via the proton-mediated conduction as proposed in the Grotthuss or the Vehicle mechanism. [ABSTRACT FROM AUTHOR]

X-ray structures of prepared nickel(II) and copper(II) dicarboxylate complexes. Mononuclear complexes with chelating thiodiacetate and bridging mode of thiodiacetate were proved. The dinuclear copper complex is formed with a dithiodipropionate bridging ligand. Nitrogen atoms complete the coordination sphere. [Display omitted] • Mononuclear and binuclear nickel complex with thiodiacetate was structurally characterized. • New binuclear copper complex with a dithiodipropionate bridge was studied. • All complexes show moderate antibacterial activities. Series of nickel and copper complexes with dicarboxylic acids (2,2′-thiodiacetic acid, 3,3′–thiodipropionic acid, 3,3′-dithiodipropionic acid, and fumaric acid) and N- donor ligands (1,2–diaminopropane, 1,3-diaminopropane, 1,10-phenanthroline and N,N,N′,N″,N″– pentamethyldiethylenetriamine) were synthesized and characterized using elemental analysis, IR spectroscopy and single-crystal X-ray diffraction. These coordination compounds were tested for their antibacterial activities in vitro. The complexes demonstrated moderated antibacterial activity against Gram-positive and Gram-negative bacteria and could potentially be applied to treat skin wounds. [ABSTRACT FROM AUTHOR]

[Display omitted] • Isolation of new metal azolate/carboxylate frameworks with Co(II) and Cd(II). • [Co 3 (HPZTC) 2 (H 2 O) 6 ]·2H 2 O (MAC-1) features 1-D chains alternating monomeric and dimeric units. • [Co(H 2 PZTC)(DMF)(H 2 O)] 2 (MAC-2) contains 1-D hydrogen-bonded strands of dimeric units. • [Cd 2 (PZTC)(H 2 O) 2 ] (MAC-3) shows a 3-D non-porous network. The tetratopic ligand 1- H -pyrazol-3,4,5-tricarboxylic acid (H 4 PZTC) has been used for the first time to prepare the new metal azolate/carboxylate (MAC) frameworks [Co 3 (HPZTC) 2 (H 2 O) 6 ]·2H 2 O (MAC-1), [Co(H 2 PZTC)(DMF)(H 2 O)] 2 (MAC-2) and [Cd 2 (PZTC)(H 2 O) 2 ] (MAC-3), along either conventional or solvothermal routes. As assessed by thermogravimetric analysis, before decomposition the three MAC frameworks undergo partial decarboxylation over 200 °C. Powder X-ray diffraction unveiled 1-D chains alternating monomeric and dimeric units in MAC-1 , 1-D hydrogen bonded strands of dimeric units in MAC-2 and a 3-D non-porous network in MAC-3. [ABSTRACT FROM AUTHOR]

We are reporting the structural and magnetic characterization of a Mn(III) mononuclear complex based on a Schiff-base ligand with carboxylate pendant arm. Very strong symmetric H-interaction drives a one dimensional organization of this complex, densely packed through C–H⋯π further interactions. Low temperature magnetic behaviour appears governed by local ion zero field splitting obscuring any possible weak exchange interaction through the symmetric H-bond pathway. [ABSTRACT FROM AUTHOR]

Three new zinc coordination polymers, [Zn(L)] n ·2 n (H 2 O) ( 1 ), [Zn 2 (L)(μ 2 -OH) 2 ] n ·1.5 n (H 2 O) ( 2 ), [Zn 3 (L) 2 (glu)] n ( 3 ), [H 2 L = 4′-(4-carboxyphenyl)-6′-carboxycalte-2,2′-bipyridine, H 2 glu = glutaric acid] have been hydrothermally synthesized and characterized by elemental analysis, infrared spectra and single crystal X-ray diffraction. Compound 1 is a 2D structure with the hcb topological net. Compound 2 is a microporous 2D layer structure with [Zn 4 O 4 ] eight-membered rings. Compound 3 exhibits a self-penetrating 3D framework structure, which shows a new interesting topological net with the point symbol of {12 3 }. Luminescent studies indicated that compound 3 could be an efficient multifunctional luminescent material for high-sensitivity sensing metal cations and small organic molecules, especially for Fe 3+ and Cu 2+ , methanol and nitrobenzene. [ABSTRACT FROM AUTHOR]

Hydrothermal reaction of a metal nitrate, 2,5-furandicarboxylic acid (H 2 fdc), and the long-spanning dipyridylamide ligand bis(4-pyridylformyl)piperazine (bpfp) produced three coordination polymers which were structurally characterized by single-crystal X-ray diffraction. {[Cd 2 (fdc) 2 (bpfp)(H 2 O) 4 ]·10H 2 O} n ( 1 ) possesses 1D 3-connected coordination polymer ladders co-crystallized with decameric water molecule clusters. {[Cu(fdc)(bpfp)(H 2 O) 2 ]·2H 2 O} n ( 2 ) exhibits (4,4) grid coordination polymer layers stacked in an unusual parallel ABCD pattern. {[Ni(fdc)(bpfp)(H 2 O) 2 ]·4H 2 O} n ( 3 ) also manifests (4,4) grid coordination polymer layers, but these engage in 2D + 2D → 3D mutually inclined interpenetration. Hydrothermal reaction of metal nitrates, 2,5-thiophenedicarboxylic acid (H 2 tdc), bpfp afforded {[Zn(tdc)(bpfp)(H 2 O)]·2H 2 O} n ( 4 ), {[Cd(tdc)(bpfp)(H 2 O)]·2H 2 O} n ( 5 ), {[Ni 2 (tdc) 2 (bpfp) 2 (H 2 O) 4 ]·3H 2 O} n ( 6 ), and {[Cu(tdc)(bpfp)(H 2 O) 2 ]·3H 2 O} n ( 7 ). Compounds 4 and 5 exhibit (4,4) sawtooth coordination polymer layer motifs that engage in relatively uncommon 2D + 2D → 3D parallel interpenetration. Compounds 6 and 7 both showed 2D + 2D → 3D mutually inclined interpenetration of parallel sets of (4,4) grid layer motifs, but with different orientations of the heterocycles within their respective metal/tdc chain submotifs. Thermal properties of all new materials were also investigated. The luminescent cadmium and zinc derivatives 1 , 4 , and 5 were assayed as potential detectors for nitrobenzene in methanol suspension. [ABSTRACT FROM AUTHOR]