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Antibiotic resistance is a significant global concern, necessitating the development of either new antibiotics or advanced delivery methods. With this in mind, we report on the synthesis and characterisation of a new family of Metal-Organic Frameworks (MOFs), OnG6 MOFs, designed to act as multi-drug carriers for bacterial infection treatment. OnG6 is based on the pro-drug 4,4'-azodisalicylic acid (AZDH 4 ), which in vivo produces two equivalents of para -aminosalicylic acid (ASA), a crucial drug for M. tuberculosis treatment. X-ray and computational studies revealed that OnG6 MOFs are mesoporous MOFs with etb topology and an [M 2 (AZD)] formula (M = Zn, OnG6-Zn; Mg, OnG6-Mg; Cu, OnG6-Cu; and Co, OnG6-Co), featuring 1-dimensional channel type pores of 25 Å diameter. OnG6 MOFs are the first reported MOFs bearing the ligand AZDH 4 , joining the family of mesoporous MOFs arranged in a honeycomb pattern. They absorb isoniazid (INH) and ciprofloxacin (CIPRO) with the former being a specific antibiotic for M. tuberculosis , and the latter being a broader-spectrum antibiotic. The stability of the MOFs and their capacity for antibiotic uptake depend on the nature of the metal ion, with OnG6-Mg demonstrating the highest drug absorption. The antimicrobial activity of these species was assessed against S. aureus and E. coli , revealing that the carriers containing CIPRO displayed optimal efficacy.

The use of 2-pyridyl oximes in metal complexes chemistry has been extensively investigated in the last few decades as a fruitful source of species with interesting magnetic properties. In this work, the initial combination of pyridine-2-amidoxime (pyaoxH 2 ) and 2-methyl pyridyl ketoxime (mpkoH) with isonicotinic acid (HINA) and 3,5-pyrazole dicarboxylic acid (H 3 pdc) has provided access to three new compounds, [Ni 4 (INA) 2 (pyaox) 2 (pyaoxH) 2 (DMF) 2 ] ( 1 ), [Co 5 (mpko) 6 (mpkoH) 2 (OMe) 2 (H 2 O)](ClO 4 ) 6 ( 2 ), and [Co 5 (OH)(Hpdc) 5 (H 2 pdc)] ( 3 ). 1 displays a square-planar metal topology, being the first example that bears simultaneously HINA and pyaoxH 2 in their neutral or ionic form. The neighbouring Ni 4 units in 1 are held together through strong intermolecular hydrogen bonding interactions, forming a three-dimensional supramolecular framework. 2 and 3 are mixed-valent Co 4 III Co II and Co 2 III Co II 3 compounds with a bowtie and trigonal bipyramidal metal topology, accordingly. Direct current and alternate current magnetic susceptibility studies revealed that the exchange interactions between the Ni II ions in 1 are ferromagnetic ( J = 1.79(4) cm -1 ), while 2 exhibits weak AC signals in the presence of a magnetic field. The syntheses, crystal structures, and magnetic properties of 1-3 are discussed in detail.

Metal-organic frameworks (MOFs) are promising multifunctional porous materials for biomedical and environmental applications. Here, we report synthesis and characterization of a new MOF based on the tetrahedral secondary building unit [Zn 4 O(CBAB) 3 ] n (NUIG4), where CBABH 2 = 4-((4-carboxybenzylidene)amino)benzoic acid. NUIG4 belongs to the family of MOFs with primitive cubic pcu topology, being a rare example with 4-fold interpenetration. The pore architecture enables unprecedentedly high doxorubicin (DOX) loading capacity (1955 mg DOX/g NUIG4) with pH-controlled release. Solid-state NMR and ab initio modeling confirmed formation of aromatic π-π stacking interactions between DOX and the framework. Preliminary cell-line experiments suggested a protective effect of NUIG4 on healthy HDF cells against DOX toxicity. NUIG4 also displays potential for adsorptive small-molecule gas separation, with a BET surface area of 1358 m 2 g -1 and high selectivity of 2.75 for C 2 H 2 over CO 2 .

The goal of this work is to model the nature of the chemical species [CdCl 2 (extractant) 2 ] that are formed during the solvent (or liquid-liquid) extraction of the toxic cadmium(II) from chloride-containing aqueous media using hydrophobic 2-pyridyl ketoximes as extractants. Our coordination chemistry approach involves the study of the reactions between cadmium(II) chloride dihydrate and phenyl 2-pyridyl ketoxime (phpaoH) in water-containing acetone. The reactions have provided access to complexes [CdCl 2 (phpaoH) 2 ]∙H 2 O ( 1 ∙H 2 O) and {[CdCl 2 (phpaoH)]} n ( 2 ); the solid-state structures of which have been determined by single-crystal X-ray crystallography. In both complexes, phpaoH behaves as an N , N '-bidentate chelating ligand. The complexes have been characterized by solid-state IR and Raman spectra, and by solution 1 H NMR spectra. The preparation and characterization of 1 ∙H 2 O provide strong evidence for the existence of the species [CdCl 2 (extractant) 2 ] that have been proposed to be formed during the liquid-liquid extraction process of Cd(II), allowing the efficient transfer of the toxic metal ion from the aqueous phase into the organic phase., Competing Interests: The authors declare no conflict of interest.

The use of pyridine-2-amidoxime (pyaoxH 2 ) in Ni chemistry has provided access to a dodecanuclear complex and a hexadecanuclear Ni cluster, namely [Ni 12 (pyaox) 6 (pyaoxH) 6 (MeOH) 2 Cl 2 ]Cl 4 ·5MeOH (1·5MeOH) and [Ni 16 (pyaox) 8 (pyaoxH) 8 (MeOH) 4 ](SO 4 ) 4 ·10H 2 O·26MeOH (2·10H 2 O·26MeOH). Complex 1·5MeOH was isolated by the reaction of NiCl 2 ·6H 2 O, pyaoxH 2 and NaOMe in a 1 : 1 : 2 molar ratio in MeOH in 60% yield. Treatment of NiSO 4 ·6H 2 O with pyaoxH 2 and NEt 3 in a 1 : 1 : 2 molar ratio in MeOH afforded 2·10H 2 O·26MeOH in good yield (65%). The two compounds display a multi-decker configuration based on stacked Ni 4 layers, {Ni 4 (pyaox) 2 (pyaoxH) 2 } 2+ x (x = 3, 1·5MeOH; x = 4, 2·10H 2 O·26MeOH); each deck consists of two square planar and two octahedral Ni II centres. The number of decks observed in 1·5MeOH and 2·10H 2 O·26MeOH depends on the nature of the inorganic anion that is present in the reaction system, which provides elements of synthetic control towards new high nuclearity Ni II species. 2·10H 2 O·26MeOH is the first structurally characterized complex of any metal displaying a quadruple-decker configuration, being also the highest nuclearity metal cluster bearing pyaoxH 2 and the highest nuclearity Ni II cluster with any type of 2-pyridyl oxime. Each cluster cation displays ferromagnetic exchange between the octahedral Ni II ions resulting in a spin ground state of S = 6 for 1 and S = 8 for 2. Magnetothermal studies have been performed and discussed for both clusters.

The reactions of various copper(ii) sources with 2-acetylpyridine, (py)(me)CO, and 2-benzoylpyridine, (py)(ph)CO, under strongly basic conditions have been studied and novel ligand transformations have been discovered. Reaction of Cu(ClO4)2·6H2O and (py)(me)CO in the presence of NBu4(n)OMe (1 : 1 : 1) in CHCl3 gave a mixture of [Cu2Cl2(HLA)2](ClO4)2 (1) and [Cu2Cl2(LB)2(ClO4)2] (2), where HLA is 3-hydroxy-1,3-di(pyridin-2-yl)-butane-1-one and LB is the zwitterionic-type ligand 3-hydroxy-1-methyl-3-(pyridin-2-yl)-3H-indolizin-4-ium. The ligand HLA is formed through an aldol reaction-type mechanism, while the formation of LB takes place via an intramolecular nucleophilic attack of the remote 2-pyridyl nitrogen atom on the positive carbonyl carbon of HLA, after the transformation of the latter through deprotonation and dehydration. The Cu(II) ions in 1 are bridged by two 2.1111 HLA ligands resulting in a long Cu(II)Cu(II) distance (5.338 Å); the metal ions in 2 are triply bridged by the alkoxide oxygen atoms of the two 2.21 LB ligands and one 2.1100 perchlorato group. The absence of α-hydrogens in (py)(ph)CO leads the reactivity of this ligand in the presence of Cu(II) to different pathways. The Cu(ClO4)2·6H2O/(py)(ph)CO/NBu4(n)OMe reaction mixture in MeOH/H2O (25 : 1 v/v) gave the dinuclear cationic complex [Cu2{(py)(ph)CO}2(LC)2](ClO4)2 (3), where LC(-) is the anion of (methoxy)(phenyl)(pyridin-2-yl)methanol formed in situ via the nucleophilic addition of MeO(-) to the carbonyl carbon of (py)(ph)CO upon Cu(II) coordination. The Cu(II) ions in the cation are doubly bridged by the deprotonated oxygen atoms of the two LC(-) ligands. Replacement of Cu(ClO4)2·6H2O with Cu(NO3)2·3H2O and NBu4(n)OMe with NMe4OH and the decrease of the H2O concentration in the above reaction system yielded the tetranuclear coordination cluster [Cu4(OMe)2(NO3)4{(py)(ph)CO}2(LC)2] (4). The Cu(II) centres in this complex define a parallelogram. Two parallel sides of the parallelogram are each supported by deprotonated oxygen atoms belonging to a 2.21 LC(-) ligand and a 2.2 MeO(-) group. The metal ions that define each of the other two sides are singly bridged by an oxygen atom of a 2.210 nitrato group. No bridging exists between the Cu(II) ions that define the two diagonals of the parallelogram. Replacement of MeOH with EtOH in the reaction system that gave 4 resulted in the dinuclear complex [Cu2(NO3)2(LD)2)(EtOH)] (5), LD(-) being the anion of (ethoxy)(phenyl)(pyridin-2-yl)methanol. The Cu(II) ions are doubly bridged by the alkoxide oxygen atoms of the two 2.21 LD(-) ligands. The 1 : 1 : 1 Cu(NO3)2·3H2O/(py)(ph)CO/NMe4OH reaction system in CH3NO2 gave the dinuclear complex [Cu2(NO3)2(LE)2] (6), where LE(-) is the anion of 2-nitro-1-phenyl-1-(pyridin-2-yl)ethanol. The OH(-) ion abstracts one of the methyl hydrogens of CH3NO2, and once the carbanion (-):CH2NO2 is formed it attacks the positive (δ+) carbonyl carbon of (py)(ph)CO; as the carbanion forms the new C-C bond, the π electrons of the carbonyl group of the original ligand are transferred completely to oxygen forming the alkoxide-type ligand LE(-). The Cu(II) ions are doubly bridged by the alkoxide oxygen atoms of the two 2.21 LE(-) ligands. Simplified mechanistic views of the Cu(II)-assisted formation of the transformed ligands are proposed. Dc magnetic susceptibility studies in the 2-300 K range for the representative complexes 3-6 reveal the presence of very strong antiferromagnetic Cu(II)Cu(II) exchange interactions in the dinuclear complexes 3, 5, and 6 and within the dimeric {Cu2(OMe)(NO3){(py)(ph)CO}(LC)}(+) subunits of 4. The strong antiferromagnetic coupling is discussed in terms of the large Cu-O-Cu angles (101.0-102.9°) in the dinuclear, planar {Cu2O2} units/subunits of 3-6.

Unusual {Ni(II)(3)Ln(III)(μ-OR)(6)}(3+) complexes with a "star" topology have been prepared with ligands derived from the metal-promoted reduction of di-2-pyridyl ketone under solvothermal conditions; the Dy(III) member shows weak single-molecule-magnet behavior.

The initial employment of 2-pyridinealdoxime in 3d/4f chemistry has led to a Ni(II)(8)Dy(III)(8) cluster with an unprecedented metal topology; the compound has an unusual structure, is the highest-nuclearity metal oxime cluster to date, and exhibits slow magnetization relaxation.

Using monoanionic forms of di-2-pyridyl ketone as the only primary ligand, triangular Ni(2)M (M = lanthanide, Y) complexes with interesting magnetic properties have been synthesized.

The reactions of methyl(2-pyridyl)ketone oxime, (py)C(Me)NOH, with manganese(II) sulfate monohydrate have been investigated. The reaction between equimolar quantities of MnSO(4) . H(2)O and (py)C(Me)NOH in H(2)O lead to the dinuclear complex [Mn(2)(SO(4))(2){(py)C(Me)NOH}(4)] . (py)C(Me)NOH, 1 . (py)C(Me)NOH, while employment of NaOMe as base affords the compound [Mn(HCO(2))(2){(py)C(Me)NOH}(2)] (2). The structures of both compounds have been determined by single crystal X-ray diffraction. In both complexes, the organic ligand chelates through its nitrogen atoms. The IR data are discussed in terms of the nature of bonding and the structures of the two complexes.

The reactions of phenyl(2-pyridyl)ketone oxime (py)C(ph)NOH, with nickel(II) sulfate hexahydrate under reflux, in the absence of an external base, have been investigated. The reaction of NiSO4 x 6H2O with two equivalents of (py)C(ph)NOH in H2O/MeOH leads to the dinuclear complex [Ni2(SO4)2[(py)C(ph)NOH]4] (1), while an excess of the organic ligand affords the 1:3 cationic complex [Ni[(py)C(ph)NOH]3](SO4) (2). Compound 1 is transformed into 2 by a reaction with an excess of ligand in refluxing H(2)O/MeOH. Reactions of 1 and 2 with a limited amount of LiOH give the known cluster [Ni6(SO4)4(OH)[(py)C(ph)NO]3[(py)C(ph)NOH]3(H2O)3]. The structures of 1 and 2 have been determined by single-crystal X-ray crystallography. In both complexes the organic ligand chelates through its 2-pyridyl and oxime nitrogen atoms. The metal centers of 1 are bridged by two eta1:eta1:micro sulfato ligands; each metal ion has the cis-cis-trans deposition of the coordinated sulfato oxygen, pyridyl nitrogen and oxime nitrogen atoms, respectively. The cation of 2 is the fac isomer considering the positions of the coordinated pyridyl and oxime nitrogen atoms. The crystal structures of both complexes are stabilized by hydrogen bonds. Compounds 1 and 2 join a small family of structurally characterized metal complexes containing the neutral or anionic forms of phenyl(2-pyridyl)ketone oxime as ligands. The IR spectra of the two complexes are discussed in terms of the nature of bonding and their structures. From the vibrational spectroscopy viewpoint, the SO4(2-) groups in 1 and 2 appear to have lower symmetries compared with those deduced from X-ray crystallography; this is attributed to the participation of sulfates in hydrogen bonding interactions.