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A three-dimensional terbium(III) coordination polymer of formula [Tb(bttb) 0.5 (2,5-pzdc) 0.5 ] n (1) [H 4 bttb = 1,2,4,5-tetrakis(4'-carboxyphenyl)benzene and H 2 -2,5-pzdc = 2,5-pyrazinedicarboxylic acid] was obtained under hydrothermal conditions. The bttb 4- tetraanion in 1 adopts the bridging and chelating-bridging pseudo-oxo coordination modes while the 2,5-pzdc 2- dianion exhibits a rather unusual bis-bidentate bridging pseudo-oxo coordination mode, both ligands being responsible for the stiffness of the resulting 3D structure. Solid-state photoluminescent measurements illustrate that 1 exhibits remarkable green luminescence emission, the most intense band occurring in the region of 550 nm ( 5 D 4 → 7 F 5 ) with lifetimes at the millisecond scale. Thermometric performances of 1 reveal a maximum relative sensitivity ( S m ) of 0.76% K -1 at 295 K (δ T = 0.05 K), constituting a Tb III ratiometric solid luminescent thermometer over the physiological temperature range. Variable-temperature static (dc) magnetic susceptibility measurements for 1 in the temperature range 2.0-300 K show the expected behavior for the depopulation of the splitted m J levels of the 7 F 7 ground state of the magnetically anisotropic terbium(III) ion plus a weak antiferromagnetic interaction through the carboxylate bridges. No significant out-of-phase magnetic susceptibility signals were observed for 1 in the temperature range 2.0-10.0 K, either in the absence or presence of a static dc magnetic field.

Herein, we describe the synthesis, crystal structure, and electronic properties of {[K 2 (dmso)(H 2 O) 5 ][Ni 2 (H 2 mpba) 3 ]·dmso·2H 2 O} n ( 1 ) and [Ni(H 2 O) 6 ][Ni 2 (H 2 mpba) 3 ]·3CH 3 OH·4H 2 O ( 2 ) [dmso = dimethyl sulfoxide; CH 3 OH = methanol; and H 4 mpba = 1,3-phenylenebis(oxamic acid)] bearing the [Ni 2 (H 2 mpba) 3 ] 2- helicate, hereafter referred to as {Ni II 2 }. SHAPE software calculations indicate that the coordination geometry of all the Ni II atoms in 1 and 2 is a distorted octahedron (O h ) whereas the coordination environments for K1 and K2 atoms in 1 are Snub disphenoid J84 (D 2d ) and distorted octahedron (O h ), respectively. The {Ni II 2 } helicate in 1 is connected by K + counter cations yielding a 2D coordination network with sql topology. In contrast to 1 , the electroneutrality of the triple-stranded [Ni 2 (H 2 mpba) 3 ] 2- dinuclear motif in 2 is achieved by a [Ni(H 2 O) 6 ] 2+ complex cation, where the three neighboring {Ni II 2 } units interact in a supramolecular fashion through four R 2 2 (10) homosynthons yielding a 2D array. Voltammetric measurements reveal that both compounds are redox active (with the Ni II /Ni I pair being mediated by OH - ions) but with differences in formal potentials that reflect changes in the energy levels of molecular orbitals. The Ni II ions from the helicate and the counter-ion (complex cation) in 2 can be reversibly reduced, resulting in the highest faradaic current intensities. The redox reactions in 1 also occur in an alkaline medium but at higher formal potentials. The connection of the helicate with the K + counter cation has an impact on the energy levels of the molecular orbitals; this experimental behavior was further supported by X-ray absorption near-edge spectroscopy (XANES) experiments and computational calculations.

Shrimp is one of the most traded fishery products in the world. The shrimp-farming water ionic composition is fundamental to the growth and survival of these specimens. Therefore, this study is aimed to develop a method for the simultaneous separation of Cl - , SO 4 2- , NO 3 - , NO 2 - , and HCO 3 - in this sample by capillary zone electrophoresis with UV indirect detection, without any prior sample treatment, besides dilution. The background electrolyte (BGE) was composed of CrO 4 2- (60 mmol L -1 ), cetyltrimethylammonium bromide (CTAB, 2.5 mmol L -1 ), acetonitrile (0.875% (v/v)), and methanol (2.625% (v/v)). The mixture design optimized the BGE composition. Acetonitrile and methanol changed the degree of solvation of the anions, which decreased the radius, a phenomenon proven by calculating the radius of anions in all the conditions of the mixture design. The optimized and validated method allowed the simultaneous determination of the five above-mentioned anions in 10 min.

In this work, we present the synthetic pathway, a refined structural description, complete solid-state characterization and the magnetic properties of four new cobalt(ii) compounds of formulas [Co(H 2 O) 6 ][Co 2 (H 2 mpba) 3 ]·2H 2 O·0.5dmso (1), [Co(H 2 O) 6 ][Co 2 (H 2 mpba) 3 ]·3H 2 O·0.5dpss (2), [Co 2 (H 2 mpba) 2 (H 2 O) 4 ] n ·4nH 2 O (3), and [Co 2 (H 2 mpba) 2 (CH 3 OH) 2 (H 2 O) 2 ] n ·0.5nH 2 O·2ndpss (4) [dpss = 2,2'-dipyridyldisulfide and H 4 mpba = 1,3-phenylenebis(oxamic) acid], where 2 and 4 were obtained from [Co(dpss)Cl 2 ] (Pre-I) as the source of cobalt(ii). All four compounds are air-stable and were prepared under ambient conditions. 1 and 2 were obtained from a slow diffusion method [cobalt(ii) : H 2 mpba 2- molar ratio used 1 : 1] and their structures are made up of [Co 2 (H 2 mpba) 3 ] 2- anionic helicate units and [Co(H 2 O) 6 ] 2+ cations, exhibiting supramolecular three-dimensional structures. Interestingly, a supramolecular honeycomb network between the helicate units interacting with each other through R 2 2 (10) type hydrogen bonds occurs in 2 hosting one co-crystallized dpss molecule. On the other hand, for the first time, linear (3) and zigzag (4) cobalt(ii) chains were isolated by slow evaporation of stirred solutions of mixed solvents with cobalt(ii) : H 2 mpba 2- in 1 : 2 molar ratio at room temperature. Magnetic measurements of Pre-I revealed a quasi magnetically isolated S = 3/2 spin state with a significant second-order spin-orbit contribution as expected for tetrahedrally coordinated cobalt(ii) ions. The analysis of the variable temperature static (dc) magnetic susceptibility data through first- (1 and 3) and second-order spin-orbit coupling models (2 and 4) reveals the presence of magnetically non-interacting high-spin cobalt(ii) ions with easy-axis (1 and 4)/easy-plane magnetic anisotropies (2 and 4) with low rhombic distortions. Dynamic (ac) magnetic measurements for Pre-I and 1-4 below 8.0 K show that they are examples of field-induced Single-Ion Magnets (SIMs).

Ethnopharmacological Relevance: Species Cissus gongylodes has been used in the traditional medicine in South America and India for the treatment of urolithiasis, biliary and inflammatory problems without any scientific evidence., Aim of the Study: This work was developed to investigate for the first time the anti-inflammatory and anti-urolithiatic activities of leaf decoction of C. gongylodes., Materials and Methods: Decoction was subjected to anti-inflammatory evaluation by the in vivo assay of ear oedema and quantification of the main mediators of inflammation PGE 2 and LTB 4 , and the cytokine TNF-α. The decoction's anti-urolithiatic activity was determined by different in vitro assays to evaluate the inhibition and dissolution of the most prevalent types of kidney stones: calcium oxalate (CaOx) and struvite. Diffusion in gel technique and fresh urine of a patient with renal stone were used to investigate the inhibition and dissolution of CaOx, respectively, and the single diffusion gel growth technique was used to evaluate the inhibition and dissolution of struvite crystals. The decoction was chemically characterized by UHPLC-ESI-HRMS analysis., Results: Decoction showed in vivo anti-inflammatory activity by potent decreasing the level of both the main mediators of inflammation and dose-dependent in vitro anti-urolithiatic action by inhibition and dissolution of both type of crystals, CaOx and struvite., Conclusions: Results obtained corroborate the reports of the traditional use of the decoction of Cissus gongylodes. Besides, it showed multi-target mechanisms actions, inhibition of the main inflammatory pathways, and inhibition/dissolution of the most prevalent types of crystals on urolithiasis. These actions make the decoction a promissory source to the development of new and more efficient drugs., Competing Interests: Declaration of competing interest None to declare., (Copyright © 2020 Elsevier B.V. All rights reserved.)

We herein present the synthesis, spectroscopic analysis, description of the crystal structures and magnetic properties of four new complexes of the formula [{Cu(opba)(H 2 O) 1.2 }{Cu(dmphen)(SCN)} 2 ]·dmf (1), [{Cu(opba)} 2 {Cu(dmphen)Cl} 4 ]·1.5dmf·2.5dmso (2), [{Cu(opba)} 2 {Cu(dmphen)Br} 4 ]·dmf·2.3dmso (3) and [{Cu(opba)}{Cu(dmphen)(dca)} 2 ] n (4) [H 4 opba = N,N'-1,2-phenylenebis(oxamic acid), dmphen = 2,9-dimethyl-1,10-phenanthroline and dca = dicyanamide anion]. 1 is a neutral tricopper(ii) complex where an inner [Cu(opba)] 2- fragment adopts a bis-bidentate coordination mode towards two outer [Cu(dmphen)(NCS)] + units. 2 and 3 are bis-trinuclear species where two oxamato-bridged [Cu(opba){Cu(dmphen)X} 2 ] [X = Cl - (2) and Br - (3)] tricopper(ii) entities are connected by two single X ions involving the central and one of the peripheral copper(ii) ions. 4 is a neutral chain made up of oxamato-bridged [Cu(opba){Cu(dmphen)(dca)} 2 ] fragments linked through a single end-to-end dicyanamide ligand that connects the central copper(ii) ion with one of the peripheral copper(ii) ions. Magnetic susceptibility measurements on polycrystalline samples of 1-4 in the temperature range 1.9-300 K show the occurrence of strong antiferromagnetic interactions between the copper(ii) ions through the oxamate bridge [J = -328(2) (1), -288(2) (2), -431(2) (3) and -370(1) cm -1 (4), the Hamiltonian being defined as H = -J(S 1 ·S 2 + S 1 ·S 3 )] and a weak ferromagnetic coupling across the equatorial-axial exchange pathway provided by the single halide bridge [j = +3.08(3) (2) and +2.34(1) cm -1 (3)]. These values are analyzed by simple orbital symmetry considerations and compared with those reported in the literature for polynuclear copper(ii) complexes with these bridging ligands.

In the series described in this work, the hydrothermal synthesis led to oxidation of the 5-methyl-pyrazinecarboxylate anion to the 2,5-pyrazinedicarboxylate dianion (2,5-pzdc) allowing the preparation of three-dimensional (3D) lanthanide(III) organic frameworks of formula {[Ln 2 (2,5-pzdc) 3 (H 2 O) 4 ]·6H 2 O} n [Ln = Ce (1), Pr (2), Nd (3), and Eu (4)] and {[Er 2 (2,5-pzdc) 3 (H 2 O) 4 ]·5H 2 O} n (5). Single-crystal X-ray diffraction on 1-5 reveals that they crystallize in the triclinic system, P1̅ space group with the series 1-4 being isostructural. The crystal structure of the five compounds are 3D with the lanthanide(III) ions linked through 2,5-pzdc 2- dianions acting as two- and fourfold connectors, building a binodal 4,4-connected (4·6 4 8)(4 2 6 2 8 2 )-mog network. The photophysical properties of the Nd(III) (3) and Eu(III) (4) complexes exhibit sensitized photoluminescence in the near-infrared and visible regions, respectively. The photoluminescence intensity and lifetime of 4 were very sensitive due to the luminescence quenching of the 5 D 0 level by O-H oscillators of four water molecules in the first coordination sphere leading to a quantum efficiency of 11%. Variable-temperature magnetic susceptibility measurements for 1-5 reveal behaviors as expected for the ground terms of the magnetically isolated rare-earth ions [ 2 F 5/2 , 2 H 4 , 4 I 9/2 , 7 F 0 , and 4 I 15/2 for Ce(III), Pr(III), Nd(III), Eu(III), and Er(III), respectively] with M J = 0 (2 and 4) and ±1/2 (1, 3, and 5). Q-band electron paramagnetic resonance measurements at low temperature corroborate these facts. Frequency-dependent alternating-current magnetic susceptibility signals under external direct-current fields in the range of 100-2500 G were observed for the Kramers ions of 1, 3, and 5, indicating slow magnetic relaxation (single-ion magnet) behavior. In these compounds, τ -1 decreases with decreasing temperature at any magnetic field, but no Arrhenius law can simulate such a dependence in all the temperature range. This dependence can be reproduced by the contributions of direct and Raman processes, the Raman exponent (n) reaching the expected value (n = 9) for a Kramers system.

A novel series of copper(II) coordination polymers [Cu2(O2CC8H9)4(pyz)]n (1), [Cu2(O2CC8H9)4(dps)]n (2), {[Cu(O2CC8H9)2(dps)(H2O)]·H2O}n (3), {[NaCu(O2CC8H9)2(bpm)(NO3)]·H2O}n (4), and [Cu4(O2CC8H9)6(OH)2(bpp)2]n (5) [O2CC8H9− = 3-phenylpropionate anion, pyz = pyrazine, dps = di(4-pyridyl)sulfide, bpm = 2,2′-bipyrimidine, and bpp = 1,3-bis(4-pyridyl)propane] have been synthesized and magneto-structurally investigated. Compounds 1 and 2 belong to a large group of copper(II) carboxylates where bis-monodentate pyz (1) and dps (2) ligands connect the paddle-wheel [CuII2(μ-O2CC8H9)4] units leading to alternating copper(II) chains. The structure of 3 consists of uniform chains of trans-[CuII(O2CC8H9)2] units linked by the bis-monodentate dps ligand. Compound 4 consists of heterobimetallic chains where [NaI2CuII2(μ-O2CC8H9)4(NO3)2] units are doubly bridged by bis-bidentate bpm ligands. Compound 5 is also a chain compound whose structure is made up by tetranuclear [CuII4(μ3-OH)2(μ-O2CC8H9)4(O2CC8H9)2] units which are doubly bridged by bis-monodentate bpp ligands. The magnetic properties were investigated in the temperature range 1.8–300 K. Strong antiferromagnetic interactions across the quadruple syn–syn carboxylate are observed in 1 and 2 [J = −378 (1) and −348 cm−1 (2)] whereas a weak ferromagnetic coupling through the double out-of-plane oxo(carboxylate) bridge occurs in 4 [J = +2.66 cm−1], the spin Hamiltonian being defined as H = −JS1·S2 with S1 = S2 = SCu = 1/2. A quasi Curie law is observed for 3 (θ = −0.36 cm−1), the bis-monodentate dps ligand being a very poor mediator of magnetic interactions. The analysis of the magnetic properties of 5 is quite complex because of the presence of two crystallographically independent tetracopper(II) units with single-μ-hydroxo, di-μ-hydroxo, μ3-hydroxo and single-μ-hydroxo plus double syn,syn carboxylate bridges in each one. The nature and values of the magnetic couplings for 5 obtained by fitting (intermediate, strong and weak antiferromagnetic interactions for the three former exchange pathways respectively, and intermediate ferromagnetic interactions for the latter one) were substantiated by DFT type calculations.

A new compound of formula (Bu4N)2[Mn2{Cu(opba)}2ox] (1) [Bu4N(+) = tetra-n-butylammonium cation, H4opba = 1,2-phenylenebis(oxamic acid), and H2ox = oxalic acid] has been synthesized and magneto-structurally investigated. The reaction of manganese(II) acetate, [Cu(opba)](2-), and ox(2-) in dimethyl sulfoxide yielded single crystals of 1. The structure of 1 consists of heterobimetallic oxamato-bridged Cu(II)Mn(II) chains which are connected through bis-bidentate oxalate coordinated to the manganese(II) ions to afford anionic heterobimetallic layers of 6(3)-hcb net topology. The layers are interleaved by n-Bu4N(+) counterions. Each copper(II) ion in 1 is four-coordinate in a square planar environment defined by two amidate-nitrogen and two carboxylate-oxygen atoms from the two oxamate groups of the obpa ligand. The manganese(II) ion is six-coordinate in a somewhat distorted octahedral surrounding that is built by two oxalate-oxygen and four carbonyl-oxygen atoms from two [Cu(opba)](2-) units. The magnetic properties of 1 in the temperature range 1.9-300 K correspond to those expected for the coexistence of intralayer antiferromagnetic interactions of the type copper(II)-manganese(II) across oxamato and manganese(II)-manganese(II) through oxalato bridges plus a weak spin canting in the very low temperature domain. Simulation of the magnetic data through quantum Monte Carlo methodology reveals the magnitude of the intralayer magnetic interactions [J(CuMn) = -32.5(3) cm(-1), and J(MnMn) = -2.7(3) cm(-1)], their values being within the range of those previously observed in lower nuclearity systems.

We herein present the synthesis and X-ray structures of five copper(II) complexes of formulae [Cu(bpca)(CF3SO3)(H2O)]·H2O (1), [Cu(bpca)(Phpr)(H2O)]·3/2H2O (2), {[Cu(bpca)]2[Cu(opba)(H2O)]}·H2O (3), {[Cu(bpca)]2(H2opba)}2·6H2O (4) and [Cu(bpca)(EtH2opba)]n (5), where bpca = bis(2-pyridylcarbonyl)amidate, Phpr = 3-phenylpropionate, CF3SO3(−) = triflate (anion of the trifluoromethanesulphonic acid), H4opba = N,N′-1,2-phenylenebis(oxamic acid), and EtH3opba = monoethyl ester derivative of the H4opba. 1 and 2 are mononuclear copper(II) complexes where the copper atom is five-coordinate in distorted square pyramidal surroundings with a tridentate bpca and a water molecule (1)/carboxylate oxygen (2) building the basal plane and a triflate oxygen (1)/water molecule (2) filling the apical position. 3 is a neutral tricopper(II) complex where the [Cu(opba)(H2O)]2− unit acts as a bis-bidentate ligand toward two peripheral [Cu(bpca)]+ fragments. The three crystallographically independent copper(II) ions in 3 are five-coordinate with two nitrogen and two oxygen atoms (inner copper atom)/three bpca-nitrogen and an oxamate oxygen (outer copper atom) building the basal plane plus a water molecule (inner copper)/an oxamate oxygen (outer copper) in the apical position (inner copper atom) of somewhat distorted square pyramidal surroundings. 4 is a centrosymmetric tetracopper(II) compound where four [Cu(bpca)]+ fragments are assembled by two H2opba2− groups adopting an unusual bidentate/bis-monodentate bridging mode. The two crystallographically independent copper(II) ions in 4 are also five-coordinate having the three bpca-nitrogens in basal positions, the other two sites of the distorted square pyramid being filled by two oxygens of either a bidentate oxamate (at one copper centre) or two bis-monodentate oxamates (at the other copper atom). 5 is a zigzag chain of [Cu(bpca)(H2O)]+ units which are connected through the EtH2opba− ligand adopting a bidentate/monodentate bridging mode across the monodeprotonated oxamate group. Each copper(II) ion in 5 is six-coordinate in an elongated octahedral CuN3O3 chromophore. The magnetic properties of 3–5 were investigated in the temperature range 1.9–300 K. 3 exhibits an intermediate intramolecular antiferromagnetic interaction [J = -65.8(2) cm(-1) with the Hamiltonian H = -J(S(Cu1)·S(Cu2) + S(Cu2)·S(Cu3))] which leads to a low-lying spin doublet at low temperatures. A weak antiferromagnetic coupling between the inner copper(II) ions occurs in 4 [J = -2.36(2) cm(-1), H = -JS1·S2)] and a very small intrachain antiferromagnetic interaction is observed in 5 [J = -0.17(1) cm(-1) with H = -J∑(i)S(i)·S(i+1)]. These values are analyzed by means of simple orbital symmetry considerations and compared with those previously reported for parent systems.

From the reaction between a dinuclear paddle-wheel carboxylate, namely [Cu2mu-(O2CCH2C4H3S)4] (1), and the flexible ligand 1,3-bis(4-pyridyl)propane (BPP) a neutral 2-D coordination polymer [[Cu2(O2CCH2C4H3S)4mu-(BPP)2]]n (2) was obtained. Compounds 1 and 2 were characterized by means of elemental analysis, thermal analysis (TG/DSC), vibrational spectroscopy, and electron paramagnetic resonance (EPR). The crystal structure of 2 reveals that each Cu(II) is coordinated by two nitrogen atoms from different BPP ligands and two 3-thiopheneacetate groups within a distorted square planar geometry in a trans-[N, N, O, O] arrangement. The BPP ligand adopts a TG conformation bridging two copper centers giving rise to a 1-D sinusoidal polymeric chain along the crystallographic c axis. Adjacent 1-D chains are extended into a 2-D coordination network through pairs of monatomic carboxylate bridges in direction of the b axis. This bridging mode affords centrosymmetric dimeric units Cu2O2, and therefore, the copper ions are involved in a CuN2O2O' chromophore displaying a (4 + 1) square pyramidal coordination in the resultant 2-D polymeric network. The polycrystalline X-band EPR spectrum of 2 at room temperature is characteristic of a triplet state with nonnegligible zero-field splitting in agreement with the crystal structure. Crystal data for 2: monoclinic, space group P2(1)/c, a = 9.4253(10) A, b = 10.9373(10) A, c = 23.6378(10) A, beta = 98.733(4) degrees, Z = 2.