NaI Ions Research Articles

Structural characterization of a new samarium–sodium heterometallic coordination polymer

Lanthanide-containing materials are of interest in the field of crystal engineering because of their unique properties and distinct structure types. In this context, a new samarium–sodium heterometallic coordination polymer, poly[tetrakis(μ2-2-formyl-6-methoxyphenolato)samarium(III)sodium(I)], {[SmNa(C8H7O3)4]·solvent} n (Sm-1), was synthesized and crystallized via slow evaporation from a mixture of ethanol and acetonitrile. The compound features alternating SmIII and NaI ions, which are linked by ortho-vanillin (o-vanillin) ligands to form a mono-periodic chain-like coordination polymer. The chains propagate along the [001] direction. Residual electron density of disordered solvent molecules in the void space could not be reasonably modeled, thus the SQUEEZE function was applied. The structural, vibrational, and optical properties are reported.

A Dy-based complex with the magnetic relaxation behavior regulated by enclosing one DyIII ion into a Calix[8]arene ligand

A new DyNa complex [DyIIINaI(CH3CO2)2(DMF)3(H6C8A)]·4DMF (1, DMF = N,N-dimethylformamide, H8C8A = p-tert-butylcalix[8]arene) was obtained and it was characterized by elemental analyses, IR spectroscopy, single-crystal X-ray diffraction analyses, PXRD and magnetic properties. In 1, one DyIII and one NaIII were linked by two O atoms from two CH3CO2− and the two metal ions were enclosed into a H8C8A. The remaining coordination sites of the DyIII and NaI ions were occupied by three O atoms from three DMF coordinated molecules. The DyIII ion in 1 adopts eight coordinate with a triangular dodecahedron. Magnetic property studies indicated complex 1 show slow magnetic relaxation behavior under 1000 Oe applied dc field. Additionally, the orientation of the anisotropy axis for the DyIII in 1 was estimated by Magellan program and the anisotropic axis is aligned along Dy1-O2 bond with an angle of 12.608°.

Field-induced single molecule magnet behavior of a DyIII-NaI one-dimensional chain extended by acetate ions

A novel DyIII-NaI one-dimensional chain, namely [DyIIINaI(L)(CH3CO2)2]n·2CH3CN (1, H2L = N1,N3‑bis(3‑methoxysalicylidene)diethylenetriamine), was synthesized by treating H2L, di-2-pyridyl ketone (dpk), and NaHCO3 with Dy(CH3CO2)2·6H2O in acetonitrile. Complex 1 was characterized by elemental analyses, IR spectroscopy, single-crystal X-ray diffraction analyses and magnetic properties. Structural analyses revealed that 1 consists of a neutral one-dimensional (1D) chain. In each [DyNa] unit, one DyIII and one NaI ions are bridged by two phenoxido O atoms from one L2− ligand and one carboxyl O atom from one CH3CO2−. Moreover, the [DyNa] units were further connected by two carboxyl O atoms from another CH3CO2−. The magnetic studies revealed that 1 exhibits the field-induced single molecule magnet behavior with an effective energy of 13.21 K. The orientation of the anisotropy axes for the DyIII in 1 was estimated by Magellan program, indicating that the directionality of the anisotropic axes is almost collinear to the Dy1-O8 bond, with an angle of 3.085°.

Field-induced slow relaxation of a manganese(III)-based single-ion magnet

A field-induced MnIII-based single-ion magnet with axially elongated Jahn–Teller distortion was well isolated in a layered complex by diamagnetic NaI ions, which exhibits an effective thermal-activated energy barrier of 12.9cm−1 under 2.0kOe dc field resulting from strongly axial anisotropy of the high-spin MnIII ion.

Syntheses and Structures of Homodinuclear (Na–Na) and Heterodinuclear (Cu–Na, Cu–K) Metal Complexes

The study of polynuclear metal complexes has gained great recognition over the last decade owing to their fascinating topological structures, various properties, and potential applications as functional solid materials in luminescence, catalysis, and magnetic materials. A large number of heterodinuclear 3d–4f and 3d–3d′ complexes have been widely studied due to their functional applications. To our knowledge, structurally characterised heterodinuclear (3d–Na, 3d–K) and homodinuclear (Na–Na) metal complexes are rare. Three metal complexes, [CuIINaI(HL1)2(SbF6)]n (1), [CuIIKI(HL1)2(PF6)]n (2), and [Na2(H2L2)2] (3), were synthesised by two kinds of ligands, o-vanillin (HL1) and N,N′-ethylene-bis(3-methoxysalicylideneimine) (H2L2). The structures of heterodinuclear complexes 1 and 2 are both one-dimensional chain structures, including transition metal ions (CuII) and main group metal ions (NaI and KI). However, the complex 3, as a homodinuclear metal complex, only has one kind of centre, a NaI ion. The structures of complexes 1–3 were determined by single crystal X-ray crystallographic studies.

A series of [NaMnIII3MnII] clusters constructed using a multidentate Schiff-base ligand and decorated with different auxiliary ligands

Four new polynuclear clusters [NaMnIII3MnII(HL)3(μ4-O)(μ1,1-N3)3]ClO4·CH3CH2OH·(H2O)3 (1), [NaMnIII3MnII(HL)3(μ4-O)(μ1,1-N3)2(μ1,3-N3)]ClO4·CH3CH2OH·H2O (2), [NaMnIII3MnII(HL)3(μ4-O)(HCOO)3]ClO4·(H2O)4 (3) and [NaMnIII3MnII(HL)3(μ4-O)(PhCOO)(H2O)2](ClO4)2·H2O·PhCOO·PhCOOH·CH3OH (4) have been obtained via self-assembly between 3-((2-hydroxy-3-methoxybenzylidene)amino)propane-1,2-diol (H3L: condensed from o-vanillin and 3-amino-1,2-propanediol) and the auxiliary bridges (N3−, HCOO−, PhCOO−, H2O) with Mn(ClO4)2·6H2O in the air-exposed methanol solution. The structures of 1–4 all contain [NaMnIII3MnII] units and show a very similar trigonal propeller-like shape. The valences of the metal ions were determined by detection of the Jahn–Teller distortion visible for MnII,III, and confirmed by bond-valence sum (BVS) calculations. Three MnIII ions and one MnII ion take the shape of a super-tetrahedron with the MnII ion lying above the triangular [Mn3O] plane constructed from three MnIII ions linked by a central μ4-O atom. The NaI ion which lies below the [Mn3O] plane is linked with MnIII ions through the oxygen atoms from Schiff base ligands. The main structural difference in the four clusters is caused by the different bridging modes among MnIII ions. A structural comparison of 1–4 demonstrates that the auxiliary ligands play a key role in governing the coordination motifs. Moreover, the magnetic properties of these clusters exhibit dominating antiferromagnetic exchange interaction between spin carriers of MnII,III.

Poly[1H-imidazol-3-ium [di-μ-nitrato-sodium

In the title compound {(C3H5N2)[Na(NO3)2]}n, the NaI ion is coordinated by eight O atoms from three bidentate nitrate anions and two O atoms from two monodentate nitrate anions, displaying a bicapped trigonal–prismatic geometry. The imidazolium cation is essentially planar (r.m.s. deviation for all non-H atoms = 0.0018 Å). In the crystal, the NaI ions are connected by bridging nitrate ligands, forming layers parallel to (010). The imidazolium cations are sandwiched between these layers. Weak C—H⋯O hydrogen bonds link the layers into a three-dimensional network. In addtion, π–π inter­actions between the imidazolium rings [centroid–centroid distance = 3.588 (3) Å] are observed.

Diversity in supramolecular self-assembly through hydrogen-bonding interactions of non-coordinated aliphatic –OH group in a series of heterodinuclear CuIIM (M = NaI, ZnII, HgII, SmIII, BiIII, PbII and CdII)

The syntheses, and structural characterization of seven heterodinuclear complexes: [CuII (HL)NaI(NO3)(MeOH)] (1), [CuII(HL)ZnII(H2O)(NO3)](NO3) (2), [CuII(HL)HgII(Cl)2] (3), [CuII(H2O)(HL)SmIII(NO3)3] (4), [CuII(H2O)(HL)BiIII(NO3)3] (5), [CuII(HL)PbII(NO3)2] (6) and [CuII(HL)CdII(NO3)2] (7) are reported, where H3L=N,N′-bis(3-methoxysalicylaldiimine)-1,3-propylene-2-ol. Compounds 1 and 3 crystallize in the monoclinic P21/n space group, 4, 5 and 7 in the monoclinic P21/c space group, while the space group of complexes 2 and 6 is triclinic P1¯. The X-ray crystallography reveals that the structures of all the complexes consist of diphenoxo-bridged heterometallic cores in which CuII metal ion is trapped in N2O2 compartment of the Schiff-base ligand, while the second metal ion is present in the larger and open O4 [O(phenoxo)2O(methoxy)2] compartment. NaI and ZnII ions in 1 and 2, respectively, are six coordinated, while PbII ion in 6 and CdII ion in 7 are eight coordinated. HgII ion in 3 is six coordinated, while both SmIII and BiIII ions in 4 and 5, respectively, are surrounded by 10 oxygen atoms involving four O atoms from the outer compartment of the ligand and six from three chelating nitrates. In all the cases, non-coordinated –OH group plays significant role in the construction of diverse supramolecular aggregates through hydrogen bonding: two dimensional (2D) in 1 and 3, one dimensional (1D) in 2, 4, 5 and 6, while dimeric in 7. In addition to the structural diversity, the structural resemblance of bismuth(III) with member of a lanthanum family, samarium(III), is noted. In fact, they are found to be isostructural and isomorphous in the present study. Most importantly, compound 3 exhibits a rare feature of helical twisting for the coordinated Schiff-base ligand that arises due to the fact that the metal ion is too large to fit into the wider O4 compartment.

Proton Current through Stalled Na/K-ATPase Pumps: Three Residues Point to a Possible Route and Mechanism

Na/K pumps export 3 Nai ions for every 2 Ko ions imported, and so generate outward current. But Na/K pumps stalled in Ko-free and Nao-free solution pass an inward current that is greatly augmented by lowering pHo to 6. We studied this inward current in Xenopus oocytes expressing Xenopus α1 Na/K pumps made relatively ouabain-resistant by C113Y or Q120R/N131D mutations. The inward current was abolished by arresting pumps with 10 mM ouabain or by activating them with Ko, but not by obstructing either end of the principal ion transport pathway - by BeFx action at the cytoplasmic side, or by modification of an introduced target Cys at the extracellular side. We explored whether, instead, a conformational equilibrium might expose one or more protonatable side chains alternately to extracellular and cytoplasmic solutions, allowing proton current flow down a proton electrochemical gradient. One at a time, we neutralized (E>Q, D>N) carboxylate side chains in cation coordination sites I and II (E336 in TM4; E788 in TM5; D813 and D817 in TM6) and in the proposed third-Na binding site (D935 in TM8; E963 in TM9), and mutated (H>A/N) a nearby His (H921 in TM8). Despite these mutations, low pHo robustly activated inward current in all but D935N, E963Q, and D935N/E963Q stalled pumps. D935 and E963 are 9-10 Å apart in the E2P.2K Na/K-ATPase crystal structures, with a Tyr (Y780 in TM5) equidistant between them with its side chain pointing toward E963. The mutation Y780F almost abolished low-pHo-activated inward current in stalled Na/K pumps. We suggest that, in stalled Na/K pumps, E963 recruits an extracellular proton and, after a conformational change, delivers it (via Y780) to D935, which releases it to the cytoplasm, generating inward current. [NIH HL36783]

Luminescence of unique 1D tube-like lactate lanthanide coordination polymers

Two lactate lanthanide coordination polymers, {[LnNa(lactate)4]·2(H2O)}n (Ln = Sm (1) and Eu (2)), have been synthesized through the salt elimination reactions. X-ray diffraction analysis reveals that complexes 1 and 2 are isomorphic featured 1D tube-like structure incorporating with two distinct coordination models of lactate. Further, the alternative coordinated LnIII and NaI ions with lactate forms a novel coordination framework. The XRD spectra demonstrate that the complex decomposes step by step with the increasing temperature. Complex 2 exhibits essential characteristic luminescence of EuIII ion.

Synthesis, Structure, Photoluminescence and Thermal Properties of Sodium Ethene‐Bis‐Nitrobenzenesulfonate

AbstractAbstract. Sodium ethene‐bis‐nitrobenzenesulfonate, [Na2(ENS)·6H2O]n(1) was synthesized through coupling reaction of o‐nitrotoluenesulfonic acid in NaOH solution and characterized by single crystal X‐ray diffraction, elemental analysis, IR and 1H NMR spectroscopy, XRPD, DSC and TGA (where ENS2– = ethene‐bis‐nitrobenzenesulfonate). The asymmetrical unit of (1) consists of two octahedral NaI ions, and the neighboring metal centers are bridged by μ2 water molecules resulting in the formation of an inorganic tetranuclear unit. The tetranuclear units were connected through the ENS2– ligands into a 2D topology net. The weak π–π stacking and H‐bonding interactions further stabilized the structure. The crystals of (C7H6NO5S)–·(H5O2)+ (2) were obtained by post‐processing the unreacted raw material to recycle. Furthermore, the rigidity and the conjugation effect of the aromatic system in compound 1 were increased through the coordination interactions of metal atoms to ligands, resulting in the emission coming from ligand enhanced with red‐shifting about 9 nm of the maximal wavelength. The conjugation effects and the steric arrangement of the substituent groups play the main role to the luminescence intensity and red‐shift effect.

Poly[bis(μ7-3-sulfonato-L-alaninato)sodiumzinc

The hydro­thermal reaction of Zn(CH3COO)2, NaOH and l-cysteic acid produced the title compound, [Na2Zn(C3H5NO5S)2]n. The ZnII cation is situated on an inversion centre and is in a distorted octa­hedral environment, being chelated by two deprotoned l-cysteic acid ligands through two amino N atoms and two carb­oxy­lic O atoms, with the two axial positions occupied by two carb­oxy­lic O atoms from two other l-cysteic acid ligands. Each l-cysteic acid ligand bridges five NaI ions via its sulfonate group and two ZnII ions via its carboxyl group, forming a three-dimensional framework. Weak N—H⋯O hydrogen bonding is observed in the crystal structure.

Aquabis[N′-(1,3-dithiolan-2-ylidene)-2-hydroxybenzohydrazidato(0.5−)-κ2 N′,O]sodium(I)

The title compound, [Na(C10H9.5N2O2S2)2(H2O)], is a mol­ecular sodium complex with N′-(1,3-dithio­lan-2-yl)-2-hy­droxy­benzohydrazide ligands with the negative charge spread evenly over both, and a water mol­ecule. The NaI ion coordination is distorted trigonal–bipyramidal, formed by two N and three O atoms, with the NaI ion lying on a twofold rotation axis. Intra­molecular N—H⋯O hydrogen bonds occur. Mol­ecules pack as discrete units and the crystal packing is stabilized by strong O—H⋯O hydrogen bonds, which give rise to chains along [010]; the chains are inter­linked by strong O—H⋯O hydrogen bonds.

Alkali-Metal-Templated Assemblies of New 3D Lead(II) Tetrachloroterephthalate Coordination Frameworks

A series of novel metal–organic frameworks (MOFs) have been assembled from PbII and 2,3,5,6-tetrachloro-1,4-benzenedicarboxylic acid (H2BDC-Cl4) by simply adding different alkali metal ions as templates. When only lead nitrate is used, a robust 3D open framework [Pb(BDC-Cl4)(MeOH)2]n (1) with pts topology can be obtained. Incorporating the lighter LiI or NaI ions into the above PbII/BDC-Cl4 system results in two unique isostructural 3D PbII–LiI and PbII–NaI heterometallic frameworks, {[PbLi2(BDC-Cl4)(μ2-OH)2](H2O)}n (2) and [PbNa2(BDC-Cl4)(μ2-OH)2]n (3), which are built from the combination of a 3D rod-packing PbII-carboxylate framework and a 3D NaI–BDC-Cl4 (or LiI–BDC-Cl4) network. When the heavier KI ion is applied, the similar reaction affords a 3D MOF [Pb2(BDC-Cl4)2(DMF)3]n (4), which represents the first pillar-layered PbII coordination network with a (3,5)-connected gra topology. The results illustrate the powerful effect of the alkali-metal templates in MOFs assemblies. The solid-state properties such as thermal stability and luminescence of 1–4 have also been studied.

Poly[tetra-μ2-L-lactato-indium(III)sodium(I)

The asymmetric unit of the title compound, [InNa(C(3)H(5)O(3))(4)](n), consists of one In(III) ion, one Na(I) ion and four crystallographically independent L-lactate monoanions. The coordination of the In(III) ion is composed of five carboxylate O and two hydroxy O atoms in a distorted pentagonal-bipyramidal coordination geometry. The Na(I) ion is six-coordinated by four carboxylate O atoms and two hydroxy O atoms from four L-lactate ligands in a distorted octahedral geometry. Each In(III) ion is coordinated by four surrounding L-lactate ligands to form an [In(L-lactate)(4)](-) unit, which is further linked by Na(I) ions through Na-O bonds to give a two-dimensional layered structure. Hydrogen bonds between the hydroxy groups and carboxylate O atoms are observed between neighbouring layers.

Poly[μ2-aqua-(μ3-2,5-dichlorobenzenesulfonato)sodium

In the title compound, [Na(C6H3Cl2O3S)(H2O)]n, the NaI ion is penta­coordinated by three dichloro­benzene­sulfonate anions and two water mol­ecules, forming a distorted trigonal-bipyramidal geometry. The NaI ions are bridged by the sulfonate groups and the water mol­ecules, leading to a polymeric layer structure parallel to the bc plane in which O—H⋯O hydrogen bonds are observed.

Catena-Poly[sodium-di-μ-aqua-sodium-bis[μ-2,2,2-trichloro-N-(dimorpholinophosphoryl)acetamide

The title compound, [Na2(C10H16Cl3N3O4P)2(H2O)2]n, can be considered as a two-dimensional coordination polymer in which one-dimensional chains are connected to each other by inter­molecular C—H⋯O hydrogen bonds involving the water mol­ecules. The NaI ion is five-coordinated in a distorted trigonal-bipyramidal geometry. The connection between the two NaI ions is facilitated by the two μ-O atoms of the carbonyl group of the 2,2,2-trichloro-N-(dimorpholino­phosphor­yl)acetamide (CAPh) ligand. A bridging coordination of the CAPh ligand via the carbonyl O atom is observed for the first time. The bridging water mol­ecules form inter­molecular O—H⋯O hydrogen bonds with the O atoms of the morpholine rings and the phosphoryl groups of neighboring CAPh mol­ecules.

Catena-Poly[[aqua-sodium(I)]-μ-[2,2'-(disulfanedi-yl)bis-(pyridine N-oxide)]-μ-(pyridine-2-thiol-ato 1-oxide)

There are two monomeric units in the asymmetric unit of the polymeric title compound, [Na(C5H4NOS)(C10H8N2O2S2)(H2O)]n. The NaI ions are six coordinated by four O atoms, one S atom and one water mol­ecule, forming a slightly distorted octa­hedral geometry. An intra­molecular O—H⋯O hydrogen bond stabilizes the conformation of the mol­ecule. The crystal packing is consolidated by inter­molecular O—H⋯O, O—H⋯N and O—H⋯S hydrogen bonds, π–π inter­actions [with centroid–centroid distances of 3.587 (2) Å] together with weak C—H⋯π inter­actions. The mol­ecules are linked into polymeric chains along the b-axis direction.

Catena-Poly[[(ethanol-κO)sodium(I)]-di-μ-aqua-[(rac-2′-hydroxy-1,1′-binaphthyl-2-yl phosphato-κO)sodium]-tri-μ-aqua

The asymmetric unit of the polymeric title compound, [Na2(C20H13O5P)(C2H6O)(H2O)5]n, consists of two NaI ions, one 2′-hydr­oxy-1,1′-binaphthyl-2-yl phosphate anion, one ethanol ligand and five water molecules of crysallization. Each NaI ion has a distorted octa­hedral coordination geometry. The phosphate anion coordinates to one NaI ion and the ethanol mol­ecule coordinates to the other. The five water mol­ecules bridge the NaI ions, forming an inorganic chain structure along the b axis. The chains are connected by O—H⋯O hydrogen bonds into an organic–inorganic hybrid layer parallel to (001).

Microsolvation of the Sodium and Iodide Ions and Their Ion Pair in Acetonitrile Clusters: A Theoretical Study

The structural and thermodynamic properties of Na+(CH3CN)n, I-(CH3CN)n, and NaI(CH3CN)n clusters have been investigated by means of room-temperature Monte Carlo simulations with model potentials developed to reproduce the properties of small clusters predicted by quantum chemistry. Ions are found to adopt an interior solvation shell structure, with a first solvation shell containing approximately 6 and approximately 8 acetonitrile molecules for large Na+(CH3CN)n and I-(CH3CN)n clusters, respectively. Structural features of Na+(CH3CN)n are found to be similar to those of Na+(H2O)n clusters, but those of I-(CH3CN)n contrast with those of I-(H2O)n, for which "surface" solvation structures were observed. The potential of mean force calculations demonstrates that the NaI ion pair is thermodynamically stable with respect to ground-state ionic dissociation in acetonitrile clusters. The properties of NaI(CH3CN)n clusters exhibit some similarities with NaI(H2O)n clusters, with the existence of contact ion pair and solvent-separated ion pair structures, but, in contrast to water clusters, both types of ion pairs adopt a well-defined interior ionic solvation shell structure in acetonitrile clusters. Whereas contact ion pair species are thermodynamically favored in small clusters, solvent-separated ion pairs tend to become thermodynamically more stable above a cluster size of approximately 26. Hence, ground-state charge separation appears to occur at larger cluster sizes for acetonitrile clusters than for water clusters. We propose that the lack of a large Na+(CH3CN)n product signal in NaI(CH3CN)n multiphoton ionization experiments could arise from extensive stabilization of the ground ionic state by the solvent and possible inhibition of the photoexcitation mechanism, which may be less pronounced for NaI(H2O)n clusters because of surface solvation structures. Alternatively, increased solvent evaporation resulting from larger excess energies upon photoexcitation or major solvent reorganization on the ionized state could account for the observed solvent-selectivity in NaI cluster multiphoton ionization.