Selective CO2 adsorption and proton conductivity in the two-dimensional Zn(ii) framework with protruded water molecules and flexible ether linkers

A novel 2D nickel(ii) complex (1) has been successfully synthesized using a 2,2′-bipyridyl, polycarboxylsulfonate ligand H4SBTC and Ni2+ ions. Owing to the presence of abundant water molecules, hydrogen bond networks and other protons, 1 and its hybrid membranes demonstrate high proton conductivity.

Download Full-text

Crystal structures of {[Cu(Lpn)2][Fe(CN)5(NO)]·H2O}nand {[Cu(Lpn)2]3[Cr(CN)6]2·5H2O}n[where Lpn = (R)-propane-1,2-diamine]: two heterometallic chiral cyanide-bridged coordination polymers

Acta Crystallographica Section E Crystallographic Communications ◽

10.1107/s2056989015005253 ◽

2015 ◽

Vol 71 (4) ◽

pp. 392-397

Author(s):

Olha Sereda ◽

Helen Stoeckli-Evans

Keyword(s):

Hydrogen Bonds ◽

Coordination Polymers ◽

Three Dimensional ◽

Water Molecules ◽

Two Dimensional ◽

Asymmetric Unit ◽

Compound I ◽

Distorted Octahedral ◽

Coordination Spheres ◽

Compound Ii

The title compounds,catena-poly[[[bis[(R)-propane-1,2-diamine-κ2N,N′]copper(II)]-μ-cyanido-κ2N:C-[tris(cyanido-κC)(nitroso-κN)iron(III)]-μ-cyanido-κ2C:N] monohydrate], {[Cu(Lpn)2][Fe(CN)5(NO)]·H2O}n, (I), and poly[[hexa-μ-cyanido-κ12C:N-hexacyanido-κ6C-hexakis[(R)-propane-1,2-diamine-κ2N,N′]dichromium(III)tricopper(II)] pentahydrate], {[Cu(Lpn)2]3[Cr(CN)6]2·5H2O}n, (II) [where Lpn = (R)-propane-1,2-diamine, C3H10N2], are new chiral cyanide-bridged bimetallic coordination polymers. The asymmetric unit of compound (I) is composed of two independent cation–anion units of {[Cu(Lpn)2][Fe(CN)5)(NO)]} and two water molecules. The FeIIIatoms have distorted octahedral geometries, while the CuIIatoms can be considered to be pentacoordinate. In the crystal, however, the units align to form zigzag cyanide-bridged chains propagating along [101]. Hence, the CuIIatoms have distorted octahedral coordination spheres with extremely long semicoordination Cu—N(cyanido) bridging bonds. The chains are linked by O—H...N and N—H...N hydrogen bonds, forming two-dimensional networks parallel to (010), and the networks are linkedviaN—H...O and N—H...N hydrogen bonds, forming a three-dimensional framework. Compound (II) is a two-dimensional cyanide-bridged coordination polymer. The asymmetric unit is composed of two chiral {[Cu(Lpn)2][Cr(CN)6]}−anions bridged by a chiral [Cu(Lpn)2]2+cation and five water molecules of crystallization. Both the CrIIIatoms and the central CuIIatom have distorted octahedral geometries. The coordination spheres of the outer CuIIatoms of the asymmetric unit can be considered to be pentacoordinate. In the crystal, these units are bridged by long semicoordination Cu—N(cyanide) bridging bonds forming a two-dimensional network, hence these CuIIatoms now have distorted octahedral geometries. The networks, which lie parallel to (10-1), are linkedviaO—H...O, O—H...N, N—H...O and N—H...N hydrogen bonds involving all five non-coordinating water molecules, the cyanide N atoms and the NH2groups of the Lpn ligands, forming a three-dimensional framework.

Download Full-text

Crystal structure of the new hybrid material bis(1,4-diazoniabicyclo[2.2.2]octane) di-μ-chlorido-bis[tetrachloridobismuthate(III)] dihydrate

Acta Crystallographica Section E Crystallographic Communications ◽

10.1107/s2056989015019933 ◽

2015 ◽

Vol 71 (11) ◽

pp. 1384-1387

Author(s):

Marwen Chouri ◽

Habib Boughzala

Keyword(s):

Crystal Structure ◽

Aqueous Solution ◽

Hydrogen Bonds ◽

Room Temperature ◽

Molar Ratio ◽

Water Molecules ◽

Site Symmetry ◽

Two Dimensional ◽

Slow Evaporation ◽

Solution Ph

The title compound bis(1,4-diazoniabicyclo[2.2.2]octane) di-μ-chlorido-bis[tetrachloridobismuthate(III)] dihydrate, (C6H14N2)2[Bi2Cl10]·2H2O, was obtained by slow evaporation at room temperature of a hydrochloric aqueous solution (pH = 1) containing bismuth(III) nitrate and 1,4-diazabicyclo[2.2.2]octane (DABCO) in a 1:2 molar ratio. The structure displays a two-dimensional arrangement parallel to (100) of isolated [Bi2Cl10]4−bioctahedra (site symmetry -1) separated by layers of organic 1,4-diazoniabicyclo[2.2.2]octane dications [(DABCOH2)2+] and water molecules. O—H...Cl, N—H...O and N—H...Cl hydrogen bonds lead to additional cohesion of the structure.

Download Full-text

Waterproof molecular monolayers stabilize 2D materials

Proceedings of the National Academy of Sciences ◽

10.1073/pnas.1909500116 ◽

2019 ◽

Vol 116 (42) ◽

pp. 20844-20849 ◽

Cited By ~ 4

Author(s):

Cong Su ◽

Zongyou Yin ◽

Qing-Bo Yan ◽

Zegao Wang ◽

Hongtao Lin ◽

...

Keyword(s):

Transition Metal ◽

Theoretical Analysis ◽

2D Materials ◽

Transition Metal Dichalcogenides ◽

Water Molecules ◽

Two Dimensional ◽

Ambient Conditions ◽

Molecular Monolayers ◽

Metal Dichalcogenides ◽

Van Der Waals Materials

Two-dimensional van der Waals materials have rich and unique functional properties, but many are susceptible to corrosion under ambient conditions. Here we show that linear alkylamines n-CmH2m+1NH2, with m = 4 through 11, are highly effective in protecting the optoelectronic properties of these materials, such as black phosphorus (BP) and transition-metal dichalcogenides (TMDs: WS2, 1T′-MoTe2, WTe2, WSe2, TaS2, and NbSe2). As a representative example, n-hexylamine (m = 6) can be applied in the form of thin molecular monolayers on BP flakes with less than 2-nm thickness and can prolong BP’s lifetime from a few hours to several weeks and even months in ambient environments. Characterizations combined with our theoretical analysis show that the thin monolayers selectively sift out water molecules, forming a drying layer to achieve the passivation of the protected 2D materials. The monolayer coating is also stable in air, H2 annealing, and organic solvents, but can be removed by certain organic acids.

Download Full-text

ELECTRO-OSMOTIC FRACTIONATION OF HYDROGEN ISOTOPES IN ELECTROLYTIC SOLUTIONS USING COMPOSITE PROTON-PERMEABLE MEMBRANES

Visnyk of Taras Shevchenko National University of Kyiv Geology ◽

10.17721/1728-2713.92.02 ◽

2021 ◽

pp. 11-16

Author(s):

O. Pushkar'ov ◽

A. Zubko ◽

I. Sevruk ◽

V. Dolin

Keyword(s):

Hydrogen Bonds ◽

Proton Conductivity ◽

Tritiated Water ◽

High Mobility ◽

Hydrogen Isotopes ◽

Water Molecules ◽

Proton Conducting ◽

Partial Dissociation ◽

Surface Modified ◽

Conducting Membranes

Based on the analysis of the features of electroosmotic processes that are implemented in proton-conducting membranes, the possibility of fractioning hydrogen isotopes in electrolytes formed using tritiated water (HTO) is estimated. The interaction of the solution with the membranes in their channels leads to polarization and partial dissociation of the electrolyte molecules. In water molecules, when protium is replaced by a heavy isotope of hydrogen, the energy of breaking of hydrogen bonds increases and the process of their dissociation proceeds predominantly according to the scheme: HTO ↔ H+ + TO—. A part of the released protons can join water molecules to form the H3O+ ion. H3O+ and TO— ions are more mobile than other singly charged ions. The main characteristic that determines the suitability of electroosmotic membranes to the fractionation of hydrogen isotopes is proton conductivity. The released protons have anomalously high mobility due to their small size, tunnel and relay movement through hydrogen bonds between adjacent polar groups in the channels of the proton-conducting membranes. To ensure high proton conductivity in the pores and channels of the membranes, modifying substances are fixed, which contain the groups: –ОН- , –NH2, –NH, –SH, –COOH, –SO3H, acid salts and oxides, containing surface proton-conducting groups. To create proton-conducting membranes, it is possible to use surface-modified β-alumina (β-Al2O3(H3O+)) and protonated (H3O+) montmorillonite with ionic conductivity (5х103 – 4х104 Ohm х cm–1). The most effective are surface modifiers with negatively charged sulfonic groups. The imposition of an external electric field leads to the movement of ions in the electrolyte, which leads to a redistribution of the isotope ratio in the near-anode and cathode spaces.

Download Full-text

Crystal structures of 2-methylpyridinium hydrogen 2,3-bis(4-methylbenzoyloxy)succinate and bis-[4-methylpyridinium hydrogen 2,3-bis(4-methylbenzoyloxy)succinate] pentahydrate

Acta Crystallographica Section E Crystallographic Communications ◽

10.1107/s2056989017012981 ◽

2017 ◽

Vol 73 (10) ◽

pp. 1483-1487

Author(s):

P. Sivakumar ◽

S. Israel ◽

G. Chakkaravarthi

Keyword(s):

Hydrogen Bonds ◽

Pyridine Ring ◽

Crystal Packing ◽

Water Molecules ◽

Two Dimensional ◽

Asymmetric Unit ◽

Aromatic Rings ◽

Π Interactions ◽

Dimensional Network ◽

Anions And Cations

The title salt (I), C6H8N+·C20H17O8−, comprises a 2-methylpyridinium cation and a 2,3-bis(4-methylbenzoyloxy)succinate mono-anion while the salt (II), 2C6H8N+·2C20H17O8−·5H2O, consists of a pair of 4-methylpyridinium cations and 2,3-bis(4-methylbenzoyloxy)succinate mono-anions and five water molecules of solvation in the asymmetric unit. In (I), the dihedral angle between the aromatic rings of the anion is 40.41 (15)°, comparing with 43.0 (3) and 85.7 (2)° in the conformationally dissimilar anion molecules in (II). The pyridine ring of the cation in (I) is inclined at 23.64 (16) and 42.69 (17)° to the two benzene moieties of the anion. In (II), these comparative values are 4.7 (3), 43.5 (3)° and 43.5 (3), 73.1 (3)° for the two associated cation and anion pairs. The crystal packing of (I) is stabilized by inter-ionic N—H...O, O—H...O and C—H...O hydrogen bonds as well as weak C—H...π interactions, linking the ions into infinite chains along [100]. In the crystal packing of (II), the anions and cations are also linked by N—H...O and O—H...O hydrogen bonds involving also the water molecules, giving a two-dimensional network across (001). The crystal structure is also stabilized by weak C—H...O and C—H...π interactions.

Download Full-text

The Layered Structure of Cu2(H2O)4[C4H4N2][C6H2(COO)4]·2H2O

10.31219/osf.io/456p8 ◽

2019 ◽

Author(s):

Roberto Köferstein

Keyword(s):

Nitrogen Atom ◽

Single Crystals ◽

Silica Gel ◽

Layered Structure ◽

Water Molecules ◽

Two Dimensional ◽

Space Group ◽

Distorted Octahedral ◽

Oxygen Atoms

Triclinic single crystals of Cu2(H2O)4[C4H4N2][C6H2(COO)4]·2H2O have been grown in anaqueous silica gel. Space group P-1 (Nr. 2), a = 723.94(7) pm, b = 813.38(14) pm, c = 931.0(2) pm, α = 74.24(2)°, β = 79.24(2)°, γ = 65.451(10)°, V = 0.47819(14) nm3, Z = 1. Cu2+ is coordinated in a distorted, octahedral manner by two water molecules, three oxygen atoms ofthe pyromellitate anions and one nitrogen atom of pyrazine (Cu—O 194.1(2)–229.3(3) pm;Cu–N 202.0(2) pm). The connection of Cu2+ and [C6H2(COO)4)]4− yields infinite strands,which are linked by pyrazine molecules to form a two-dimensional coordination polymer.Thermogravimetric analysis in air showed that the dehydrated compound was stable between175 and 248 °C. Further heating yielded CuO.

Download Full-text

V2O2F4(H2O)2·H2O: a new V4+layer structure related to VOF3

Acta Crystallographica Section C Structural Chemistry ◽

10.1107/s2053229615024122 ◽

2016 ◽

Vol 72 (1) ◽

pp. 80-83 ◽

Cited By ~ 2

Author(s):

Cameron Black ◽

Philip Lightfoot

Keyword(s):

Ionic Liquids ◽

Title Compound ◽

Solvothermal Synthesis ◽

Layer Structure ◽

Three Dimensional ◽

Water Molecules ◽

Frustrated Magnets ◽

Two Dimensional ◽

Triangular Lattices ◽

Solvothermal Conditions

VIVoxyfluorides are of interest as frustrated magnets. The successful synthesis of two-dimensionally connected vanadium(IV) oxyfluoride structures generally requires the use of ionic liquids as solvents. During solvothermal synthesis experiments aimed at producing two- and three-dimensional vanadium(IV) selenites with triangular lattices, the title compound, diaquatetra-μ-fluorido-dioxidodivanadium(IV) monohydrate, V2O2F4(H2O)2·H2O, was discovered and features a new infinite V4+-containing two-dimensional layer comprised of fluorine-bridged corner- and edge-sharing VOF4(H2O) octahedral building units. The synthesis was carried out under solvothermal conditions. The V4+centre exhibits a typical off-centring, with a short V=O bond and an elongatedtrans-V—F bond. Hydrogen-bonded water molecules occur between the layers. The structure is related to previously reported vanadium oxyfluoride structures, in particular, the same layer topology is seen in VOF3.

Download Full-text

Diaquabis[N-(2-fluorobenzyl)-N-nitrosohydroxylaminato-κ2O,O′]nickel(II)

Acta Crystallographica Section E Structure Reports Online ◽

10.1107/s1600536814002876 ◽

2014 ◽

Vol 70 (3) ◽

pp. m98-m99

Author(s):

Olga Kovalchukova ◽

Ali Sheikh Bostanabad ◽

Adam Stash ◽

Svetlana Strashnova ◽

Igor Zyuzin

Keyword(s):

Hydrogen Bonds ◽

Organic Ligands ◽

Water Molecules ◽

Chelating Ligands ◽

Two Dimensional ◽

Organic Species ◽

Octahedral Environment ◽

Dimensional Network ◽

Distorted Octahedral ◽

Coordinated Water

In the centrosymmetric title compound, [Ni(C7H6FN2O2)2(H2O)2], the NiIIcation is in a slightly distorted octahedral environment and is surrounded by four O atoms from the N—O groups of the organic ligands [Ni—O = 2.0179 (13) and 2.0283 (12) Å], and two water molecules [Ni—O = 2.0967 (14) Å]. TheN-(2-fluorobenzyl)-N-nitrosohydroxylaminate monoanions act as bidentate chelating ligands. In the crystal, the Ni cations in the columns are shifted in such a way that the coordinated water molecules are involved in the formation of hydrogen bonds with the O atoms of the organic species of neighbouring molecules. Thus, a two-dimensional network parallel to (100) is built up by hydrogen-bonded molecules.

Download Full-text

A two-dimensional silver(I) coordination polymer constructed from 4-aminophenylarsonate and triphenylphosphane: poly[[(μ3-4-aminophenylarsonato-κ3N:O:O)(triphenylphosphane-κP)silver(I)] monohydrate]

Acta Crystallographica Section C Structural Chemistry ◽

10.1107/s2053229615003885 ◽

2015 ◽

Vol 71 (4) ◽

pp. 258-261 ◽

Cited By ~ 1

Author(s):

Zu-Ping Xiao ◽

Meng Wen ◽

Chun-Ya Wang ◽

Xi-He Huang

Keyword(s):

Hydrogen Bonding ◽

Coordination Mode ◽

Aqueous Ammonia ◽

Van Der Waals Interactions ◽

Water Molecules ◽

Stacking Interactions ◽

Two Dimensional ◽

Solvent Water ◽

Hydrogen Bonding Interactions ◽

Amine Groups

The title compound, {[Ag(C6H7AsNO3)(C18H15P)]·H2O}n, has been synthesized from the reaction of 4-aminophenylarsonic acid with silver nitrate, in aqueous ammonia, with the addition of triphenylphosphane (PPh3). The AgIcentre is four-coordinated by one amino N atom, one PPh3P atom and two arsonate O atoms, forming a severely distorted [AgNPO2] tetrahedron. Two AgI-centred tetrahedra are held together to produce a dinuclear [Ag2O2N2P2] unit by sharing an O–O edge. 4-Aminophenylarsonate (Hapa−) adopts a μ3-κ3N:O:O-tridentate coordination mode connecting two dinuclear units, resulting in a neutral [Ag(Hapa)(PPh3)]nlayer lying parallel to the (10\overline{1}) plane. The PPh3ligands are suspended on both sides of the [Ag(Hapa)(PPh3)]nlayer, displaying up and down orientations. There is anR22(8) hydrogen-bonded dimer involving two arsonate groups from two Hapa−ligands related by a centre of inversion. Additionally, there are hydrogen-bonding interactions involving the solvent water molecules and the arsonate and amine groups of the Hapa−ligands, and weak π–π stacking interactions within the [Ag(Hapa)(PPh3)]nlayer. These two-dimensional layers are further assembled by weak van der Waals interactions to form the final architecture.

Download Full-text