Confining Liquid Electrolytes in a Nitrogen-Rich Nanoporous Carbon Sponge for Superior Lithium-Ion Conduction.

Solid-state Li-ion batteries are recognized as highly promising energy storage devices due to their ability to overcome issues related to the inferior cycle life and potential risks of traditional liquid Li-ion batteries. However, developing solid-state electrolytes with fast Li-ion conductivity continues to be a major challenge. In this study, we present a family of quasi-solid-state electrolytes (QSSEs) synthesized by confining liquid electrolytes within a N-rich porous carbon sponge, exhibiting superior Li-ion conduction for solid-state battery applications.

A Superior Ionic Conducting Plastic Crystal Near Room Temperature with Electrical Bistability and Magnetic Transition.

Multifunctional ionic plastic crystals (IPCs) are a class of unique materials that exhibit a wide range of advanced applications. In this work, we proposed a strategy for the design of multifunctional, superior ion-conducting IPCs with bistability in both magnetic and electric properties, moreover, we successfully prepared and thoroughly characterized such an IPC, [PMPyr][Ni(mnt)] (1; PMPyr=N-propyl-N-methylpyrrolidinium, and mnt=maleonitriledithiolate). Plastic crystal 1 exhibits superior ion conduction near room temperature, and its ion conductivity reaches the order of 10 S cm at 373 K.

Polymorph transformation in a mixed-stacking nickel-dithiolene complex with the derivative of 4,4'-bipyridinium.

In this study, two polymorphs of the [1,1'-dibutyl-4,4'-bipyridinium][Ni(mnt)] salt () were synthesized. The dark-green polymorph (designated as 1-g) was prepared under ambient conditions by the rapid precipitation method in aqueous solutions. Subsequently, the red polymorph (labeled as 1-r) was obtained by subjecting 1-g to ultrasonication in MeOH at room temperature.

Thermochromism of rapid responses to temperature changes mechanochromism in a Ni-dithiolene complex salt.

A thermochromic or mechanochromic material can switch between at least two stable states in response to changes in temperature or static pressure/strain. In this study, we investigated a Ni-dithiolene dianion salt, 1,1'-diheptyl-4,4'-bipyridinium bis(maleonitriledithiolato)nickelate (1), and found that its cations and anions stack alternately to form a uniform mixed stack. These mixed stacks then combine to form a molecular solid through Coulomb and van der Waals interactions.

synthesis of hierarchical NiCo-MOF@NiCo(OH) heterostructures for enhanced pseudocapacitor and oxygen evolution reaction performances.

Integrating the merits of different components to construct heterostructures for energy storage and conversion has attracted intensive attention. Herein, taking advantage of bimetallic MOFs and transition bimetal hydroxide, we have successfully used nanoflower-like Ni1-xCox(OH)2 as both the precursor and template to in situ construct three dimensional (3D) NiCo-MOF@Ni1-xCox(OH)2 (denoted as MOF@TMH) hierarchical heterostructures. Benefiting from the optimized composition with hierarchical heterostructures assembled by ultrathin nanosheets, MOF@TMH-2 possesses rich effective active sites and high electrochemical reactivity, delivering superior pseudocapacitor performance with a specific capacitance of 1855.

A 3D open-framework iron hydrogenophosphate showing high proton conductance under water and aqua-ammonia vapor.

Herein we report the first example of the proton conductivity of an open-framework metal phosphate (NH(CH)NH)-[Fe(OH)(HPO)(PO)]·4HO under aqua-ammonia vapor. Its optimized proton conductivity is 5 × 10 S cm at 313 K and aqua-ammonium vapor from 1 M NH·HO solution. That is approximately two orders of magnitude greater than the maximum value under water vapor (8.

Dielectric Relaxation and Beyond Limiting Behavior of Alternating-Current Conductivity in a Supermolecular Ferroelectric.

A cyclen-based hybrid supermolecule crystal, [(FeCl )(cyclen)]Cl (1), where cyclen=1,4,7,10-tetraazacyclododecane, was prepared using a liquid-liquid diffusion approach. The variable crystal structures exhibit that compound 1 belongs to an orthorhombic crystal system, Pna2 space group (point group C ) in the temperature range of 150-400 K. This hybrid supermolecule shows a dielectric relaxation behavior around room temperature, and the ferroelectric nature of 1 has been directly verified by hysteresis measurements.

Wide Magnetic Thermal Memory Effect (∼55 K) Above Room Temperature Coupled to a Structure Phase Transition of Lattice Symmetry Reduction in High-Temperature Phase in an S = 1/2 Spin Chain Molecule Crystal.

One-dimensional (1D) S = 1/2 Heisenberg antiferromagnetic (AFM) chain system shows frequently a spin-Peierls-type transition owing to strong spin-lattice coupling. From high-temperature phase (HTP) to low-temperature phase (LTP), the spin chain distortion leads to the reduction in lattice symmetry in LTP, called the symmetry breaking (SB) phase transition. Herein, we report the first example of 1D S = 1/2 AFM molecular crystal, [Et( n-Pr)N][Ni(dmit)] (Et( n-Pr)N = triethylpropylammonium, dmit = 2-thioxo-1,3-dithiole-4,5-dithiolate), which shows a structural phase transition with lattice symmetry increase in LTP, which is contrary to the SB phase transition.

Extra Water- and Acid-Stable MOF-801 with High Proton Conductivity and Its Composite Membrane for Proton-Exchange Membrane.

Proton-exchange membranes (PEMs), characterized by selectively permitting the transfer of protons and acting as a separator in electrochemical devices, have attracted immense attention. The composite membrane, fabricated from organic polymer matrix and high proton-conducting metal-organic framework (MOF), integrates the excellent physical and chemical performances of the polymer and MOF, achieving collective properties for good-performance PEMs. In this study, we demonstrate that MOF-801 shows remarkable proton conductance with σ = 1.

[(18-Crown-6)K][Fe(1)Cl(1) ] [Fe(2)Cl(2) ] : A Multifunctional Molecular Switch of Dielectric, Conductivity and Magnetic Properties.

Multifunctional materials that exhibit different physical properties in a single phase have potential for use in multifunctional devices. Herein, we reported an organic-inorganic hybrid compound [(18-crown-6)K][Fe(1)Cl(1) ] [Fe(2)Cl(2) ] (1) by incorporating KCl and FeCl into a 18-crown-6 molecule, which acts as a host of the six O atoms providing a lone pair of electrons to anchor the guest potassium cation, and [FeCl ] as a counterion for charge balance to construct a complex salt. This salt exhibited a one-step reversible structural transformation giving two separate high and low temperature phases at 373 K, which was confirmed by systematic characterizations including differential scanning calorimetry (DSC) measurements, variable-temperature structural analyses, and dielectric, impedance, variable-temperature magnetic susceptibility measurements.

Open-Framework Chalcogenide Showing Both Intrinsic Anhydrous and Water-Assisted High Proton Conductivity.

Proton-conducting materials have attracted increasing interest because of the promising technological applications as key components in various electrochemical devices. It is of great significance for technique application to seek superior proton-conducting materials, operating under both anhydrous and humidified conditions in a wide temperature range. Herein we demonstrate the proton conductance of an open-framework chalcogenide, (CHNH)AgSnS (1), and the postsynthesis product 2 achieved by doping hydrochloric acid into 1.

Both Dielectrics and Conductance Anomalies in an Open-Framework Cobalt Phosphate.

Switchable conducting or dielectric materials, as the key component, show important technological applications in modern electrical and electronic devices, including data communication, phase shifters, varactors, and rewritable optical data storage. To explore new types of switchable conducting or dielectric materials could significantly accelerate the development of efficient electrical and electronic devices. Herein we present the first example of switchable conducting and dielectric material, which is based on an open-framework phosphate, (CNH)CoPO.

Proton Conductance of a Superior Water-Stable Metal-Organic Framework and Its Composite Membrane with Poly(vinylidene fluoride).

Proton-exchange membranes (PEMs) as separators have important technological applications in electrochemical devices, including fuel cells, electrochemical sensors, electrochemical reactors, and electrochromic displays. The composite membrane of a proton-conducting metal-organic framework (MOF) and an organic polymer combines the unique physical and chemical nature of the polymer and the high proton conductivity of the MOF, bringing together the best of both components to potentially fabricate high-performance PEMs. In this study, we have investigated the proton-transport nature of a zirconium(IV) MOF, MOF-808 (1).

Water assisted high proton conductance in a highly thermally stable and superior water-stable open-framework cobalt phosphate.

Proton-conducting materials show important technological applications as key components in energy conversion, electrochemical sensing and electrochromic devices; the exploration for new types of proton-conducting materials is crucial for the development of efficient electrochemical devices. In this study, we investigated the proton transport nature of an inorganic-organic hybrid crystal of open-framework cobalt phosphate, (CNH)CoPO. The structure of the hybrid crystal consists of the [CoPO] anionic framework, and the proton carriers, Hen cations (en = ethylenediamine), are located in the pores to compensate the negative charges of the inorganic framework.

Three orders of magnitude enhancement of proton conductivity of porous coordination polymers by incorporating ion-pairs into a framework.

A clathrate NH4Br@HKUST-1 has been prepared by means of soaking the metal-organic-framework, HKUST-1, in ammonium bromide saturated ethanol solution at ambient temperature. Both NH4Br@HKUST-1 and HKUST-1 show the same framework structure. The formula of the clathrate is approximately expressed as Cu3(BTC)2(NH4Br)1.

Investigation of the structure and ionic conductivity of intercalated kaolinites with potassium acetate in hydrous and anhydrous phases.

The intercalated kaolinite with potassium acetate (K-KAc), with ca. 91.9% intercalation ratio, was prepared.

Crystal structure of bis-[1-(4-bromo-benz-yl)pyridinium] bis-(1,2-di-cyano-ethene-1,2-di-thiol-ato-κ(2) S,S')nickelate(II).

The asymmetric unit of the title salt, (C12H11BrN)2[Ni(C4N2S2)2], consists of one 1-(4-bromo-benz-yl)pyridinium cation and one half of a complex [Ni(mnt)2](2-) (mnt(2-) is the maleo-nitrile-dithiol-ate dianion). The Ni(2+) ion is located on an inversion centre and is coordinated by four S atoms from two mnt(2-) ligands, exhibiting a square-planar coordination environment. In the cation, the planes of the pyridinium and benzene rings make a dihedral angle of 69.

Observation of intramolecular vibrations cooperating with the magnetic phase transition in a nickel-bis-dithiolene compound.

A new one-dimensional (1-D) ion-pair compound, [1,7-bis(1-methylimidazolium)heptane][Ni(mnt)(2)](2) (mnt(2-) = maleonitriledithiolate), was synthesized and characterized structurally and magnetically. This compound shows a spin-Peierls-type transition at around 235 K. Its crystal structure belongs to the monoclinic system with space group C2/c and the magnetic [Ni(mnt)(2)](-) anions form uniform stacks in the high-temperature (HT) phase.

Observation of divergent isotope effects as well as metal ion-modulated T(C) and spin-canting nature in isostructural supramolecular magnets.

The ion-pair complexes of [4-NH(2)-PyH][M(mnt)(2)] (M = Pt for 1 and Ni for 3) and their deuterated analogues [4-NH(2)-PyD][M(mnt)(2)] (M = Pt for 2 and Ni for 4) are isostructural with each other. Four complexes crystalline in monoclinic space group C2/c, whose asymmetric unit consists of two halves of [M(mnt)(2)](-) anions and one cation, show quite similar cell parameters and almost identical packing structures as well. In the crystals of 1-4, two types of crystallographically inequivalent [M(mnt)(2)](-) anions construct individual layers, which are separated by the cation layer; the supramolecular networks are formed via the H-bonding interactions between the [M(mnt)(2)](-) and 4-NH(2)-PyH(+) (or 4-NH(2)-PyD(+)) ions as well as the weakly ππ stacking interactions between the [M(mnt)(2)](-) anions.

Observation of metal ion dependent packing structures and magnetic behaviors of metal-bis-1, 2-dithiolene complexes.

The crystal structures and magnetic properties were investigated experimentally and theoretically for two S = ½ spin chain complexes, which consist of [M(mnt)(2)](-) (M = Pt for 1 or Pd for 2) with 1-(4'-bromo-2'-flurobenzyl)-4-aminopyridinium (1-BrFBz-4-NH(2)Py(+)). The 1-BrFBz-4-NH(2)Py(+) cations exhibit different molecular conformations and arrangements in 1 and 2; the [M(mnt)(2)](-) anions form regular stacks in 1, whereas they form irregular stacks in 2. In addition, the intermolecular interactions between the [M(mnt)(2)](-) anions and cations are also different from each other in the crystals of 1 and 2.

Stack pattern of the countercation-modulating magnetic property of low-dimensional [Pt(mnt)₂]⁻ monoanion spin systems.

Three [1-N-(4'-R-benzyl)-4-aminopyridinium][Pt(mnt)(2)] compounds were structurally and magnetically characterized, where the substituent was attached to the para-position of the phenyl ring (R = CN (1), Cl (2), and H (3); mnt(2-) = maleonitriledithiolate). 1 and 2 crystallized in the monoclinic space group P2(1)/c, with the cations and anions forming segregated columnar stacks. Their structural differences involved two aspects: (1) both anion and cation stacks were regular in 1 and irregular in 2; (2) the neighboring cations were arranged in the boat-type pattern in 1, whereas these cations were in the chair-type pattern in 2 within the cation stack.

A low-dimensional molecular spin system with two steps of magnetic transitions and liquid crystal property.

A low-dimensional compound [C(6)-Apy][Ni(mnt)(2)] (1, where mnt(2-) = maleonitriledithiolate, C(6)-Apy(+) = 4-amino-1-hexylpyridinium) has been designed and synthesized, which has layer arrangement of anions and cations and shows two steps of magnetic transitions. The low temperature magnetic transition has an uncommon hysteresis loop, while the crystal structure investigations disclosed no structural transition with the magnetic transition. The high temperature magnetic transition exhibits two remarkable features: (1) it synchronously occurs with a crystalline-to-mesophase transition in the first heating process and (2) the structural changes that accompany the solid-mesophase transition are irreversible.

Inorganic-organic hybrid compounds based on face-sharing octahedral [PbI3]∞ chains: self-assemblies, crystal structures, and ferroelectric, photoluminescence properties.

Eight inorganic-organic hybrid compounds with a formula of [R-Bz-1-APy][PbI(3)] (R-Bz-1-APy(+) = mono-substituted benzylidene-1-aminopyridinium Schiff base derivative; R = m-CN (1), m-CH(3) (2), H (3), p-F (4), p-Cl (5), p-Br (6), o-Cl (7), o-Br (8)) have been synthesized and characterized structurally. The common characteristic of the crystal structures of 1-8 is that the inorganic components form straight and face-sharing octahedral [PbI(3)](∞) chains and the Schiff base cations surround the [PbI(3)](∞) chains to form molecular stacks. The substituent (R) on the phenyl ring of the Schiff base cation clearly influences the packing structures of 1-8, and the hybrid compound crystallizes in the space group P6(3) when R = CN (1) in the meta-position of the phenyl ring, and in a central symmetric space group when R is in the ortho- or para-position of the phenyl ring.

catena-Poly[[diaqua-bis(diphenyl-acetato)-zinc(II)]-μ-4,4'-bipyridine].

In the title compound, [Zn(C(14)H(11)O(2))(2)(C(10)H(8)N(2))(H(2)O)(2)](n), the Zn(II) ion lies on a crystallographic inversion center and is in a slightly distorted octahedral coordination enviroment. 4,4'-Bipyridine ligands act as bridging ligands, connecting Zn(II) ions into a chain along the b-axis direction. In the crystal structure, these chains are linked by inter-molecular O-H⋯O hydrogen bonds to form a two-dimensional network parallel to the ab plane.

Bis[1-(2,6-dichloro-benz-yl)-3-methyl-pyrazin-1-ium] bis-(maleonitrile-dithiol-ato)nickelate(II).

In the crystal structure of the title compound, (C(12)H(11)Cl(2)N(2))(2)[Ni(C(4)N(2)S(2))(2)], the Ni(II) complex dianion is located on an inversion centre. The Ni(II) atom is coordinated by four S atoms in a square-planar geometry. In the cation, the dihedral angle between the benzene and pyrazine rings is 85.