Coordination polymer glass from a protic ionic liquid: proton conductivity and mechanical properties as an electrolyte.

High proton conducting electrolytes with mechanical moldability are a key material for energy devices. We propose an approach for creating a coordination polymer (CP) glass from a protic ionic liquid for a solid-state anhydrous proton conductor. A protic ionic liquid (dema)(HPO), with components which also act as bridging ligands, was applied to construct a CP glass (dema)[Zn(HPO)(HPO)].

A New Dimension for Coordination Polymers and Metal-Organic Frameworks: Towards Functional Glasses and Liquids.

There are two categories of coordination polymers (CPs): inorganic CPs (i-CPs) and organic ligand bridged CPs (o-CPs). Based on the successful crystal engineering of CPs, we here propose noncrystalline states and functionalities as a new research direction for CPs. Control over the liquid or glassy states in materials is essential to obtain specific properties and functions.

A Dual-Ligand Porous Coordination Polymer Chemiresistor with Modulated Conductivity and Porosity.

Single-ligand-based electronically conductive porous coordination polymers/metal-organic frameworks (EC-PCPs/MOFs) fail to meet the requirements of numerous electronic applications owing to their limited tunability in terms of both conductivity and topology. In this study, a new 2D π-conjugated EC-MOF containing copper units with mixed trigonal ligands was developed: Cu (HHTP)(THQ) (HHTP=2,3,6,7,10,11-hexahydrotriphenylene, THQ=tetrahydroxy-1,4-quinone). The modulated conductivity (σ≈2.

Crystal melting and glass formation in copper thiocyanate based coordination polymers.

Crystal melting and glass formation of coordination polymers (CPs) and metal-organic frameworks (MOFs) are rare thermal events. To expand the library of melting CP/MOFs, we utilized anti-crystal engineering in ionic liquids to construct CPs. A combination of Cu+ and 4,4'-bipyridin-1-ium derivatives afforded four melting CPs showing stable liquid and glassy states.

Author Correction: Chemical Adsorption and Physical Confinement of Polysulfides with the Janus-faced Interlayer for High-performance Lithium-Sulfur Batteries.

A correction to this article has been published and is linked from the HTML and PDF versions of this paper. The error has been fixed in the paper.

Chemical Adsorption and Physical Confinement of Polysulfides with the Janus-faced Interlayer for High-performance Lithium-Sulfur Batteries.

We design the Janus-like interlayer with two different functional faces for suppressing the shuttle of soluble lithium polysulfides (LPSs) in lithium-sulfur batteries (LSBs). At the front face, the conductive functionalized carbon fiber paper (f-CFP) having oxygen-containing groups i.e.

A proton-hopping charge storage mechanism of ionic one-dimensional coordination polymers for high-performance supercapacitors.

A proton-conducting coordination polymer of anionic one-dimensional (1D) chains of Zn phosphate and protonated imidazole with the formula of [Zn(HPO)(HPO)](ImH) has been used as a novel supercapacitor material in aqueous electrolytes. This material stores charges via a proton-hopping mechanism.

Synthesis of Oligodiacetylene Derivatives from Flexible Porous Coordination Frameworks.

Oligodiacetylenes (ODAs) with alternating ene-yne conjugated structure are significant materials for optical and electronic properties. Due to the low solubility of ODAs in common solvents, the synthetic approaches are limited. Here we disclose a new synthetic approach of ODAs without a side alkyl chain using a porous coordination polymer (PCP) as a sacrificial template.

Increase in Electrical Conductivity of MOF to Billion-Fold upon Filling the Nanochannels with Conducting Polymer.

Redox-active pyrrole (Py) monomers were intercalated into 1D nanochannels of [Cd(NDC)0.5(PCA)]·Gx (H2NDC = 2,6-napthalenedicarboxylic acid, HPCA = 4-pyridinecarboxylic acid, G = guest molecules) (1) - a fluorescent 3D MOF (λem = 385 nm). Subsequent activation of 1⊃Py upon immersing into iodine (I2) solution resulted in an increment of the bulk electrical conductivity by ∼9 orders of magnitude.

Encapsulating Mobile Proton Carriers into Structural Defects in Coordination Polymer Crystals: High Anhydrous Proton Conduction and Fuel Cell Application.

We describe the encapsulation of mobile proton carriers into defect sites in nonporous coordination polymers (CPs). The proton carriers were encapsulated with high mobility and provided high proton conductivity at 150 °C under anhydrous conditions. The high proton conductivity and nonporous nature of the CP allowed its application as an electrolyte in a fuel cell.

High hydroxide conductivity in a chemically stable crystalline metal-organic framework containing a water-hydroxide supramolecular chain.

A chemically stable cationic MOF encapsulating an in situ formed water-hydroxide supramolecular anionic chain is realized for high hydroxide (OH(-)) ion conductivity in the solid-state (Type A). High OH(-) ion conductivity and low activation energy of the MOF demonstrate the advantage of the in situ incorporation of OH(-) ions to achieve efficient OH(-) ion conduction in the solid-state.

A Nitro-Functionalized Metal-Organic Framework as a Reaction-Based Fluorescence Turn-On Probe for Rapid and Selective H2 S Detection.

The toxic gas H2 S has recently emerged as one of the important signaling molecules in biological systems. Thus understanding the production, distribution, and mode of action of H2 S in biological system is important, but the fleeting and reactive nature of H2 S makes it a daunting task. Herein we report a biocompatible, nitro-functionalized metal-organic framework as reaction-based fluorescence turn-on probe for fast and selective H2 S detection.

Aqueous phase selective detection of 2,4,6-trinitrophenol using a fluorescent metal-organic framework with a pendant recognition site.

Prompt and selective detection of nitro explosives in the aqueous phase is in high demand to meet homeland security and environmental concerns. Herein we report the chemically stable porous metal organic framework UiO-68@NH2 with a pendant recognition site for selective detection of the nitro-aromatic explosive TNP in the aqueous phase. The pendant Lewis basic amine moieties are expected to selectively interact with TNP via electrostatic interactions and act as recognition sites for TNP.

Metal-organic framework based highly selective fluorescence turn-on probe for hydrogen sulphide.

Hydrogen sulphide (H2S) is known to play a vital role in human physiology and pathology which stimulated interest in understanding complex behaviour of H2S. Discerning the pathways of H2S production and its mode of action is still a challenge owing to its volatile and reactive nature. Herein we report azide functionalized metal-organic framework (MOF) as a selective turn-on fluorescent probe for H2S detection.

A fluorescent metal-organic framework for highly selective detection of nitro explosives in the aqueous phase.

Selective and sensitive nitro explosive detection by a porous luminescent metal-organic framework has been reported. For the first time MOF based selective explosive detection in the presence of other nitro analytes in aqueous media is demonstrated.

Stimulus-responsive metal-organic frameworks.

Materials that can recognize the changes in their local environment and respond by altering their inherent physical and/or chemical properties are strong candidates for future "smart" technology materials. Metal-organic frameworks (MOFs) have attracted a great deal of attention in recent years owing to their designable architecture, host-guest chemistry, and softness as porous materials. Despite this fact, studies on the tuning of the properties of MOFs by external stimuli are still rare.

Two-in-one: inherent anhydrous and water-assisted high proton conduction in a 3D metal-organic framework.

The development of solid-state proton-conducting materials with high conductivity that operate under both anhydrous and humidified conditions is currently of great interest in fuel-cell technology. A 3D metal-organic framework (MOF) with acid-base pairs in its coordination space that efficiently conducts protons under both anhydrous and humid conditions has now been developed. The anhydrous proton conductivity for this MOF is among the highest values that have been reported for MOF materials, whereas its water-assisted proton conductivity is comparable to that of the organic polymer Nafion, which is currently used for practical applications.

Structural dynamism and controlled chemical blocking/unblocking of active coordination space of a soft porous crystal.

A three-dimensional biporous soft porous coordination polymer containing active coordination space, made of cadmium(II) and a tripodal carboxylate ligand bearing ether linkages, was synthesized and characterized. Guest-dependent dynamic activities in the active coordination space of the soft porous crystal have been explored. We have demonstrated controlled chemical blocking and unblocking of active pores of the dynamic framework along with guest-dependent contraction and expansion of the channels by single-crystal-to-single-crystal structural transformation studies.

Amino acid based dynamic metal-biomolecule frameworks.

On the move: Two isostructural, homochiral Cu(II) coordination frameworks based on amino acids (D- and L-PGA) were synthesized. Dynamic behavior by solid-state structural transformation in single-crystal-to-single-crystal fashion was demonstrated. The extent of structural dynamism was shown by guest inclusion studies.

Zn(II) coordination polymer of an in situ generated 4-pyridyl (4Py) attached bis(amido)phosphate ligand, [PO2(NH4Py)2]- showing preferential water uptake over aliphatic alcohols.

Two polymorphic 2D-coordination polymers of composition [ZnL(HCO2)]∞ were synthesized from an in situ generated ligand [PO2(NH(4)Py)2](-) (L(-)). The ligand L(-) was generated by a facile metal-assisted P-N bond hydrolysis reaction from the corresponding phosphonium salt 1, [P(NH(4)Py)4]Cl, or from the neutral phosphoric triamide 2, [PO(NH(4)Py)3]. The de-solvated sample of the polymer [ZnL(HCO2)]∞ features polar micropores and shows a type I isotherm for CO2 sorption whereas a type II behaviour was observed for N2.

Bistable dynamic coordination polymer showing reversible structural and functional transformations.

A bistable dynamic coordination polymer [Ni(pca)(bdc)(0.5)(H(2)O)(2)] having a two-dimensional (2D) zigzag sheet structure is synthesized solvothermally. Topological analysis revealed that the frameworks have an hcb type of uninodal net.

Selective CO2 adsorption in a robust and water-stable porous coordination polymer with new network topology.

A robust and water-stable porous coordination polymer [Cd(NDC)(0.5)(PCA)]·G(x) (1) (H(2)NDC = 2,6-napthalenedicarboxylic acid, HPCA = 4-pyridinecarboxylic acid, G = guest molecules) with new network topology has been synthesized solvothermally. The framework is 3D porous material and forms a 1D channel along the c-axis, with the channel dimensions ~9.