On-Demand Tunable Electrical Conductance Anisotropy in a MOF-Polymer Composite.

Property optimization through orientation control of metal-organic framework (MOF) crystals that exhibit anisotropic crystal structures continues to garner tremendous interest. Herein, an electric field is utilized to post-synthetically control the orientation of conductive layered Cu(HHTP) (HHTP = 2,3,6,7,10,11-hexahydroxytriphenylene) crystals dispersed in an electronically insulating poly(ethylene glycol) diacrylate (PEGDA) oligomer matrix. Optical and electrical measurements are performed to investigate the impact of the electric field on the alignment of Cu(HHTP) crystals and the formation of aggregated microstructures, which leads to an ≈5000-fold increase in the conductivity of the composite.

Universal Strategy for Inorganic Nanoparticle Incorporation into Mesoporous Liquid Crystal Polymer Particles.

Developing inorganic-organic composite polymers necessitates a new strategy for effectively controlling shape and optical properties while accommodating guest materials, as conventional polymers primarily act as  carriers that transport inorganic substances. Here, a universal approach is introduced utilizing mesoporous liquid crystal polymer particles (MLPs) to fabricate inorganic-organic composites. By leveraging the liquid crystal phase, morphology and optical properties are precisely controlled through the molecular-level arrangement of the host, here monomers.

Reactive high-spin iron(IV)-oxo sites through dioxygen activation in a metal-organic framework.

In nature, nonheme iron enzymes use dioxygen to generate high-spin iron(IV)=O species for a variety of oxygenation reactions. Although synthetic chemists have long sought to mimic this reactivity, the enzyme-like activation of O to form high-spin iron(IV) = O species remains an unrealized goal. Here, we report a metal-organic framework featuring iron(II) sites with a local structure similar to that in α-ketoglutarate-dependent dioxygenases.

Utilization of Physical Anisotropy in Metal-Organic Frameworks via Postsynthetic Alignment Control with Liquid Crystal.

Metal-organic frameworks (MOFs) represent crystalline materials constructed from combinations of metal and organic units to often yield anisotropic porous structures and physical properties. Postsynthetic methods to align the MOF crystals in bulk remain scarce yet tremendously important to fully utilize their structure-driven intrinsic properties. Herein, we present an unprecedented composite of liquid crystals (LCs) and MOFs and demonstrate the use of nematic LCs to dynamically control the orientation of MOF crystals with exceptional order parameters (as high as 0.

Permanent Porosity in the Room-Temperature Magnet and Magnonic Material V(TCNE).

Materials that simultaneously exhibit permanent porosity and high-temperature magnetic order could lead to advances in fundamental physics and numerous emerging technologies. Herein, we show that the archetypal molecule-based magnet and magnonic material V(TCNE) (TCNE = tetracyanoethylene) can be desolvated to generate a room-temperature microporous magnet. The solution-phase reaction of V(CO) with TCNE yields V(TCNE)·0.

Fabrication of Scratched Nanogrooves for Highly Oriented Cell Alignment and Application as a Wound Healing Dressing.

Using improper wound care materials may cause impaired wound healing, which can involve scar formation and infection. Herein, we propose a facile method to fabricate a cell-alignment scaffold, which can effectively enhance cell growth and migration, leading to the reproduction of cellular arrangements and restoration of tissues. The principle is scratching a diamond lapping film that gives uniaxial nanotopography on substrates.

Racemized photonic crystals for physical unclonable function.

As Internet of Things-based technologies continue to digitalize our society, the development of secure and robust identification systems against evolving adversaries remains a grave challenge. Recently, physical unclonable functions (PUFs) have garnered tremendous scientific interest due to their intrinsic randomness, which makes them difficult to counterfeit. Herein, we present a facile approach for fabricating optical PUFs using spontaneous mirror symmetry breaking of molecular self-assembly.

Magnetic ordering through itinerant ferromagnetism in a metal-organic framework.

Materials that combine magnetic order with other desirable physical attributes could find transformative applications in spintronics, quantum sensing, low-density magnets and gas separations. Among potential multifunctional magnetic materials, metal-organic frameworks, in particular, bear structures that offer intrinsic porosity, vast chemical and structural programmability, and the tunability of electronic properties. Nevertheless, magnetic order within metal-organic frameworks has generally been limited to low temperatures, owing largely to challenges in creating a strong magnetic exchange.

A Single-Ion Conducting Borate Network Polymer as a Viable Quasi-Solid Electrolyte for Lithium Metal Batteries.

Lithium-ion batteries have remained a state-of-the-art electrochemical energy storage technology for decades now, but their energy densities are limited by electrode materials and conventional liquid electrolytes can pose significant safety concerns. Lithium metal batteries featuring Li metal anodes, solid polymer electrolytes, and high-voltage cathodes represent promising candidates for next-generation devices exhibiting improved power and safety, but such solid polymer electrolytes generally do not exhibit the required excellent electrochemical properties and thermal stability in tandem. Here, an interpenetrating network polymer with weakly coordinating anion nodes that functions as a high-performing single-ion conducting electrolyte in the presence of minimal plasticizer, with a wide electrochemical stability window, a high room-temperature conductivity of 1.

Charge Delocalization and Bulk Electronic Conductivity in the Mixed-Valence Metal-Organic Framework Fe(1,2,3-triazolate)(BF) .

Metal-organic frameworks are of interest for use in a variety of electrochemical and electronic applications, although a detailed understanding of their charge transport behavior, which is of critical importance for enhancing electronic conductivities, remains limited. Herein, we report isolation of the mixed-valence framework materials, Fe(tri)(BF) (tri = 1,2,3-triazolate; x = 0.09, 0.

Electronic effects of ligand substitution on spin crossover in a series of diiminoquinonoid-bridged Fe(II)2 complexes.

A series of four isostructural Fe(II)2 complexes, [(TPyA)2Fe2((X)L)](2+) (TPyA = tris(2-pyridylmethyl)amine; (X)L(2-) = doubly deprotonated form of 3,6-disubstituted-2,5-dianilino-1,4-benzoquinone; X = H, Br, Cl, and F), were synthesized to enable a systematic study of electronic effects on spin crossover behavior. Comparison of X-ray diffraction data for these complexes reveals the sole presence of high-spin Fe(II) at 225 K and mixtures of high-spin and low-spin Fe(II) at 100 K, which is indicative of incomplete spin crossover. In addition, crystal packing diagrams show that these complexes are well-isolated from one another in the solid state, owing primarily to the presence of bulky tetra(aryl)borate counteranions, such that spin crossover is likely not significantly affected by intermolecular interactions.

An azophenine radical-bridged Fe2 single-molecule magnet with record magnetic exchange coupling.

One-electron reduction of the complex [(TPyA)2Fe(II)2((NPh)L(2-))](2+) (TPyA = tris(2-pyridylmethyl)amine, (NPh)LH2 = azophenine = N,N',N",N'''-tetraphenyl-2,5-diamino-1,4-diiminobenzoquinone) affords the complex [(TPyA)2Fe(II)2((NPh)L(3-•))](+). X-ray diffraction and Mössbauer spectroscopy confirm that the reduction occurs on (NPh)L(2-) to give an S = 1/2 radical bridging ligand. Dc magnetic susceptibility measurements demonstrate the presence of extremely strong direct antiferromagnetic exchange between S = 2 Fe(II) centers and (NPh)L(3-•) in the reduced complex, giving an S = 7/2 ground state with an estimated coupling constant magnitude of |J| ≥ 900 cm(-1).