Metal-Organic Network-Forming Glasses

The crystal–liquid–glass phase transition of coordination polymers (CPs) and metal–organic frameworks (MOFs) offers attractive opportunities as a new class of amorphous materials. Unlike conventional glasses, coordination chemistry allows the utilization of rational design concepts to fine-tune the desired properties. Although the glassy state has been rare in CPs/MOFs, it exhibits diverse advantages complementary to their crystalline counterparts, including improved mass transport, optical properties, mechanical properties, and the ability to form grain-boundary-free monoliths. This Review discusses the current achievements in improving the understanding of anomalous phase transitions in CPs/MOFs. We elaborate on the criteria for classifying CP/MOF glasses and comprehensively discuss the three common strategies employed to obtain a glassy state. We include all CP/MOF glass research progress since its inception, discuss the current challenges, and express our perspective on future research directions

Proton-conductive coordination polymer glass for solid-state anhydrous proton batteries

Designing solid-state electrolytes for proton batteries at moderate temperatures is challenging as most solid-state proton conductors suffer from poor moldability and thermal stability. Crystal–glass transformation of coordination polymers (CPs) and metal–organic frameworks (MOFs) via melt-quenching offers diverse accessibility to unique properties as well as processing abilities. Here, we synthesized a glassy-state CP, [Zn₃(H₂PO₄)₆(H₂O)₃](1, 2, 3-benzotriazole), that exhibited a low melting temperature (114 °C) and a high anhydrous single-ion proton conductivity (8.0 × 10⁻³ S cm⁻¹ at 120 °C). Converting crystalline CPs to their glassy-state counterparts via melt-quenching not only initiated an isotropic disordered domain that enhanced H⁺ dynamics, but also generated an immersive interface that was beneficial for solid electrolyte applications. Finally, we demonstrated the first example of a rechargeable all-solid-state H+ battery utilizing the new glassy-state CP, which exhibited a wide operating-temperature range of 25 to 110 °C

Synthesis of magnesium ZIF-8 from Mg(BH₄)₂.

Porous Mg(2-methyl imidazolate)2 (Mg-ZIF-8) was synthesised from Mg(BH4)2 as a precursor under an Ar atmosphere. It possesses an uncommon tetrahedral Mg(2+)-N coordination geometry that is stabilised by the formation of a framework, and it exhibits a Brunauer-Emmett-Teller surface area greater than 1800 m(2) g(-1)

(4-Carb­oxy-2-sulfonato­benzoato-κ2 O 1,O 2)bis­(1,10-phenanthroline-κ2 N,N′)manganese(II)

In the title complex, [Mn(C8H4O7S)(C12H8N2)2], the MnII atom is chelated by one 4-carb­oxy-2-sulfonato­benzoate anion and two phenathroline (phen) ligands in a distorted octa­hedral MnN4O2 geometry. The benzene ring of the 4-carb­oxy-2-sulfonato­benzoate anion is twisted with respect to the two phen ring systems at dihedral angles of 66.38 (9) and 53.56 (9)°. In the crystal, inter­molecular O—H⋯O and C—H⋯O hydrogen bonding links the mol­ecules into chains running parallel to [100]. Inter­molecular π–π stacking is also observed between parallel phen ring systems, the face-to-face distance being 3.432 (6) Å

Üsküdar mesireleri

Taha Toros Arşivi, Dosya No: 63-Salacak-Üsküdarİstanbul Kalkınma Ajansı (TR10/14/YEN/0033) İstanbul Development Agency (TR10/14/YEN/0033