Host–Guest Hydrogen Bonding Varies the Charge‐State Behavior of Magnetic Sponges

Abstract

The electron‐donor(D) and ‐acceptor(A)‐assembled D2A‐layer framework [{Ru2(m‐FPhCO2)4}2TCNQ(OMe)2]⋅nDCE (1‐nDCE; m‐FPhCO2−=m‐fluorobenzoate; TCNQ(OMe)2=2,5‐dimethoxyl‐7,7,8,8‐tetracyanoquinodimethane; DCE=1,2‐dichloroethane) undergoes drastic charge‐ordered state variations via three distinct states that are a two‐electron‐transferred state (2e‐I), a charge‐disproportionated state (1.5e‐I), and a one‐electron‐transferred state (1e‐I), depending on the degree of solvation by nDCE. The pristine form 1‐4DCE has a paramagnetic 2e‐I state, which eventually produces the solvent‐free form 1 in 1.5e‐I via an intermediate state 1‐nDCE (n≤1) in 1e‐I. Resolvation of 1 stabilizes 1‐DCE, allowing it to switch between 1.5e‐I and 1e‐I, and to become ferrimagnetic with a Tc of 30 K (1.5e‐I) and 88 K (1e‐I). The stabilization of the 1e‐I state of 1‐DCE is due to the presence of host–guest hydrogen bonding that enables to suppress the electron‐donation ability of D even in an identical framework with 1.

Physicochemical properties and density functional theory calculation of octahedral UiO-66 with Bis(Trifluoromethanesulfonyl)imide ionic liquids

“…The neighbouring atoms can interact well as the alkyl chain moving towards the surface of UiO-66 [ 47 ]. These hydrogen bonds could be contributing to the host-guest interactions of IL and UiO-66 which also stabilizes the framework structure, as evidenced by the thermal analysis from DSC curves [ [48] , [49] , [50] ].…”

1,2,5-Thiadiazole 1,1-dioxides and Their Radical Anions: Structure, Properties, Reactivity, and Potential Use in the Construction of Functional Molecular Materials

“…The oxo- and dioxothiadiazoles can be easily reduced to stable radical anions [ 21 ] and are therefore of potential use to the molecular magnetism community. However, this group of compounds seems to be completely omitted as potential building blocks for the construction of molecule-based magnetic materials [ 22 , 23 ] compared to other organic radicals (nitronyl nitroxides [ 24 , 25 , 26 , 27 ], verdazyl [ 28 , 29 , 30 ], semiquinones [ 31 , 32 ], or TCNE and TCNQ derivatives [ 33 , 34 ]) which have been used extensively to obtain all-organic magnets [ 35 ], Single Molecule Magnets [ 36 , 37 ], or Single Chain Magnets (SCMs) [ 24 , 38 , 39 , 40 , 41 ], among many other functional magnetic materials. This review focuses on 1,2,5-thiadiazole 1,1-dioxides ( Figure 1 a) and their radical anions [ 42 ], which constitute perhaps the prime example of the dioxothiadiazole family, and summarizes the current state-of-the-art in the field of 1,2,5-thiadiazole 1,1-dioxides with the aim of shedding light on the extraordinary possibilities and applications of this heterocyclic moieties with respect to the design and preparation of switchable/functional molecular materials.…”

Influence of the Increasing Number of Organic Radicals on the Structural, Magnetic, and Electrochemical Properties of the Copper(II)–Dioxothiadiazole Family of Complexes

“…Even though the library of organic radicals is enormous, 3 , 20 , 37 − 40 only a few classes dominate the field of molecular magnetism, and these are verdazyls, 41 , 42 nitronyl nitroxides, 43 , 44 semiquinones, 45 , 46 and TTF, TCNE, and TCNQ derivatives. 47 − 52 The popularity of these four groups is dictated by their stability, chemical tunability, coordination abilities promoting strong magnetic interactions, and electrochemical properties providing electron transfer and enabling various types of switching properties.…”