Modulation of the electronic states and magnetic properties of nickel catecholdithiolene complex by oxidation-coupled deprotonation

Abstract

Magnetic properties of nickel catecholdithiolene complexes with unique hydrogen-bond networks were modulated by oxidation-coupled deprotonations and controlled with crystallization conditions.

Proton–electron-coupled functionalities of conductivity, magnetism, and optical properties in molecular crystals

“…[64][65][66][77][78][79][80][81][82] Herein, focus is on the usage of catechol-or alchoxybenzene-substituted metal dithiolene complexes to develop new proton-d/p-electron-coupled materials. 38,39,83,84 This chapter discusses our recent progress on proton-electron-coupled functionalities using metal dithiolene complexes.…”

“…Case in point, metal catecholdithiolene complexes (Fig. 5a) can exhibit up to four degrees of deprotonation because of the four hydroxy groups, 38,83,84 and one-or multi-electron redox abilities due to the metal dithiolene skeleton, thus inducing the formation of stable, multi-PCET states.…”

“…In Section 3.3, magnetism correlated with multi-step redox and deprotonation-coupled systems will be introduced. 38 As for the proton-d/p-electron-coupled optical functionality, 39 a novel vapochromism based on the electron transfer from H-bond formation for metal complexes has been discovered. Consequentially, the changes in the visible-light absorption and luminescence properties with vapor sorption, as well as its mechanism, are described in Section 4.…”

“…In Section 3.3, magnetism correlated with multi-step redox and deprotonation-coupled systems will be introduced. 38…”

Ambipolar Nickel Dithiolene Complex Semiconductors: From One- to Two-Dimensional Electronic Structures Based upon Alkoxy Chain Lengths

“…Our group recently developed single-crystalline metal bis­(dithiolene) complexes, − including nickel-centered planar structures with catechol substituents . The highly distributed d/π-conjugated systems with fused catechol groups satisfy the HOMO and LUMO levels for ambipolar semiconductors (requirement i), although catechol groups are easily deprotonated upon oxidation.…”