Issue 33, 2021

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

Abstract

Electronic-state modulation utilizing the electrostatic properties and dynamics of hydrogen-bonding (H-bonding) protons is an effective strategy for realizing novel electron–proton-coupled functionalities. However, material developments based on this strategy have been limited to a few π-electron systems; thus, the realization of solid-state electron–proton-coupled functionalities is challenging. Here, we successfully synthesized new crystals based on nickel catecholdithiolene complexes, which are d/π-electron systems with H-bonds, exhibiting various deprotonation/oxidation states brought about via solution processes. In these crystals, unique three-dimensional framework or two-dimensional sheet structures are formed by intermolecular H-bonds between the complexes, including anionic [O–H⋯O] H-bonds (dO⋯O ∼ 2.59 Å), which were advantageous for proton transfer in solid states. Importantly, detailed analyses revealed that the nickel complexes in the crystals were in various oxidation/deprotonation states. Accordingly, the magnetic properties changed from paramagnetic to non-magnetic with the oxidation of the complexes through proton-coupled electron transfer in solution processes. Density functional theory calculations revealed that the d/π electronic states of the nickel complexes in each crystal are significantly modulated depending on the deprotonation/oxidation states. We propose a possible mechanism for the oxidation-coupled deprotonation of the nickel complex, where various oxidation/deprotonation states can be obtained as crystals and controlled by recrystallization conditions, which is realized by the characteristic d/π-conjugation property and (de)protonation/redox activity of the nickel catecholdithiolene complex. The findings provide a further possibility to construct d/π-electron–proton-coupled collective functionalities based on this complex, together with significant insights for exploring novel electron–proton-coupled functionalities in the solid state.

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

Supplementary files

Article information

Article type
Paper
Submitted
09 mar 2021
Accepted
23 apr 2021
First published
18 maj 2021

J. Mater. Chem. C, 2021,9, 10718-10726

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

S. Yokomori, S. Dekura, A. Ueda, R. Kumai, Y. Murakami and H. Mori, J. Mater. Chem. C, 2021, 9, 10718 DOI: 10.1039/D1TC01111A

To request permission to reproduce material from this article, please go to the Copyright Clearance Center request page.

If you are an author contributing to an RSC publication, you do not need to request permission provided correct acknowledgement is given.

If you are the author of this article, you do not need to request permission to reproduce figures and diagrams provided correct acknowledgement is given. If you want to reproduce the whole article in a third-party publication (excluding your thesis/dissertation for which permission is not required) please go to the Copyright Clearance Center request page.

Read more about how to correctly acknowledge RSC content.

Social activity

Spotlight

Advertisements