Redox-Induced Hydrogen Bond Reorientation Mimicking Electronic Coupling in Mixed-Valent Diruthenium and Macrocyclic Tetraruthenium Complexes

Fink D, Staiger A, Orth N, Linseis M, Ivanovic-Burmazovic I, Winter RF (2020)

Publication Type: Journal article

Publication year: 2020

Journal

Inorganic Chemistry American Chemical Society

Book Volume: 59

Pages Range: 16703-16715

Journal Issue: 22

DOI: 10.1021/acs.inorgchem.0c02695

Abstract

We present the coordination-driven self-assembly of three tetranuclear metallacycles containing intracyclic NH2, OH, or OMe functionalities through the combination of various isophthalic acid building blocks with a divinylphenylene diruthenium complex. All new complexes of this study were characterized by means of nuclear magnetic resonance spectroscopy, ultrahigh-resolution ESI mass spectrometry, cyclic and square wave voltammetry and, in two cases, X-ray diffraction. The hydroxy functionalized macrocycle 4-BOH and the corresponding half-cycle 2-OH stand out, as their intracyclic OH···O hydrogen bonds stabilize their mixed-valent one- (2-OH, 4-BOH) and three-electron-oxidized states (4-BOH). Despite sizable redox splittings between all one-electron waves, the mixed-valent monocations and trications do not exhibit any intervalence charge-transfer band, assignable to through-bond electronic coupling, but nevertheless display distinct IR band shifts of their charge-sensitive Ru(CO) tags. We ascribe these seemingly contradicting observations to a redox-induced shuffling of the OH···O hydrogen bond(s) to the remaining, more electron-rich, reduced redox site.

Authors with CRIS profile

Nicole Orth Lehrstuhl für Bioanorganische Chemie Ivana Ivanovic-Burmazovic Lehrstuhl für Bioanorganische Chemie

Involved external institutions

Universität Konstanz DE Germany (DE)

How to cite

APA:

Fink, D., Staiger, A., Orth, N., Linseis, M., Ivanovic-Burmazovic, I., & Winter, R.F. (2020). Redox-Induced Hydrogen Bond Reorientation Mimicking Electronic Coupling in Mixed-Valent Diruthenium and Macrocyclic Tetraruthenium Complexes. Inorganic Chemistry, 59(22), 16703-16715. https://dx.doi.org/10.1021/acs.inorgchem.0c02695

MLA:

Fink, Daniel, et al. "Redox-Induced Hydrogen Bond Reorientation Mimicking Electronic Coupling in Mixed-Valent Diruthenium and Macrocyclic Tetraruthenium Complexes." Inorganic Chemistry 59.22 (2020): 16703-16715.

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