At the Borderline between Metal-Metal Mixed Valency and a Radical Bridge Situation: Four Charge States of a Diruthenium Complex with a Redox-Active Bis(mer-tridentate) Ligand
The result's identifiers
Result code in IS VaVaI
<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F61388955%3A_____%2F18%3A00491162" target="_blank" >RIV/61388955:_____/18:00491162 - isvavai.cz</a>
Result on the web
<a href="http://dx.doi.org/10.1021/acs.inorgchem.8b00173" target="_blank" >http://dx.doi.org/10.1021/acs.inorgchem.8b00173</a>
DOI - Digital Object Identifier
<a href="http://dx.doi.org/10.1021/acs.inorgchem.8b00173" target="_blank" >10.1021/acs.inorgchem.8b00173</a>
Alternative languages
Result language
angličtina
Original language name
At the Borderline between Metal-Metal Mixed Valency and a Radical Bridge Situation: Four Charge States of a Diruthenium Complex with a Redox-Active Bis(mer-tridentate) Ligand
Original language description
The complex ions [(LRu)-Ru-3(mu,eta(3):eta(3)-BL)RuL3](n+) (1(n+), L-3 = 4,4',4 ''-tri-tert-butyl-2,6,2',6 ''-terpyridine and H2BL2- = 1,2-bis(salicyloyl)-hydrazide(2-)) were isolated with PF6- or ClO4- counterions (n = 1) and as bis(hexafluorophosphate) (n = 2). Structural, electrochemical, and spectroscopic characterization reveals the monocation as intermediate (K-c = 10(8.2)) in the three-step reversible redox system 1(0/+/2+/3+). The 1(+) ion has the molecule bridged (Ru-Ru 4.727 angstrom) ruthenium centers involved in five- and six- membered chelate rings, and it exhibits long-wavelength absorptions at lambda(max) 2240, 1660, and 1530 nm (epsilon(max) = 1000, 3000, and 8000 M-1 cm(-1) respectively), which would be compatible with a (RuRuII)-Ru-III mixed-valent situation or with a coordinated radical ion bridge. In fact, EPR and DFT analysis of 1(+) reveals that the spin is equally distributed over the ligand bridge and over both metals. The oxidized paramagnetic ions 1(2+) and 1(3+) have been studied by H-1 NMR and EPR and by TD-DFT supported UV-vis-NIR and MIR (mid-IR) spectroelectrochemistry. The capacity of various kinds of bis(mer-tridentate) bridging ligands (pi donors or pi acceptors, cyclometalated or noncyclometalated) for mediating metal-metal interactions is discussed.
Czech name
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Czech description
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Classification
Type
J<sub>imp</sub> - Article in a specialist periodical, which is included in the Web of Science database
CEP classification
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OECD FORD branch
10403 - Physical chemistry
Result continuities
Project
<a href="/en/project/LTC17052" target="_blank" >LTC17052: Electron-transfer dynamics in complex molecular systems</a><br>
Continuities
P - Projekt vyzkumu a vyvoje financovany z verejnych zdroju (s odkazem do CEP)
Others
Publication year
2018
Confidentiality
S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů
Data specific for result type
Name of the periodical
Inorganic Chemistry
ISSN
0020-1669
e-ISSN
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Volume of the periodical
57
Issue of the periodical within the volume
7
Country of publishing house
US - UNITED STATES
Number of pages
10
Pages from-to
3983-3992
UT code for WoS article
000429283200055
EID of the result in the Scopus database
2-s2.0-85044829743