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
Identifikátory výsledku
Kód výsledku v 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>
Výsledek na webu
<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>
Alternativní jazyky
Jazyk výsledku
angličtina
Název v původním jazyce
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
Popis výsledku v původním jazyce
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.
Název v anglickém jazyce
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
Popis výsledku anglicky
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.
Klasifikace
Druh
J<sub>imp</sub> - Článek v periodiku v databázi Web of Science
CEP obor
—
OECD FORD obor
10403 - Physical chemistry
Návaznosti výsledku
Projekt
<a href="/cs/project/LTC17052" target="_blank" >LTC17052: Dynamika přenosu elektronu v komplexních molekulárních systémech</a><br>
Návaznosti
P - Projekt vyzkumu a vyvoje financovany z verejnych zdroju (s odkazem do CEP)
Ostatní
Rok uplatnění
2018
Kód důvěrnosti údajů
S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů
Údaje specifické pro druh výsledku
Název periodika
Inorganic Chemistry
ISSN
0020-1669
e-ISSN
—
Svazek periodika
57
Číslo periodika v rámci svazku
7
Stát vydavatele periodika
US - Spojené státy americké
Počet stran výsledku
10
Strana od-do
3983-3992
Kód UT WoS článku
000429283200055
EID výsledku v databázi Scopus
2-s2.0-85044829743