Homodinuclear Complexes of [Cu(dppf)](+) or [Ru(bpy)(2)](2+) with 1,4-Bis(camphorquinoneimino)benzene (bcqb) as a Redox-Active Bridging Ligand

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F61388955%3A_____%2F21%3A00544233" target="_blank" >RIV/61388955:_____/21:00544233 - isvavai.cz</a>

Výsledek na webu

<a href="http://hdl.handle.net/11104/0321264" target="_blank" >http://hdl.handle.net/11104/0321264</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1002/ejic.202100405" target="_blank" >10.1002/ejic.202100405</a>

Jazyk výsledku

angličtina

Název v původním jazyce

Homodinuclear Complexes of [Cu(dppf)](+) or [Ru(bpy)(2)](2+) with 1,4-Bis(camphorquinoneimino)benzene (bcqb) as a Redox-Active Bridging Ligand

Popis výsledku v původním jazyce

The product mu-bcqb from the reaction between p-phenylenediamine and two equivalents of camphorquinone has been used as a potentially conjugated molecular bridge between two complex fragments [Cu(dppf)](+), dppf=1,1'-bis(diphenylphosphino)ferrocene, to yield 1(2+), and between two [Ru(bpy)(2)](2+) moieties, resulting in 2(4+). The molecular structure of 1(BF4)(2) shows an intramolecular Cu-Cu distance of 8.04 angstrom and a torsionally twisted conformation of the bridge, while cyclic voltammetry, EPR, IR and UV-vis-NIR spectroelectrochemistry reveal two closely spaced one-electron reductions and a ferrocene-based two-electron oxidation. Compound 2(PF6)(4) exhibits at least three one-electron reduction waves and one 2e-oxidation, the former attributed to mu-bcqb and the latter assigned to metal-based processes showing no evidence for a Ru-Ru mixed-valent intermediate. However, intra-ligand based mixed valency with intense LLIVCT absorptions in the near infrared was observed for the metal coordinated mu-bcqb(.-) and mu-bcqb(.3-) bridges. The two examples 1(n+) and 2(n+) illustrate that a combination of physical methods is advantageous to analyze and define the correct electronic structures in complexes involving several metal centers and noninnocent ligand components.

Název v anglickém jazyce

Homodinuclear Complexes of [Cu(dppf)](+) or [Ru(bpy)(2)](2+) with 1,4-Bis(camphorquinoneimino)benzene (bcqb) as a Redox-Active Bridging Ligand

Popis výsledku anglicky

The product mu-bcqb from the reaction between p-phenylenediamine and two equivalents of camphorquinone has been used as a potentially conjugated molecular bridge between two complex fragments [Cu(dppf)](+), dppf=1,1'-bis(diphenylphosphino)ferrocene, to yield 1(2+), and between two [Ru(bpy)(2)](2+) moieties, resulting in 2(4+). The molecular structure of 1(BF4)(2) shows an intramolecular Cu-Cu distance of 8.04 angstrom and a torsionally twisted conformation of the bridge, while cyclic voltammetry, EPR, IR and UV-vis-NIR spectroelectrochemistry reveal two closely spaced one-electron reductions and a ferrocene-based two-electron oxidation. Compound 2(PF6)(4) exhibits at least three one-electron reduction waves and one 2e-oxidation, the former attributed to mu-bcqb and the latter assigned to metal-based processes showing no evidence for a Ru-Ru mixed-valent intermediate. However, intra-ligand based mixed valency with intense LLIVCT absorptions in the near infrared was observed for the metal coordinated mu-bcqb(.-) and mu-bcqb(.3-) bridges. The two examples 1(n+) and 2(n+) illustrate that a combination of physical methods is advantageous to analyze and define the correct electronic structures in complexes involving several metal centers and noninnocent ligand components.

Druh

J_imp - Článek v periodiku v databázi Web of Science

CEP obor

—

OECD FORD obor

10403 - Physical chemistry

Projekt

—

Návaznosti

I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace

Rok uplatnění

2021

Kód důvěrnosti údajů

S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů

Název periodika

European Journal of Inorganic Chemistry

ISSN

1434-1948

e-ISSN

1099-0682

Svazek periodika

2021

Číslo periodika v rámci svazku

29

Stát vydavatele periodika

DE - Spolková republika Německo

Počet stran výsledku

10

Strana od-do

2976-2985

Kód UT WoS článku

000667326200001

EID výsledku v databázi Scopus

2-s2.0-85108943207