Hybrid alpha-Diimine/Bis(chalcogenoether) Ligands for Copper(I) an Copper(II) Complexes

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F61388955%3A_____%2F18%3A00492505" target="_blank" >RIV/61388955:_____/18:00492505 - isvavai.cz</a>

Výsledek na webu

<a href="http://dx.doi.org/10.1002/zaac.201800073" target="_blank" >http://dx.doi.org/10.1002/zaac.201800073</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1002/zaac.201800073" target="_blank" >10.1002/zaac.201800073</a>

Jazyk výsledku

angličtina

Název v původním jazyce

Hybrid alpha-Diimine/Bis(chalcogenoether) Ligands for Copper(I) an Copper(II) Complexes

Popis výsledku v původním jazyce

The new ligands L = 1,4-bis(2-methylchalcogenophenyl)-2,3-dimethyl-1,4-diaza-1,3-diene [chalcogen = O (1), S (2) or Se (3)] have been studied in their coordination behavior towards Cu-I and Cu-II. Whereas the O-ether containing ligand forms complex ions [Cu(L)(2)](n+) = 4(n+), with exclusive N-coordination (n = 1) or N and weaker O coordination (n = 2), the species with E = S or Se contain tetradentate ligands in [Cu(L)](+) (5(+), 6(+)) and [Cu(L)L'](n+) [n = 1, L' = TfO- (E = S) or n = 2 and L' = H2O (E = Se)]. Molecular structures in the crystals of 5(+) and 6(+) show distorted tetrahedral N coordination at the metal and innocently behaving alpha-diimine functions, in agreement with spectroscopic and computational data. The copper(II) ions [Cu(L)L'](2+) with one tetradentate ligand L = 2 or 3 exhibit a square-pyramidal configuration at the metal. Two isolated crystalline forms of 4(2+) show weak coordination (2.636-2.96 angstrom) of three or four ether oxygen atoms, resulting in 4+3 or 4+4 coordination arrangements for N and O donors, respectively. In agreement with the rather different Cu-I and Cu-II structures the electrochemical oxidation of the copper(I) complexes and the reduction of the corresponding Cu-II species reveal an ECEC behavior within a square scheme, whereas the reduction of the Cu-I compounds, most likely at the diimine site, proceeds irreversibly. UV/Vis spectroelectrochemical results showing intense MLCT and IL absorptions were analyzed with the help of TD-DFT calculations.

Název v anglickém jazyce

Hybrid alpha-Diimine/Bis(chalcogenoether) Ligands for Copper(I) an Copper(II) Complexes

Popis výsledku anglicky

The new ligands L = 1,4-bis(2-methylchalcogenophenyl)-2,3-dimethyl-1,4-diaza-1,3-diene [chalcogen = O (1), S (2) or Se (3)] have been studied in their coordination behavior towards Cu-I and Cu-II. Whereas the O-ether containing ligand forms complex ions [Cu(L)(2)](n+) = 4(n+), with exclusive N-coordination (n = 1) or N and weaker O coordination (n = 2), the species with E = S or Se contain tetradentate ligands in [Cu(L)](+) (5(+), 6(+)) and [Cu(L)L'](n+) [n = 1, L' = TfO- (E = S) or n = 2 and L' = H2O (E = Se)]. Molecular structures in the crystals of 5(+) and 6(+) show distorted tetrahedral N coordination at the metal and innocently behaving alpha-diimine functions, in agreement with spectroscopic and computational data. The copper(II) ions [Cu(L)L'](2+) with one tetradentate ligand L = 2 or 3 exhibit a square-pyramidal configuration at the metal. Two isolated crystalline forms of 4(2+) show weak coordination (2.636-2.96 angstrom) of three or four ether oxygen atoms, resulting in 4+3 or 4+4 coordination arrangements for N and O donors, respectively. In agreement with the rather different Cu-I and Cu-II structures the electrochemical oxidation of the copper(I) complexes and the reduction of the corresponding Cu-II species reveal an ECEC behavior within a square scheme, whereas the reduction of the Cu-I compounds, most likely at the diimine site, proceeds irreversibly. UV/Vis spectroelectrochemical results showing intense MLCT and IL absorptions were analyzed with the help of TD-DFT calculations.

Druh

J_imp - Článek v periodiku v databázi Web of Science

CEP obor

—

OECD FORD obor

10403 - Physical chemistry

Projekt

Výsledek vznikl pri realizaci vícero projektů. Více informací v záložce Projekty.

Návaznosti

P - Projekt vyzkumu a vyvoje financovany z verejnych zdroju (s odkazem do CEP)

Rok uplatnění

2018

Kód důvěrnosti údajů

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

Název periodika

Zeitschrift für anorganische und allgemeine Chemie

ISSN

0044-2313

e-ISSN

—

Svazek periodika

644

Číslo periodika v rámci svazku

14

Stát vydavatele periodika

DE - Spolková republika Německo

Počet stran výsledku

10

Strana od-do

661-670

Kód UT WoS článku

000440311100009

EID výsledku v databázi Scopus

2-s2.0-85050799311