Synthesis of Square Planar Cu4 Clusters.
Angew Chem Int Ed Engl
; 61(41): e202209529, 2022 Oct 10.
Article
em En
| MEDLINE
| ID: mdl-35998086
ABSTRACT
Template-assisted synthesis of well-defined polynuclear clusters remains a challenge for [M4 ] square planar topologies. Herein, we present a tetraamine scaffold R L(NH2 )4 , where L is a rigidified resorcin[4]arene, to direct the formation of C4 -symmetric R L(NH)4 Cu4 clusters with Cu-Cu distances around 2.7â
Å, suggesting metal-metal direct interactions are operative since the sum of copper's van der Waals radii is 2.8â
Å. DFT calculations display HOMO to HOMO-3 residing all within a 0.1â
eV gap. These four orbitals display significant electron density contribution from the Cu centers suggesting a delocalized electronic structure. The one-electron oxidized [Cu4 ]+ species was probed by variable temperature X-band continuous wave-electron paramagnetic resonance (CW-EPR), which displays a multiline spectrum at room temperature. This work presents a novel synthetic strategy for [M4 ] clusters and a new platform to investigate activation of small molecules.
Texto completo:
1
Coleções:
01-internacional
Base de dados:
MEDLINE
Idioma:
En
Revista:
Angew Chem Int Ed Engl
Ano de publicação:
2022
Tipo de documento:
Article
País de afiliação:
Estados Unidos