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- Title
Synthesis of Square Planar Cu<sub>4</sub> Clusters.
- Authors
Osei, Manasseh Kusi; Mirzaei, Saber; Bogetti, Xiaowei; Castro, Edison; Rahman, Mohammad Azizur; Saxena, Sunil; Hernández Sánchez, Raúl
- Abstract
Template‐assisted synthesis of well‐defined polynuclear clusters remains a challenge for [M4] square planar topologies. Herein, we present a tetraamine scaffold RL(NH2)4, where L is a rigidified resorcin[4]arene, to direct the formation of C4‐symmetric RL(NH)4Cu4 clusters with Cu−Cu distances around 2.7 Å, suggesting metal‐metal direct interactions are operative since the sum of copper's van der Waals radii is 2.8 Å. DFT calculations display HOMO to HOMO‐3 residing all within a 0.1 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.
- Subjects
PARAMAGNETIC resonance; ELECTRON density; SMALL molecules; SQUARE; RESORCINOL; ELECTRON paramagnetic resonance spectroscopy; VAN der Waals forces; COPPER clusters
- Publication
Angewandte Chemie, 2022, Vol 134, Issue 41, p1
- ISSN
0044-8249
- Publication type
Article
- DOI
10.1002/ange.202209529