Electronic Desymmetrization of Cu3(μ3-E) Clusters (E = S, Se) Induced by Edge-to-Face π-Stacking Interactions in the
Pinar Alayoglu1, M Victoria Lorenzo Ocampo2, Zhiyu Wang2
1Department of Chemistry, University of Illinois-Chicago, Chicago, Illinois 60607, United States.
Abstract:
A pair of cyclophane-encapsulated [Cu3(μ3-E)]3+ complexes (E = S and Se) were characterized by resonant X-ray diffraction anomalous fine structure (DAFS), revealing unexpected polarization among the three Cu sites attributed to long-range effects of π-stacking interactions with cocrystallized benzene molecules. The resonant K-edge energies of individual Cu sites within the cluster molecules were found to vary as a function of distance from the cocrystallized benzene. This pattern was interpreted in the context of T-shaped, edge-to-face π-stacking with the assistance of theoretical charge density difference calculations.
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