Cross-Hyperconjugation: An Unexplored Orbital Interaction between π-Conjugated and Saturated Molecular Segments


  • We are grateful for support from the Swedish Research Council (Grant Nos. 2008-3710, 2009-362, and 2010-4858), Uppsala University through the U3MEC KoF07 initiative, and the Wenner-Gren Foundations, Göran Gustafsson Foundation, and American Scandinavia Foundation for fellowships to A.W. and J.R.S. The National Supercomputer Center (NSC) in Linköping, Sweden, and the Uppsala Multidisciplinary Center for Advanced Computational Science (UPPMAX), Uppsala, Sweden are acknowledged for generous allotment of computer time.


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Crossing a barrier: Molecules with saturated ER2 units (E=C or Si, R=electron-releasing group) inserted between two π-conjugated segments have electronic and optical properties that resemble those of cross-conjugated molecules (see figure). This cross-hyperconjugation provides a deeper understanding of the conjugation phenomenon, and is an alternative to cross-conjugation in the design of molecules for nano and materials applications.