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1,4-Disilacyclohexa-2,5-diene: a molecular building block that allows for remarkably strong neutral cyclic cross-hyperconjugation
Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - BMC.
Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - BMC.
Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - BMC, Physical Organic Chemistry.
Uppsala University, Disciplinary Domain of Science and Technology, Physics, Department of Physics and Astronomy, Molecular and condensed matter physics.
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2014 (English)In: Chemical Science, ISSN 2041-6520, Vol. 5, no 1, 360-371 p.Article in journal (Refereed) Published
Abstract [en]

2,3,5,6-Tetraethyl-1,4-disilacyclohexa-2,5-dienes with either four chloro (1a), methyl (1b), or trimethylsilyl (TMS) (1c) substituents at the two silicon atoms were examined in an effort to design rigid compounds with strong neutral cross-hyperconjugation between pi- and sigma-bonded molecular segments arranged into a cycle. Remarkable variations in the lowest electronic excitation energies, lowest ionization energies, and the first oxidation potentials were observed upon change of substituents, as determined by gas phase ultraviolet (UV) absorption spectroscopy, ultraviolet photoelectron spectroscopy (UPS), and cyclic voltammetry. A particularly strong neutral cyclic cross-hyperconjugation was observed in 1c. Its lowest electron binding energy (7.1 eV) is distinctly different from that of 1b (8.5 eV). Molecular orbital analysis reveals a stronger interaction between filled pi(C=C) and pi(SiR2) group orbitals in 1c than in 1a and 1b. The energy shift in the highest occupied molecular orbital is also reflected in the first oxidation potentials as observed in the cyclic voltammograms of the respective compounds (1.47, 0.88, and 0.46 V for 1a, 1b and 1c, respectively). Furthermore, 1,4-disilacyclohexadiene 1c absorbs strongly at 273 nm (4.55 eV), whereas 1a and 1b have no symmetry allowed excitations above 215 nm (below 5.77 eV). Thus, suitably substituted 1,4-disilacyclohexa-2,5-dienes could represent novel building blocks for the design of larger cross-hyperconjugated molecules as alternatives to traditional purely cross-p-conjugated analogues, and could allow for design of molecules with properties that are not accessible to those that are exclusively pi-conjugated.

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2014. Vol. 5, no 1, 360-371 p.
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Natural Sciences
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URN: urn:nbn:se:uu:diva-213891DOI: 10.1039/c3sc52389fISI: 000327601600045OAI: oai:DiVA.org:uu-213891DiVA: diva2:683788
Available from: 2014-01-06 Created: 2014-01-05 Last updated: 2016-03-08Bibliographically approved
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Emanuelsson, RikardHeijkenskjöld, FilipNauroozi, DjawedKarlsson, LeifFeifel, RaimundPettersson, RolandOtt, SaschaOttosson, Henrik
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