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Expanding the (Cross-)Hyperconjugation of 1,4-Disilacyclohexa-2,5-dienes to Larger Monomers and Oligomers: A Computational Investigation
Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - Ångström, Molecular Biomimetics.
Uppsala University, Disciplinary Domain of Science and Technology, Technology, Department of Engineering Sciences, Nanotechnology and Functional Materials.
Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - Ångström, Molecular Biomimetics.
2016 (English)In: RSC Advances, ISSN 2046-2069, E-ISSN 2046-2069, Vol. 6, no 43, 36961-36970 p.Article in journal (Refereed) Published
Abstract [en]

We used density functional theory calculations to examine molecules that can be regarded as expanded 1,4-disilacyclohexa-2,5-dienes as well as oligomers based on these or 1,4-disilacyclohexa-2,5-diene with the aim to identify systems with extended (cross-)hyperconjugation. Among the three "expanded 1,4-disilacyclohexa-2,5-dienes" considered cyclobutadisilole is the most interesting as it has a higher thermodynamic stability than the isomeric 1,6-disilacyclodeca-2,3,4,7,8,9-hexaene and significantly lower first electronic excitation energy than 1,6-disilacyclodeca-2,4,7,9-tetraene. Cyclobutadisilole with trimethylsilyl substituents at Si shows particularly low excitations with the first strong transition at 3.46 eV (358 nm), i.e., similar to 1.1 eV lower than in 1,4-disilacyclohexa-2,5-diene. The monomers were connected into oligomers via their Si atoms using bis(dimethylsilanediyl) linkers, and some extended hyperconjugation was revealed. The first allowed UV/Vis excitation in the cyclobutadisilole-based tetramers is calculated at 2.57 eV (482 nm), although the lowering in excitation energies when going from monomer to tetramer is merely similar to 0.5 eV and hyperconjugation has modest impact on geometries. Yet, the tetra(cyclobutadisilole) has a significantly lower first allowed excitation when compared to a previously studied tetra(1,4-disilacyclohexadiene) with first excitation at 3.9 eV (318 nm).

Place, publisher, year, edition, pages
2016. Vol. 6, no 43, 36961-36970 p.
National Category
Organic Chemistry Engineering and Technology
Research subject
Chemistry with specialization in Organic Chemistry
Identifiers
URN: urn:nbn:se:uu:diva-293564DOI: 10.1039/C6RA02732FISI: 000374561300088OAI: oai:DiVA.org:uu-293564DiVA: diva2:927980
Funder
Swedish Research Council
Available from: 2016-05-13 Created: 2016-05-13 Last updated: 2016-07-12Bibliographically approved

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Denisova, AleksandraEmanuelsson, RikardOttosson, Henrik
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