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Optimization of the Cyclic Cross-Hyperconjugation in 1,4-Ditetrelcyclohexa-2,5-dienes
Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - BMC, Physical Organic Chemistry.
Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - BMC, Physical Organic Chemistry.
Institut für Chemie, Universität Graz.
Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - BMC, Physical Organic Chemistry.
2014 (English)In: Organometallics, ISSN 0276-7333, E-ISSN 1520-6041, Vol. 33, no 12, p. 2997-3004Article in journal (Refereed) Published
Abstract [en]

Cyclic cross-hyperconjugation can exist to variable extents in 1,4-ditetrelcyclohexa-2,5-dienes, i.e., all-carbon cyclohexa-1,4-dienes and 1,4-disila/digerma/distanna/diplumbacyclohexa-2,5-dienes. In this study we first use density functional theory (DFT) computations to optimize the conjugation strength by seeking the optimal atom E and substituent group E'Me-3 in the two saturated E(E'Me-3)(2) moieties (E and E' as the same or different tetrel (group 14) elements). We reveal that the all-carbon cyclohexadienes with gradually heavier E'Me-3 substituents at the two saturated carbon atoms display significant cross-hyperconjugation. The first electronic excitations in these compounds, which formally have two isolated C=C bonds, are calculated to reach wavelengths as long as 400 nm (excitation energies of 3.1 eV). These transitions are mostly forbidden, and the lowest allowed transitions are found at 387 nm (3.2 eV). The silicon analogues are also cross-hyperconjugated, while a decline is observed in the 1,4-digerma/distanna/diplumbacyclohexa-2,5-diene. Experiments on two substituted 1,4-disilacyclohexa-2,5-dienes confirm the effect of the E'Me3 substituents, with regard to both electronic excitations and geometries as determined by UV absorption spectroscopy and X-ray crystallography, respectively. At the end, we reveal through computations how electron-donating and electron-withdrawing substituents at the C=C double bonds influence the electronic properties of the all-carbon ring. We find that the first calculated excitation, which is forbidden, can be shifted to 440 nm (2.83 eV). This shows to what extent cyclic cross-hyperconjugation can affect the electronic and optical properties of a compound with two formally isolated C=C double bonds.

Place, publisher, year, edition, pages
2014. Vol. 33, no 12, p. 2997-3004
National Category
Organic Chemistry
Research subject
Chemistry with specialization in Organic Chemistry
Identifiers
URN: urn:nbn:se:uu:diva-221022DOI: 10.1021/om5001875ISI: 000337936800008OAI: oai:DiVA.org:uu-221022DiVA, id: diva2:707530
Available from: 2014-03-24 Created: 2014-03-24 Last updated: 2017-12-12Bibliographically approved
In thesis
1. Conjugation in Organic Group 14 Element Compounds: Design, Synthesis and Experimental Evaluation
Open this publication in new window or tab >>Conjugation in Organic Group 14 Element Compounds: Design, Synthesis and Experimental Evaluation
2014 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

This thesis focuses on the chemical concept of conjugation, i.e., electron delocalization, and the effect it has on electronic and optical properties of molecules. The emphasis is on electron delocalization across a saturated σ-bonded segment, and in our studies these segments are either inserted between π-conjugated moieties or joined together to form longer chains. The electronic and optical properties of these compounds are probed and compared to those of traditionally π-conjugated compounds. The investigations utilize a combination of qualitative chemical bonding theories, quantum chemical calculations, chemical syntheses and different spectroscopic methods.

Herein, it is revealed that a saturated σ-bonded segment inserted between two π-systems can have optical and electronic properties similar to a cross-conjugated compound when substituents with heavy Group 14 elements (Si, Ge or Sn) are attached to the central atom. We coined the terminology cross-hyperconjugation for this interaction, and have shown it by both computational and spectroscopic means. This similarity is also found in cyclic compounds, for example in the 1,4-disilacyclohexa-2,5-dienes, as we reveal that there is a cyclic aspect of cross-hyperconjugation. Cross-hyperconjugation can further also be found in smaller rings such as siloles and cyclopentadienes, and we show on the similarities between these and their cross-π-conjugated analogues, the fulvenes. Here, this concept is combined with that of excited state aromaticity and the electronic properties of these systems are rationalized in terms of “aromatic chameleon” effects. We show that the optical properties of these systems can be rationally tuned and predicted through the choice of substituents and knowledge about the aromaticity rules in both ground and excited states.

We computationally examine the relation between conjugation and conductance and reveal that oligomers of 1,4-disilacyclohexa-2,5-dienes and related analogues can display molecular cord properties. The conductance through several σ-conjugated silicon compounds were also examined and show that mixed silicon and carbon bicyclo[2.2.2]octane compounds do not provide significant benefits over the open-chain oligosilanes. However, cyclohexasilanes, a synthetic precursor to the bicyclic compounds, displayed conformer-dependent electronic structure variations that were not seen for cyclohexanes. This allowed for computational design of a mechanically activated conductance switch.

Place, publisher, year, edition, pages
Uppsala: Acta Universitatis Upsaliensis, 2014. p. 70
Series
Digital Comprehensive Summaries of Uppsala Dissertations from the Faculty of Science and Technology, ISSN 1651-6214 ; 1140
Keywords
conjugation, conductance, electronic structure, Group 14 elements, hyperconjugation, molecular electronics, organosilicon chemistry
National Category
Organic Chemistry Physical Chemistry
Research subject
Chemistry with specialization in Organic Chemistry
Identifiers
urn:nbn:se:uu:diva-221683 (URN)978-91-554-8929-8 (ISBN)
Public defence
2014-05-27, B42, BMC, Husargatan 3, Uppsala, 13:15 (English)
Opponent
Supervisors
Available from: 2014-05-06 Created: 2014-04-03 Last updated: 2014-06-30
2. Hyperconjugation in Group 14 Organic Compounds: Design and Property Investigations
Open this publication in new window or tab >>Hyperconjugation in Group 14 Organic Compounds: Design and Property Investigations
2017 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

Nowadays π-conjugated molecules are widely used as materials for devices in organic and molecular electronics. This is due to the ability of such molecules to conduct electricity. However, π-conjugation leads to molecular rigidness and associated lower solubility, which limits possible applications. Meanwhile, there are other types of conjugation that do not cause molecular rigidness but still provide conductivity. One of them is so called hyperconjugation. While π-conjugation involves only p atomic orbitals, hyperconjugation is characterized by interaction of π and σ orbitals. Hyperconjugation is normally weaker than π-conjugation, thus, in order to get strongly hyperconjugated molecules they should be enhanced in some way.

In this thesis, I describe methods for design of strongly hyperconjugated molecules. It is possible to increase the strength of hyperconjugation by various methods and some of them are discussed. We performed quantum chemical calculations in order to investigate optical and geometric properties of the hyperconjugated molecules and evaluate the relative strength of hyperconjugation. In some cases, results of calculations were compared with experimental results aiming to confirm the relevance of the calculations. First, we have investigated how the change of group 14 elements in the 1,4-ditetrelocyclohexa-2,5-dienes influence the hyperconjugation strength. Next, the substituent effect was considered in fulvenes and their hyperconjugated analogs. We showed this effect from the perspective of the substituents influence on the aromatic properties of molecules in the ground and first electronically excited states. Further, the gradual shift when going from monomer to oligomers were investigated. For this hyperconjugated oligomers were constructed from 1,4-disilacyclohexa-2,5-diene and cyclobutadisilole fragments. Additionally we showed the influence of electron withdrawing and electron donating groups on hyperconjugation in siloles and 1,4-disilacyclohexa-2,5-dienes. Finally, hyperconjugation was investigated in a set of silicon-containing omni-hyperconjugated compounds.

The results obtained from this research showed that hyperconjugation strength can be increased significantly up to levels comparable to purely π-conjugated molecules. We hope that these results will be useful in development of other hyperconjugated small molecules, oligomers, and polymers, which can be further used as material for electronic devices.

Place, publisher, year, edition, pages
Uppsala: Acta Universitatis Upsaliensis, 2017. p. 61
Series
Digital Comprehensive Summaries of Uppsala Dissertations from the Faculty of Science and Technology, ISSN 1651-6214 ; 1613
Keywords
1, 4-disilacyclohexa-2, 5-diene, aromaticity, computational chemistry, conjugation, cross-hyperconjugation, hyperconjugation, group 14 elements, organosilicon chemistry, silole
National Category
Organic Chemistry
Identifiers
urn:nbn:se:uu:diva-336192 (URN)978-91-513-0190-7 (ISBN)
Public defence
2018-02-09, Häggsalen, Ångström laboratory, Lägerhyddsvägen 1, Uppsala, 09:15 (English)
Opponent
Supervisors
Available from: 2018-01-19 Created: 2017-12-12 Last updated: 2018-03-07

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Emanuelsson, RikardDenisova, AleksandraOttosson, Henrik

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