The Dominant Role of Chalcogen Bonding in the Crystal Packing of 2D/3D Aromatics

The chalcogen bond is a nonclassical σ‐hole‐based noncovalent interaction with emerging applications in medicinal chemistry and material science. It is found in organic compounds, including 2D aromatics, but has so far never been observed in 3D aromatic inorganic boron hydrides. Thiaboranes, harbori...

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Published inAngewandte Chemie International Edition Vol. 53; no. 38; pp. 10139 - 10142
Main Authors Fanfrlík, Jindřich, Přáda, Adam, Padělková, Zdeňka, Pecina, Adam, Macháček, Jan, Lepšík, Martin, Holub, Josef, Růžička, Aleš, Hnyk, Drahomír, Hobza, Pavel
Format Journal Article
LanguageEnglish
Published Weinheim WILEY-VCH Verlag 15.09.2014
WILEY‐VCH Verlag
Wiley Subscription Services, Inc
EditionInternational ed. in English
Subjects
Bonding
Bonding strength
boranes
Boron
chalcogen bonds
Charge distribution
Charging
Chemical analysis
crystal structures
Crystals
Organic compounds
Quantum chemistry
Sulfur
Three dimensional
X-ray diffraction
boranes
X-ray diffraction
chalcogen bonds
sulfur
crystal structures
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ISSN1433-7851
1521-3773
1521-3773
DOI10.1002/anie.201405901

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Summary:The chalcogen bond is a nonclassical σ‐hole‐based noncovalent interaction with emerging applications in medicinal chemistry and material science. It is found in organic compounds, including 2D aromatics, but has so far never been observed in 3D aromatic inorganic boron hydrides. Thiaboranes, harboring a sulfur heteroatom in the icosahedral cage, are candidates for the formation of chalcogen bonds. The phenyl‐substituted thiaborane, synthesized and crystalized in this study, forms sulfur⋅⋅⋅π type chalcogen bonds. Quantum chemical analysis revealed that these interactions are considerably stronger than both in their organic counterparts and in the known halogen bond. The reason is the existence of a highly positive σ‐hole on the positively charged sulfur atom. This discovery expands the possibilities of applying substituted boron clusters in crystal engineering and drug design. Chalcogen bonds of thiaboranes were found to be considerably stronger than σ‐hole bonds in organic compounds. The reason is the highly positive belt of σ‐holes on the positively charged sulfur atom. The charge distribution is the driving force for chalcogen bonding of thiaboranes.
Bibliography:istex:2E0D9D907122F70775D4DA797DBA3D01A2758165
Czech Science Foundation - No. P208/12/G016; No. P208/10/2269
ark:/67375/WNG-TC8XKMH1-3
IOCB Research Centre
ArticleID:ANIE201405901
Academy of Sciences of the Czech Republic
Czech Ministry of Education, Youth and Sports
This work was supported by research projects RVO 61388963 awarded by the Academy of Sciences of the Czech Republic. We acknowledge the financial support of the Czech Science Foundation (J.F., A.P., M.L., P.H.: grant number P208/12/G016; D.H.: grant number P208/10/2269). We also thank the Gilead Sciences and IOCB Research Centre for financial support. This work was also supported by the Operational Program Research and Development for Innovations-European Science Fund (grant number CZ.1.05/2.1.00/03.0058). This work was supported by the IT4Innovations Centre of Excellence project (CZ.1.05/1.1.00/02.0070), funded by the European Regional Development Fund and the national budget of the Czech Republic via the Research and Development for Innovations Operational Programme, as well as Czech Ministry of Education, Youth and Sports via the project Large Research, Development and Innovations Infrastructures (LM2011033).
Gilead Sciences
European Science Fund - No. CZ.1.05/2.1.00/03.0058
These authors contributed equally to this work.
This work was supported by research projects RVO 61388963 awarded by the Academy of Sciences of the Czech Republic. We acknowledge the financial support of the Czech Science Foundation (J.F., A.P., M.L., P.H.: grant number P208/12/G016; D.H.: grant number P208/10/2269). We also thank the Gilead Sciences and IOCB Research Centre for financial support. This work was also supported by the Operational Program Research and Development for Innovations—European Science Fund (grant number CZ.1.05/2.1.00/03.0058). This work was supported by the IT4Innovations Centre of Excellence project (CZ.1.05/1.1.00/02.0070), funded by the European Regional Development Fund and the national budget of the Czech Republic via the Research and Development for Innovations Operational Programme, as well as Czech Ministry of Education, Youth and Sports via the project Large Research, Development and Innovations Infrastructures (LM2011033).
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ISSN:1433-7851
1521-3773
1521-3773
DOI:10.1002/anie.201405901