Supramolecular Wiring of Benzo-1,3-chalcogenazoles through Programmed Chalcogen Bonding Interactions

Adrian Kremer, Andréa Fermi, Nicolas Biot, Johan Wouters, Davide Bonifazi

Research output: Contribution to journalArticle

Abstract

The high-yielding synthesis of 2-substituted benzo-1,3-tellurazoles and benzo-1,3-selenazoles through a dehydrative cyclization reaction has been reported, giving access to a large variety of benzo-1,3-chalcogenazoles. Exceptionally, these aromatic heterocycles proved to be very stable and thus very handy to form controlled solid-state organizations in which wire-like polymeric structures are formed through secondary N⋅⋅⋅Y bonding interactions (SBIs) engaging the chalcogen (Y=Se or Te) and nitrogen atoms. In particular, it has been shown that the recognition properties of the chalcogen centre at the solid state could be programmed by selectively barring one of its σ-holes through a combination of electronic and steric effects exerted by the substituent at the 2-position. As predicted by the electrostatic potential surfaces calculated by quantum chemical modelling, the pyridyl groups revealed to be the stronger chalcogen bonding acceptors, and thus the best ligand candidate for programming the molecular organization at the solid state. In contrast, the thiophenyl group is an unsuitable substituent for establishing SBIs in this molecular system as it gives rise to chalcogen-chalcogen repulsion. The weaker chalcogen donor properties of the Se analogues trigger the formation of feeble N⋅⋅⋅Se contacts, which are manifested in similar solid-state polymers featuring longer nitrogen-chalcogen distances.

Original languageEnglish
Pages (from-to)5665-5675
Number of pages11
JournalChemistry (Weinheim an der Bergstrasse, Germany)
Volume22
Issue number16
DOIs
Publication statusPublished - 11 Apr 2016

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Chalcogens
Electric wiring
Nitrogen
Cyclization
Surface potential
Electrostatics
Ligands
Wire
Atoms
Polymers

Keywords

  • chalcogens
  • selenium
  • self-assembly
  • supramolecular chemistry
  • tellurium
  • UV/Vis spectroscopy

Cite this

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title = "Supramolecular Wiring of Benzo-1,3-chalcogenazoles through Programmed Chalcogen Bonding Interactions",
abstract = "The high-yielding synthesis of 2-substituted benzo-1,3-tellurazoles and benzo-1,3-selenazoles through a dehydrative cyclization reaction has been reported, giving access to a large variety of benzo-1,3-chalcogenazoles. Exceptionally, these aromatic heterocycles proved to be very stable and thus very handy to form controlled solid-state organizations in which wire-like polymeric structures are formed through secondary N⋅⋅⋅Y bonding interactions (SBIs) engaging the chalcogen (Y=Se or Te) and nitrogen atoms. In particular, it has been shown that the recognition properties of the chalcogen centre at the solid state could be programmed by selectively barring one of its σ-holes through a combination of electronic and steric effects exerted by the substituent at the 2-position. As predicted by the electrostatic potential surfaces calculated by quantum chemical modelling, the pyridyl groups revealed to be the stronger chalcogen bonding acceptors, and thus the best ligand candidate for programming the molecular organization at the solid state. In contrast, the thiophenyl group is an unsuitable substituent for establishing SBIs in this molecular system as it gives rise to chalcogen-chalcogen repulsion. The weaker chalcogen donor properties of the Se analogues trigger the formation of feeble N⋅⋅⋅Se contacts, which are manifested in similar solid-state polymers featuring longer nitrogen-chalcogen distances.",
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Supramolecular Wiring of Benzo-1,3-chalcogenazoles through Programmed Chalcogen Bonding Interactions. / Kremer, Adrian; Fermi, Andréa; Biot, Nicolas; Wouters, Johan; Bonifazi, Davide.

In: Chemistry (Weinheim an der Bergstrasse, Germany), Vol. 22, No. 16, 11.04.2016, p. 5665-5675.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Supramolecular Wiring of Benzo-1,3-chalcogenazoles through Programmed Chalcogen Bonding Interactions

AU - Kremer, Adrian

AU - Fermi, Andréa

AU - Biot, Nicolas

AU - Wouters, Johan

AU - Bonifazi, Davide

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