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.
authors.affiliation: Namur Research College (NARC) and Department of Chemistry, University of Namur (UNamur), Rue de Bruxelles 61, Namur, 5000, Belgium.
authors.forename: Adrian
authors.initials: A
authors.lastname: Kremer
authors.affiliation: Namur Research College (NARC) and Department of Chemistry, University of Namur (UNamur), Rue de Bruxelles 61, Namur, 5000, Belgium.
authors.forename: Andrea
authors.initials: A
authors.lastname: Fermi
authors.affiliation: Namur Research College (NARC) and Department of Chemistry, University of Namur (UNamur), Rue de Bruxelles 61, Namur, 5000, Belgium.|School of Chemistry, Cardiff University, Park Place, CF10 3AT, Cardiff, UK.
authors.forename: Nicolas
authors.initials: N
authors.lastname: Biot
authors.affiliation: Namur Research College (NARC) and Department of Chemistry, University of Namur (UNamur), Rue de Bruxelles 61, Namur, 5000, Belgium.
authors.forename: Johan
authors.initials: J
authors.lastname: Wouters
authors.affiliation: Namur Research College (NARC) and Department of Chemistry, University of Namur (UNamur), Rue de Bruxelles 61, Namur, 5000, Belgium. BonifaziD@cardiff.ac.uk.|Department of Pharmaceutical and Chemical Sciences and, INSTM UdR Trieste, University of Trieste, Piazzale Europa 1, Trieste, 34127, Italy. BonifaziD@cardiff.ac.uk.|School of Chemistry, Cardiff University, Park Place, CF10 3AT, Cardiff, UK. BonifaziD@cardiff.ac.uk.
authors.forename: Davide
authors.initials: D
authors.lastname: Bonifazi
mesh_terms: D001393:Azoles / Q000737:chemistry*; D018011:Chalcogens / Q000737:chemistry*; D003198:Computer Simulation; D003500:Cyclization; D006860:Hydrogen Bonding; D008962:Models, Theoretical; D015394:Molecular Structure
chemical_list: D001393:Azoles; D018011:Chalcogens
keywords: UV/Vis spectroscopy; chalcogens; selenium; self-assembly; supramolecular chemistry; tellurium