Geminal Charge-Assisted Tetrel Bonds in Bis-Pyridinium Methylene Salts

Miriam Calabrese; Andrea Pizzi; Andrea Daolio; Maurizio Ursini; Antonio Frontera; Nicola Demitri; Carsten Lenczyk; Jakub Wojciechowski; Giuseppe Resnati

doi:10.1021/acs.cgd.2c01386

Geminal Charge-Assisted Tetrel Bonds in Bis-Pyridinium Methylene Salts

Cryst Growth Des. 2023 Feb 14;23(3):1898-1902. doi: 10.1021/acs.cgd.2c01386. eCollection 2023 Mar 1.

Authors

Miriam Calabrese¹, Andrea Pizzi¹, Andrea Daolio¹, Maurizio Ursini¹, Antonio Frontera², Nicola Demitri³, Carsten Lenczyk⁴, Jakub Wojciechowski⁵, Giuseppe Resnati¹

Affiliations

¹ NFMLab, Department of Chemistry, Materials, and Chemical Engineering "Giulio Natta", Politecnico di Milano, 20133 Milano, Italy.
² Department of Chemistry, Universitat de les Illes Balears, Crta. de Valldemossa km 7.5, 07122 Palma de Mallorca, Baleares, Spain.
³ Elettra Sincrotrone Trieste, S.S. 14 Km 163.5 in Area Science Park, Basovizza, 34149 Trieste, Italy.
⁴ Bruker AXS GmbH, Oestliche Rheinbrueckenstr. 49, 76187 Karlsruhe, Germany.
⁵ Rigaku Europe SE, Hugenottenallee 167. Neu-Isenburg 63263, Germany.

Abstract

C(sp³) atoms are known to act as electrophilic sites in self-assembly processes, and in all cases reported till now, they form only one interaction with nucleophiles; that is, they function as monodentate tetrel bond donors. This manuscript reports experimental (X-ray structural analysis) and theoretical evidence (DFT calculations), proving that the methylene carbon in bis-pyridinium methylene salts establishes two short and directional C(sp³)···anion interactions; that is, they function as bidentate tetrel bond donors.