Semicoordination Bond Breaking and Halogen Bond Making Change the Supramolecular Architecture of Metal-Containing Aggregates

Lev E. Zelenkov, Daniil M. Ivanov, Evgeniy K. Sadykov, Nadezhda A. Bokach, Bartomeu Galmés, Antonio Frontera, Vadim Yu Kukushkin

Research outputpeer-review

9 Citations (Scopus)

Abstract

The complex [Ni(S2COEt)2] (1) and 1,4-diiodotertafluorobenzene (1,4-FIB) or 1,3,5-triiodotrifluorobenzene (1,3,5-FIB) were cocrystallized to form solid adducts 1·2(1,4-FIB) and 1·2(1,3,5-FIB), respectively; the structures of the adducts were studied by X-ray crystallography. The introduction of any one of the FIBs dramatically changed the supramolecular architecture of 1, and the structure-directing interactions changed from predominantly Ni···S semicoordination (in 1) to I···S halogen bonding between an FIB and the electron-donating S atoms of 1 (in the adducts). The semicoordination bond breaking and halogen bond making upon the interaction of 1 with the FIBs make the employed crystal engineering approach relevant (or even similar) to the molecular synthesis of metal species. The DFT study indicates that the strength of both types of interactions in the adducts are comparable (-3.0 to -4.9 kcal/mol and -4.3 to -4.9 kcal/mol) but very different in regard to their physical nature. If the electrostatics determine the I···S halogen bonds, the Ni···S semicoordination bonding is basically dominated by orbital effects.

Original languageEnglish
Pages (from-to)6956-6965
Number of pages10
JournalCrystal Growth and Design
Volume20
Issue number10
DOIs
Publication statusPublished - 7 Oct 2020

Scopus subject areas

  • Chemistry(all)
  • Materials Science(all)
  • Condensed Matter Physics

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