π-Hole···dz2[PtII] Interactions with Electron-Deficient Arenes Enhance the Phosphorescence of PtII-Based Luminophores

Антон Викторович Рожков, Иван Ананьев, Rosa Gomila, Antonio Frontera, Вадим Юрьевич Кукушкин

Research output: Contribution to journalArticlepeer-review

20 Scopus citations

Abstract

Two phosphorescent PtII-based cyclometalated complexes were co-crystallized with perfluorinated arenes to give 1:1 co-crystals. The X-ray study revealed that each of the complexes is embraced by arenesF to give infinite reverse sandwich structures. In four out of six structures, a dz2 orbital of PtII is directed to the arenesF ring via π-hole···dz2[PtII] interactions, whereas in the other two structures, the filled dz2 orbital is directed toward the arene C atoms. Computed molecular electrostatic potential surfaces of the arenesF and the complexes, noncovalent interaction indexes for the co-crystals, and natural bond orbital calculations indicate that π-hole···dz2[PtII] contacts (and, generally, the stacking) are of electrostatic origin. The solid-state photophysical study revealed up to 3.5-fold luminescence quantum yield and 15-fold lifetime enhancements in the co-crystals. This increase is associated with the strength of the π-hole···dz2[PtII] contact that is dependent on the π-acidity of the areneF and its spatial characteristics.

Original languageEnglish
Pages (from-to)9308–9314
Number of pages7
JournalInorganic Chemistry
Volume59
Issue number13
DOIs
StatePublished - 6 Jul 2020

Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

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