A curious interplay in the films of N-heterocyclic carbene PtII complexes upon deposition of alkali metals

• Main Authors: Makarova, Anna A., Grachova, Elena V., Niedzialek, Dorota, Solomatina, Anastasia I., Sonntag, Simon, Fedorov, Alexander V., Vilkov, Oleg Yu., Neudachina, Vera S., Laubschat, Clemens, Tunik, Sergey P., Vyalikh, Denis V.
• Other Authors: Nature Publishing Group,
• Format: Article
• Language: English
• Published: Saechsische Landesbibliothek- Staats- und Universitaetsbibliothek Dresden 2016
• Subjects: N-heterocyclische Carbene; Photoelektronenspektroskopie; supramolekulares System; TU Dresden; Publikationsfond; N-heterocyclic carbene; photoelectron spectroscopy; supramolecular system; publicationfonds; ddc:614; rvk:XA 10000
• Online Access: http://nbn-resolving.de/urn:nbn:de:bsz:14-qucosa-215966; http://nbn-resolving.de/urn:nbn:de:bsz:14-qucosa-215966; http://www.qucosa.de/fileadmin/data/qucosa/documents/21596/srep25548.pdf

The recently synthesized series of PtII complexes containing cyclometallating (phenylpyridine or benzoquinoline) and N-heterocyclic carbene ligands possess intriguing structures, topologies, and light emitting properties. Here, we report curious physicochemical interactions between in situ PVD-grown films of a typical representative of the aforementioned PtII complex compounds and Li, Na, K and Cs atoms. Based on a combination of detailed core-level photoelectron spectroscopy and quantum-chemical calculations at the density functional theory level, we found that the deposition of alkali atoms onto the molecular film leads to unusual redistribution of electron density: essential modification of nitrogen sites, reduction of the coordination PtII centre to Pt0 and decrease of electron density on the bromine atoms. A possible explanation for this is formation of a supramolecular system "Pt complex-alkali metal ion"; the latter is supported by restoration of the system to the initial state upon subsequent oxygen treatment. The discovered properties highlight a considerable potential of the PtII complexes for a variety of biomedical, sensing, chemical, and electronic applications.