First example of the solid-state thermal cyclometalation of ligated benzophenone imine giving novel luminescent platinum(II) species
- Author(s)
- Yulia Scaffidi-Domianello, Alexey Nazarov, M Haukka, Mathea Sophia Galanski, Bernhard Keppler, Jacob Schneider, Pingwu Du, Richard M. Eisenberg, Vadim Yu Kukushkin
- Abstract
The (benzophenone imine)platinum(II) compounds trans-[PtCl 2(Ph2C=NH)(RR?SO)] [R, R? = Me, Me (2); n-Pr, n-Pr (3); (CH2)4 (4); Me, Ph (5); Me, p-MeC 6H4 (6)] were prepared by the reaction of Ph 2C=NH with K[PtCl3(RR?SO)], obtained in situ from K2[PtCl4] and the corresponding sulfoxide, giving 2-6 as well as cis-[PtCl2(Ph2C=NH)2] (1) as a minor product. The complexes were characterized by 1H, 13C, and 195Pt NMR and IR spectroscopy, electrospray ionization mass spectrometry, and C, H, and N elemental analysis. The X-ray crystallography of 1 enables confirmation of the cis configuration of the complex, while in 2 and 4·1/2CHCl3, the imine and sulfoxide ligands are mutually trans. The solid-state structure of 4·1/2CHCl3 consists of two dimeric Pt moieties representing a rather weak Pt?Pt interaction. The dimeric architecture of 4·1/2CHCl3 is enhanced by the hydrogen bonding between imine H atoms and O atoms. The orthometalation of 1 and 2-6 proceeds both in the solid phase and in a toluene suspension, leading to the formation of [PtCl{Ph(C6H4)C=NH}(Ph2C=NH)] (7) and [PtCl{Ph(C6H4)C=NH}(RR?SO)] (8-12), respectively, isolated in nearly quantitative yields. Complexes 8-12 are emissive at room temperature both in solution (?emmax ?535 nm) and in the solid state (?emmax 560-610 nm), with excited-state lifetimes of ca. 300-600 ns, representing a new family of PtII-based luminescent complexes. Compounds 8 and 10 have been characterized by X-ray analysis, confirming the square-planar coordination geometry of the metal center with the almost planar platinacycles. In 8, the asymmetric unit contains two independent Pt molecules, while in 10, it includes four Pt molecules linked by the intermolecular hydrogen-bonding network between the NH group and Cl atoms. © 2007 American Chemical Society.
- Organisation(s)
- Department of Inorganic Chemistry
- External organisation(s)
- University of Joensuu, University of Rochester, Saint Petersburg State University
- Journal
- Inorganic Chemistry
- Volume
- 46
- Pages
- 4469-4482
- No. of pages
- 14
- ISSN
- 0020-1669
- Publication date
- 2007
- Peer reviewed
- Yes
- Austrian Fields of Science 2012
- 104003 Inorganic chemistry
- Portal url
- https://ucrisportal.univie.ac.at/en/publications/3fb0f93d-1437-43a5-a008-b21359ae6d14