Quantification of Cooperativity between Metal Sites in Dinuclear Transition Metal Complexes Containing the (2‐Dimethylamino)‐4‐(2‐pyrimidinyl)pyrimidine Ligand. Issue 4 (19th April 2021)

• Record Type: Journal Article
• Authors: Wall, Tatjana; Leist, Marko; Dietrich, Fabian; Thiel, Werner R.; Gerhards, Markus
• Is Part Of: ChemPlusChem. Volume 86:Issue 4(2021)
• Page Start: 622
• Page End: 628
• Publication Date: 2021-04-19
• Subjects: cooperative effects -- density functional calculations -- fluorescence spectroscopy -- heterometallic complexes -- UV/Vis spectroscopy; Chemistry -- Periodicals; 540.5
• DOI: 10.1002/cplu.202100049
• Languages: English
• ISSNs: 2192-6506

Abstract

Abstract: A concept for the quantification of cooperative effects in transition‐metal complexes is presented. It is demonstrated for a series of novel N, N‐ (mononuclear) and C, N‐coordinated homo‐ and heterometallic binuclear complexes based on the (2‐dimethylamino)‐4‐(2‐pyrimidinyl)pyrimidine ligand, which are accessible by applying roll‐over cyclometallation. These iridium‐, platinum‐, and palladium‐containing compounds are investigated with respect to their absorption and fluorescence spectra. The cooperative effects in the electronic absorptions, i. e., the energetic shifts between mononuclear and dinuclear complexes, and free ligands are analyzed on the basis of the lowest energy π‐π* transitions and compared to calculated data, obtained from TD‐DFT calculations. Furthermore the corresponding fluorescence spectra are presented and analyzed with respect to the concept of cooperativity. Abstract : Modulated by metals : A concept for the quantification of cooperative effects for a series mono‐ and binuclear transition metal complexes with N, N‐ and C, N‐ligands is presented. The quantification is based on the metallic influence on the electronic properties, which were analyzed with UV/Vis and fluorescence spectroscopy as well as TD‐DFT calculations.