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Inorganics 2015, 3(2), 55-81; doi:10.3390/inorganics3020055

Turning-On of Coumarin Phosphorescence in Acetylacetonato Platinum Complexes of Cyclometalated Pyridyl-Substituted Coumarins

Fachbereich Chemie der Universität Konstanz, Universitätsstraße 10, D-78457 Konstanz, Germany
Author to whom correspondence should be addressed.
Academic Editors: Axel Klein and Elena Lalinde
Received: 16 January 2015 / Revised: 9 April 2015 / Accepted: 10 April 2015 / Published: 17 April 2015
(This article belongs to the Special Issue Organoplatinum Complexes)
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Two pyridine-functionalized coumarins differing with respect to the site of pyridine attachment to the coumarin dye (3 in L1 or 7 in L2) and with respect to the presence (L1) or absence (L2) of a peripheral NMe2 donor were prepared and used as cyclometalating ligands towards the Pt(acac) fragment. X-ray crystal structures of complexes 1 and 2 show strong intermolecular interactions by π-stacking and short Pt∙∙∙Pt or C-H∙∙∙O hydrogen bonding that result in the formation of sheetlike packing patterns. The NMe2 donor substituent has a profound influence on the absorption and emission properties of the free coumarin dyes; L1 emits strongly while L2 is only weakly emissive. On binding to Pt(acac) the strong fluorescence of L1 is partially quenched while coumarin phosphorescence is observed from cyclometalated L1 and L2. The ligand-centered nature of the LUMO was confirmed by IR spectroelectrochemistry while the assignment of the phosphorescence emission as ligand-based rests on the vibrational structuring, the negligible solvatochromism, the small temperature-induced Stokes shifts on cooling to 77 K, the emission lifetimes, and strong oxygen quenching. (TD-)DFT calculations confirm our experimental results and provide an assignment of the electronic transitions and the spin density distributions in the T1 state. View Full-Text
Keywords: platinum; emission; coumarin; crystal structure; quantum chemical calculations platinum; emission; coumarin; crystal structure; quantum chemical calculations

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This is an open access article distributed under the Creative Commons Attribution License which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited. (CC BY 4.0).

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Jackel, A.; Linseis, M.; Häge, C.; Winter, R.F. Turning-On of Coumarin Phosphorescence in Acetylacetonato Platinum Complexes of Cyclometalated Pyridyl-Substituted Coumarins. Inorganics 2015, 3, 55-81.

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