Room-Temperature Phosphorescence and Efficient Singlet Oxygen Production by Cyclometalated Pt(II) Complexes with Aromatic Alkynyl Ligands
Lázaro, A., Cunha, C., Bosque, R., Pina, J., Ward, J. S., Truong, K.-N., Rissanen, K., Lima, J. C., Crespo, M., Seixas de Melo, J. S., & Rodríguez, L. (2020). Room-Temperature Phosphorescence and Efficient Singlet Oxygen Production by Cyclometalated Pt(II) Complexes with Aromatic Alkynyl Ligands. Inorganic Chemistry, 59(12), 8220-8230. https://doi.org/10.1021/acs.inorgchem.0c00577
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Inorganic ChemistryAuthors
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2020Copyright
© 2020 American Chemical Society
The synthesis of five novel cyclometalated platinum(II) compounds containing five different alkynyl-chromophores was achieved by the reaction of the previously synthesized Pt–Cl cyclometalated compound (1) with the corresponding RC≡CH by a Sonogashira reaction. It was observed that the spectral and photophysical characteristics of the cyclometalated platinum(II) complexes (Pt–Ar) are essentially associated with the platinum-cyclometalated unit. Room-temperature emission of the Pt–Ar complexes was attributed to phosphorescence in agreement with DFT calculations. Broad nanosecond (ns)-transient absorption spectra were observed with decays approximately identical to those obtained from the emission of the triplet state. From the femtosecond-transient absorption (fs-TA) data, two main excited-state decay components were identified: one in the order of a few picoseconds was assigned to fast intersystem crossing to populate the triplet excited-state and the second (hundreds of ns) was associated with the decay of the transient triplet state. In general, efficient singlet oxygen photosensitization quantum yields were observed from the triplet state of these complexes.
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The authors are grateful to the Spanish Ministerio de Ciencia, Innovación y Universidades (AEI/FEDER, UE Project CTQ2016-76120-P and CTQ2015-65040-P). FCT/MCTES is acknowledged for financial support through the Associate Laboratory for Green Chemistry, LAQV-REQUIMTE (UID/QUI/50006/2013), the Coimbra Chemistry Centre (UID/QUI/00313/2019), and through Project PTDC/QUI-QFI/32007/2017 and Project “Hylight” (no. 031625) 02/SAICT/2017. We acknowledge funding by Fundo Europeu de Desenvolvimento Regional (FEDER) through Programa Operacional Factores de Competitividade (COMPETE) and project ROTEIRO/0152/2013. The research leading to these results received funding from Laserlab-Europe (grant agreement no. 284464, EC’s Seventh Framework Programme). ...License
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