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Discrete Ti-O-Ti Complexes: Visible-Light-Activated, Homogeneous Alternative to TiO2 Photosensitisers.


ABSTRACT: A series of novel bimetallic TiIV amine bis(phenolate) complexes was synthesised and fully characterised. X-ray crystallography studies revealed distorted octahedral geometries around the Ti centres with single or double oxo-bridges connecting the two metals. These robust, air- and moisture-stable complexes were employed as photosensitisers generating singlet oxygen following irradiation with visible light (420?nm) LED module in a commercial flow reactor. All five complexes showed high activity in the photo-oxygenation of ?-terpinene and achieved complete conversion to ascaridole in four hours at ambient temperature. The excellent selectivity of these photosensitisers towards ascaridole (vs. transformation to p-cymene) was demonstrated with control experiments using a traditional TiO2 catalyst. Further comparative studies employing the free pro-ligands as well as a monometallic analogue highlighted the importance of the 'TiO2 -like' moiety in the polymetallic catalysts. Computational studies were used to determine the nature of the ligand to metal charge transfer (LMCT) states and singlet-triplet gaps for each complex, the calculated trends in the UV-vis absorption spectra across the series agreed well with the experimental results.

SUBMITTER: Behm K 

PROVIDER: S-EPMC7496837 | biostudies-literature | 2020 Aug

REPOSITORIES: biostudies-literature

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Discrete Ti-O-Ti Complexes: Visible-Light-Activated, Homogeneous Alternative to TiO<sub>2</sub> Photosensitisers.

Behm Kira K   Fazekas Eszter E   Paterson Martin J MJ   Vilela Filipe F   McIntosh Ruaraidh D RD  

Chemistry (Weinheim an der Bergstrasse, Germany) 20200709 43


A series of novel bimetallic Ti<sup>IV</sup> amine bis(phenolate) complexes was synthesised and fully characterised. X-ray crystallography studies revealed distorted octahedral geometries around the Ti centres with single or double oxo-bridges connecting the two metals. These robust, air- and moisture-stable complexes were employed as photosensitisers generating singlet oxygen following irradiation with visible light (420 nm) LED module in a commercial flow reactor. All five complexes showed hig  ...[more]

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