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Photoactive platinum(II) azopyridine complexes

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Farley, Sarah J., Salassa, Luca, Pizarro, Ana M. and Sadler, Peter J. (2022) Photoactive platinum(II) azopyridine complexes. Photochemistry and Photobiology, 98 (1). pp. 92-101. doi:10.1111/php.13405 ISSN 0031-8655.

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Official URL: http://dx.doi.org/10.1111/php.13405

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Abstract

Platinum(II) complexes containing the strong π-acceptor N,N-chelating ligand phenylazopyridine (Ph-azpy) [Pt(p-R-Ph-azpy)X2], R = H, NMe2 or OH, X = Cl or N3, have been synthesized and characterized to explore the effects of monodentate ligands and phenyl substituents on their absorption spectra and photoactivation. Time-dependent density functional theory calculations showed that the complexes have a low-lying unoccupied orbital with strong σ-antibonding character toward the majority of the coordination bonds. The UV–visible absorption bands were assigned as mainly ligand-centered or metal-to-ligand charge-transfer transitions, with strong contributions from the chlorido and azido groups. In complexes with substituted Ph-azpy ligands, σ-donation from NMe2 and OH/O– groups results in a redshift of the main absorption bands compared with unsubstituted Ph-azpy complexes. The diazido complexes are photoactive in solution upon irradiation with either UVA or visible light for R = H or NMe2, or UVA only when R = OH/O–. Intriguingly, the phenolate group of the latter complex undergoes very slow protonation in solution. Biological screening was limited by poor solubility; however, initial tests showed that the phenolato diazido complex is rapidly taken up into the nuclei of HaCaT keratinocytes, which are stained intensely blue, and its cytotoxicity is increased upon irradiation with UVA light.

Item Type: Journal Article
Subjects: Q Science > QD Chemistry
R Medicine > RM Therapeutics. Pharmacology
Divisions: Faculty of Science, Engineering and Medicine > Science > Chemistry
SWORD Depositor: Library Publications Router
Library of Congress Subject Headings (LCSH): Platinum compounds, Platinum compounds -- Synthesis, Platinum compounds -- Absorption and adsorption , Phototherapy
Journal or Publication Title: Photochemistry and Photobiology
Publisher: Wiley-Blackwell Publishing, Inc
ISSN: 0031-8655
Official Date: January 2022
Dates:
DateEvent
January 2022Published
22 February 2021Available
18 February 2021Accepted
Volume: 98
Number: 1
Page Range: pp. 92-101
DOI: 10.1111/php.13405
Status: Peer Reviewed
Publication Status: Published
Access rights to Published version: Open Access (Creative Commons)
Date of first compliant deposit: 11 August 2021
Date of first compliant Open Access: 11 August 2021
RIOXX Funder/Project Grant:
Project/Grant IDRIOXX Funder NameFunder ID
G0701062[MRC] Medical Research Councilhttp://dx.doi.org/10.13039/501100000265
EP/G006792 [EPSRC] Engineering and Physical Sciences Research Councilhttp://dx.doi.org/10.13039/501100000266
EP/F034210/1[EPSRC] Engineering and Physical Sciences Research Councilhttp://dx.doi.org/10.13039/501100000266
20377Seventh Framework Programmehttp://dx.doi.org/10.13039/100011102

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