Tai, Hui-Chung, Zhao, Y., Farrer, Nicola J., Anastasi, Anna E., Clarkson, Guy J., Sadler, P. J. and Deeth, Robert J.. (2012) A Computational Approach to Tuning the Photochemistry of Platinum(IV) Anticancer Agents. Chemistry - A European Journal, Vol. 18 (No. 34). pp. 10630-10642. ISSN 0947-6539

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Abstract

Diazido Pt(IV) complexes are inert stable pro-drugs which can be photoactivated to produce Pt(II) species with promising anti-cancer activity. Our studies of the photochemistry of Pt(IV) complexes, [Pt(X)2(Y)2(Z)2]0/−1 (X=N-ligands (NH3, pyridine, etc.)/ S(CH3)2/ H−, Y=(pseudo)halogen (N3−, I−), Z=OR−, R=H, Ac, by time-dependent density functional theory (TDDFT) show close agreement with spectroscopic data. Broad exploration of cis/trans geometries, trans influences, the nature of the OR− and (pseudo)halogen ligands, electron-withdrawing/donating/delocalizing substituents on the N-ligands, and intramolecular H-bonds shows that: (i) the design of platinum(IV) complexes with intense bands shifted towards longer wavelengths (from 289 to ~330 nm) can be achieved by introducing intramolecular H-bonds involving the OH ligands and 2-hydroxyquinoline or by iodido ligands; (ii) mesomeric electron-withdrawing substituents on pyridine result in low-energy absorption with significant intensity in the visible region, and (iii) the distinct makeup of the molecular orbitals involved in the electronic transitions for cis/trans-{Pt(N3)2} isomers results in different photoproducts. In general, the comparison of the optimised geometries shows that Pt(IV) complexes with longer Pt−L bonds are more likely to undergo photoreduction with longer-wavelength light. The novel complex trans, trans, trans-[Pt(N3)2(OH)2(NH3)(4-nitropyridine)] with predicted absorption in the visible region has been synthesized. The experimental UV-Vis spectrum in aqueous solution correlates well with the intense band in the computed spectrum, whereas the overlay in the low-energy region can be improved by a solvent model. This combined computational and experimental study shows that TDDFT can be used to tune the coordination environment for optimizing photoactive Pt(IV) compounds as anticancer agents.

Item Type:	Journal Article
Subjects:	Q Science > QD Chemistry
Divisions:	Faculty of Science > Chemistry
Journal or Publication Title:	Chemistry - A European Journal
Publisher:	Wiley - V C H Verlag GmbH & Co. KGaA
ISSN:	0947-6539
Date:	2012
Volume:	Vol. 18
Number:	No. 34
Page Range:	pp. 10630-10642
Identification Number:	10.1002/chem.201200782
Status:	Peer Reviewed
Publication Status:	Published
Access rights to Published version:	Restricted or Subscription Access
URI:	http://wrap.warwick.ac.uk/id/eprint/50459

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