The Library
A computational approach to tuning the photochemistry of platinum(IV) anticancer agents
Tools
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. doi:10.1002/chem.201200782 ISSN 0947-6539.
Research output not available from this repository.
Request-a-Copy directly from author or use local Library Get it For Me service.
Official URL: http://dx.doi.org/10.1002/chem.201200782
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, Engineering and Medicine > Science > Chemistry | ||||
Journal or Publication Title: | Chemistry - A European Journal | ||||
Publisher: | Wiley - V C H Verlag GmbH & Co. KGaA | ||||
ISSN: | 0947-6539 | ||||
Official Date: | 2012 | ||||
Dates: |
|
||||
Volume: | Vol.18 | ||||
Number: | No.34 | ||||
Page Range: | pp. 10630-10642 | ||||
DOI: | 10.1002/chem.201200782 | ||||
Status: | Peer Reviewed | ||||
Publication Status: | Published | ||||
Access rights to Published version: | Restricted or Subscription Access |
Request changes or add full text files to a record
Repository staff actions (login required)
View Item |