Investigating the influence of relativistic effects on absorption spectra for platinum complexes with light-activated activity against cancer cells

Joel Creutzberg, Erik Donovan Hedegård

Research output: Contribution to journalJournal articleResearchpeer-review

Abstract

We report the first systematic investigation of relativistic effects on the UV-vis spectra of two prototype complexes for so-called photo-activated chemotherapy (PACT), trans–trans–trans-[Pt(N3)2(OH)2(NH3)2] and cis–trans–cis-[Pt(N3)2(OH)2(NH3)2]. In PACT, design of new drugs requires in-depth understanding of the photo-activation mechanisms. A first step is usually to rationalize their UV-vis spectra for which time-dependent density functional theory (TD-DFT) is an indispensable tool. We carried out TD-DFT calculations with a systematic series of non-relativistic (NR), scalar-relativistic (SR), and four-component (4c) Hamiltonians. As expected, large differences are found between spectra calculated within 4c and NR frameworks, while the most intense features (found at higher energies below 300 nm) can be reasonably well reproduced within a SR framework. It is also shown that effective core potentials (ECPs) yield essentially similar results as all-electron SR calculations. Yet the underlying transitions can be strongly influenced by spin–orbit coupling, which is only present in the 4c framework: while this can affect both intense and less intense transitions in the spectra, the effect is most pronounced for weaker transitions at lower energies, above 300 nm. Since the investigated complexes are activated with light of wavelengths above 300 nm, employing a method with explicit inclusion of spin–orbit coupling may be crucial to rationalize the activation mechanism.
Original languageEnglish
JournalPhysical Chemistry Chemical Physics
Volume22
Issue number46
Pages (from-to)27013-27023
ISSN1463-9076
DOIs
Publication statusPublished - Dec 2020
Externally publishedYes

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