Primary photochemical processes for Pt(iv) diazido complexes prospective in photodynamic therapy of tumors

Abstract

A case study of chain photoaquation of mixed-ligand Pt(iv) diazido complexes tested in PDT of tumors is performed.

Spectroscopic Studies on Photoinduced Reactions of the Anticancer Prodrug, trans,trans,trans‐[Pt(N3)2(OH)2(py)2]

“…More recently, Shushakov et al. investigated the photophysical and photochemical processes of cis,trans,cis ‐[Pt(N 3 ) 2 (OH) 2 (NH 3 ) 2 ] and trans,trans,trans ‐[Pt(N 3 ) 2 (OH) 2 (NH 3 ) 2 ] on ps and μs timescales, capturing multistage photolysis for both complexes including initial substitution of one azide by a solvent molecule 19. Overall, the present findings by TEAS open up a new path for more comprehensive ultrafast photodynamic and high‐level theory studies of 1 , which are outside the scope of the present study.…”

Diazido platinum(iv) complexes for photoactivated anticancer chemotherapy

“…[90][91][92][93] A recent study on the first stage of photodecomposition using ultrafast kinetic spectroscopy and nanosecond laser flash photolysis suggested that the photodecomposition of both cis 2 and trans 3 is a chain process beginning with the replacement of one azide ligand by a water molecule and the release of azidyl radicals. 94 Two successive Pt(III) intermediates participated in chain initiation and [Pt III (NH 3 ) 2 (OH) 2 ] + was a chain carrier. 95 In addition, [Pt(N 3 ) 3 (OH)(NH 3 )(Py)] was observed by LC-MS as a photosubstitution product of 6 as well as azide ions, indicating the release of azide ligands.…”

The Role of Triplet States in the Photodissociation of a Platinum Azide Complex by a Density Matrix Renormalization Group Method

“…Platinum­(IV) complexes, − and in particular Pt­(IV) azides, ,− count among the first and yet most promising photoactivated drug candidates because they are stable in the absence of light and only upon light irradiation release highly cytotoxic products. − Accordingly, their photoreaction pathways have been heavily investigated experimentally ,,− but less so computationally. − Thus, understanding the major photoreaction pathway at the atomic leveli.e., the dissociation of the azide ligands that recombine to nitrogen along with the reduction of the metal center to Pt­(II)remains elusive.…”