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Platinum azide complexes are appealing anticancer photochemotherapy drug candidates because they release cytotoxic azide radicals upon light irradiation. Here we present a density matrix renormalization group self-consistent field (DMRG-SCF) study of the azide photodissociation mechanism of trans,trans,trans-[Pt(N3)2(OH)2(NH3)2], including spin-orbit coupling. We find a complex interplay of singlet and triplet electronic excited states that falls into three different dissociation channels at well-separated energies. These channels can