Structural distortions from the ideal octahedral geometry are known to facilitate the photorelease of kinetically inert groups in Ru_((II))polypyridyl complexes.Building on this principle,here we report,for the first ...Structural distortions from the ideal octahedral geometry are known to facilitate the photorelease of kinetically inert groups in Ru_((II))polypyridyl complexes.Building on this principle,here we report,for the first time,the design of a water-soluble Ru_((II))complex containing a terpyridine-dicarboxylate pentadentate ligand(LH_(2)),formulated as[Ru{ptpy(COO^(-))_(2)}(DMSO)](RuL),engineered for efficient photorelease of the bound monodentate DMSO ligand in aqueous medium.This work presents a novel idea for inducing axial Ru-DMSO bond photolability from the conformational strain originating from a pentadentate ligand in an Ru_((II))complex,triggering photodissociation to create potent cytotoxic species for phototherapeutic application.The molecular identity,and photophysical and electrochemical features with solution speciation of the RuL were examined.The blue-light-triggered photo-substitution was studied to gain insight into potential adduct formation with biological targets relevant to photo-activated chemotherapeutic(PACT)uses.The geometry-optimized structure and the nature of the frontier molecular orbitals have been determined using DFT calculations.The photosubstitution quantum yield(Φ_(PS))in acetonitrile was thirteen times greater than that in water,highlighting the significant influence of solvent on the photochemical efficiency.Notably,the RuL ligand exhibited substantial cytotoxicity under light irradiation,while remaining non-cytotoxic in the dark,underscoring its potential utility in Ru_((II))-based photo-activated chemotherapy.展开更多
基金acknowledge the Indian Council of Medical Research(ICMR)(project no.2020-2677)the Council of Scientific and Industrial Research(CSIR)(project no.01(3048)/21/EMR-II)+1 种基金the Science and Engineering Research Board(SERB)(CRG/2021/000527)for financial supportDepartment of Science and Technology(DST)for a research fellowship.
文摘Structural distortions from the ideal octahedral geometry are known to facilitate the photorelease of kinetically inert groups in Ru_((II))polypyridyl complexes.Building on this principle,here we report,for the first time,the design of a water-soluble Ru_((II))complex containing a terpyridine-dicarboxylate pentadentate ligand(LH_(2)),formulated as[Ru{ptpy(COO^(-))_(2)}(DMSO)](RuL),engineered for efficient photorelease of the bound monodentate DMSO ligand in aqueous medium.This work presents a novel idea for inducing axial Ru-DMSO bond photolability from the conformational strain originating from a pentadentate ligand in an Ru_((II))complex,triggering photodissociation to create potent cytotoxic species for phototherapeutic application.The molecular identity,and photophysical and electrochemical features with solution speciation of the RuL were examined.The blue-light-triggered photo-substitution was studied to gain insight into potential adduct formation with biological targets relevant to photo-activated chemotherapeutic(PACT)uses.The geometry-optimized structure and the nature of the frontier molecular orbitals have been determined using DFT calculations.The photosubstitution quantum yield(Φ_(PS))in acetonitrile was thirteen times greater than that in water,highlighting the significant influence of solvent on the photochemical efficiency.Notably,the RuL ligand exhibited substantial cytotoxicity under light irradiation,while remaining non-cytotoxic in the dark,underscoring its potential utility in Ru_((II))-based photo-activated chemotherapy.
