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Ru(ii) complexes with diazine ligands: electronic modulation of the coordinating group is key to the design of "dual action" photoactivated agents.

ABSTRACT: Coordination complexes can be used to photocage biologically active ligands, providing control over the location, time, and dose of a delivered drug. Dual action agents can be created if both the ligand released and the ligand-deficient metal center effect biological processes. Ruthenium(ii) complexes coordinated to pyridyl ligands generally are only capable of releasing one ligand in H2O, wasting equivalents of drug molecules, and producing a Ru(ii) center that is not cytotoxic. In contrast, Ru(ii) polypyridyl complexes containing diazine ligands eject both monodentate ligands, with the quantum yield (?PS) of the second phase varying as a function of ligand pKa and the pH of the medium. This effect is general, as it is effective with different Ru(ii) structures, and demonstrates that diazine-based drugs are the preferred choice for the development of light-activated dual action Ru(ii) agents.

SUBMITTER: Havrylyuk D

PROVIDER: S-EPMC6411420 | biostudies-literature | 2018 Nov

REPOSITORIES: biostudies-literature

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Ru(ii) complexes with diazine ligands: electronic modulation of the coordinating group is key to the design of "dual action" photoactivated agents.

Havrylyuk Dmytro D Deshpande Megha M Parkin Sean S Glazer Edith C EC

Chemical communications (Cambridge, England) 20181101 88

Coordination complexes can be used to photocage biologically active ligands, providing control over the location, time, and dose of a delivered drug. Dual action agents can be created if both the ligand released and the ligand-deficient metal center effect biological processes. Ruthenium(ii) complexes coordinated to pyridyl ligands generally are only capable of releasing one ligand in H2O, wasting equivalents of drug molecules, and producing a Ru(ii) center that is not cytotoxic. In contrast, Ru ...[more]

PMID: 30338772

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Project description:The series of complexes [XRu(CO)(L-L)(L')2][PF6] (X = H, TFA, Cl; L-L = 2,2'-bipyridyl, 1,10-phenanthroline, 5-amino-1,10-phenanthroline and 4,4'-dicarboxylic-2,2'-bipyridyl; L'2 = 2PPh3, Ph2 PC2H4PPh2, Ph2PCH═CHPPh2) have been synthesized from the starting complex K[Ru(CO)3(TFA)3] (TFA = CF3CO2) by first reacting with the phosphine ligand, followed by reaction with the L-L and anion exchange with NaPF6. In the case of L-L = phenanthroline and L'2 = 2PPh3, the neutral complex Ru(Ph3P)(CO)(1,10-phenanthroline)( TFA)2 is also obtained and its solid state structure is reported. Solid state structures are also reported for the cationic complexes where L-L = phenanthroline, L2 = 2PPh3 and X = Cl and for L-L = 2,2'-bipyridyl, L2 = 2PPh3 and X = H. All the complexes were characterized in solution by a combination of 1H and 31P NMR, IR, mass spectrometry and elemental analyses. The purpose of the project was to synthesize a series of complexes that exhibit a range of excited-state lifetimes and that have large Stokes shifts, high quantum yields and high intrinsic polarizations associated with their metal-to-ligand charge-transfer (MLCT) emissions. To a large degree these goals have been realized in that excited-state lifetimes in the range of 100 ns to over 1 μs are observed. The lifetimes are sensitive to both solvent and the presence of oxygen. The measured quantum yields and intrinsic anisotropies are higher than for previously reported Ru(II) complexes. Interestingly, the neutral complex with one phosphine ligand shows no MLCT emission. Under the conditions of synthesis some of the initially formed complexes with X = TFA are converted to the corresponding hydrides or in the presence of chlorinated solvents to the corresponding chlorides, testifying to the lability of the TFA Ligand. The compounds show multiple reduction potentials which are chemically and electrochemically reversible in a few cases as examined by cyclic voltammetry. The relationships between the observed photophysical properties of the complexes and the nature of the ligands on the Ru(II) is discussed.

Dataset Information

Ru(ii) complexes with diazine ligands: electronic modulation of the coordinating group is key to the design of "dual action" photoactivated agents.

Publications

Ru(ii) complexes with diazine ligands: electronic modulation of the coordinating group is key to the design of "dual action" photoactivated agents.

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