New Ru(II) Complex for Dual Activity: Photoinduced Ligand Release and (1)O2 Production.

ABSTRACT: The new complex [Ru(pydppn)(biq)(py)](2+) (1) undergoes both py photodissociation in CH3CN with ?500 =0.0070(4) and (1)O2 production with ?? =0.75(7) in CH3 OH from a long-lived (3) ??* state centered on the pydppn ligand (pydppn=3-(pyrid-2-yl)benzo[i]dipyrido[3,2-a:2',3'-c]phenazine; biq = 2,2'-biquinoline; py=pyridine). This represents an order of magnitude decrease in the ?500 compared to the previously reported model compound [Ru(tpy)(biq)(py)](2+) (3) (tpy=2,2':6',2''-terpyridine) that undergoes only ligand exchange. The effect on the quantum yields by the addition of a second deactivation pathway through the low-lying (3) ??* state necessary for dual reactivity was investigated using ultrafast and nanosecond transient absorption spectroscopy, revealing a significantly shorter (3) MLCT lifetime in 1 relative to that of the model complex 3. Due to the structural similarities between the two compounds, the lower values of ?500 and ?? compared to that of [Ru(pydppn)(bpy)(py)](2+) (2) (bpy=2,2'-bipyridine) are attributed to a competitive excited state population between the (3) LF states involved in ligand dissociation and the long-lived (3) ??* state in 1. Complex 1 represents a model compound for dual activity that may be applied to photochemotherapy.

SUBMITTER: Loftus LM 

PROVIDER: S-EPMC4775357 | biostudies-literature | 2016 Mar

REPOSITORIES: biostudies-literature