Synthesis
and Electrochemical and Photophysical Properties
of Calixarene-Based Ruthenium(II) Complexes as Potential Multivalent
Photoreagents
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Abstract
The grafting of photoreactive and
photooxidizing Ru<sup>II</sup>(TAP) (TAP = 1,4,5,8-tetraazaphenanthrene)
complexes on calix[4 or
6]arene molecular platforms is reported. Thus, either [Ru(TAP)<sub>2</sub>(phen)]<sup>2+</sup> (phen = 1,10-phenanthroline) or [Ru(TAP)<sub>2</sub>(pytz)]<sup>2+</sup> [pytz = 2-(1,2,3-triazol-4-yl)pyridine]
complexes are anchored to the calixarenes. The data in electrochemistry,
combined with those in emission under steady state and pulsed illumination
and the determination of the associated photophysical rate constants,
indicate the presence of intramolecular luminescence quenching by
the phenol moieties of calixarene. From transient absorption studies
under pulsed laser irradiation, it is concluded that the quenching
originates from a par proton-coupled electron transfer (PCET) process.
Such an intramolecular quenching is absent when the phenol groups
of the calixarene platform are derivatized by azido arms