Effects of multiple ion loading on redox and luminescence properties of ruthenium trisphenanthroline crown ether hybrids.

Homoleptic and heteroleptic ruthenium trisphenanthrolines were prepared with azacrown ethers attached to the 4,7-positions of the phenanthrolines to maximise the electronic communication between the ruthenium and the crown ethers as complexation sites. Redox and spectral data were processed to explain the non-steady trends in the absorption and emission spectra in the series. Addition of Ba2+ entailed large shifts in the redox potential (up to 370 mV) and in the emission spectra (up to 87 nm). Due to the crowded situation of the azacrown ether units in, this complex showed a non-linear behaviour both in the redox and emission properties upon loading with Ba2+ that is postulated to originate from the intermediate formation of sandwich type complexes.