Pt(II) complexes with a terpyridylazobenzene ligand (tpyAB) were newly synthesized, and their photoluminescence properties by trans-cis isomerization of the azo moiety were investigated. In these complexes, upon excitation with 366-nm light in polar solvents such as DMF, DMSO, and propylene carbonate, trans-to-cis isomerization with significant UV-vis spectral changes occurred almost completely. Cis-to-trans isomerization was observed both by irradiation with visible light and by heat. The reduction peaks due to the terpyridine and the azo group in the cyclic voltammograms of the Pt complexes were shifted in the positive direction by trans-to-cis isomerization. Emission spectral changes due to trans-cis isomerization were observed for both the tpyAB and the Pt complexes. The significant differences in the emission properties of the complex compared to tpyAB include the observation that both the excitation and emission wavelengths were shifted to lower energy, located in the visible region. Moreover, the change in emission intensity between the trans and cis forms was more significant upon excitation with UV light, because the trans form of the complexes showed absolutely no emission. Accordingly, the azobenzene-conjugated Pt(II) terpyridine complexes promise to be doubly photofunctional materials, showing complete off-on switching of emission linked to the trans-cis conformation change.

We synthesized azobenzene-conjugated bis(terpyridine) Ru(II) and Rh(III) mononuclear and dinuclear complexes and investigated their photochemical properties on excitation of the azo pi-pi band upon 366 nm light irradiation. The Ru mononuclear complex underwent trans-to-cis photoisomerization to reach the photostationary state with only 20% of the cis form, while the Ru dinuclear complex did not isomerize at all photochemically. On the other hand, the mononuclear and dinuclear Rh complexes showed almost complete trans-to-cis photoisomerization behavior. Cis forms of the Rh complexes thermally returned to the trans form at a much slower rate than those of organic azobenzenes, but they did not isomerize photochemically. The reduction potential of the cis forms was 80 mV more negative than that of the trans forms. The photoisomerization quantum yields of the Rh complexes were strongly dependent on the polarity, viscosity, and donor site of the solvents as well as the size of the counterions. We investigated the photoisomerization process of these complexes using femtosecond absorption spectroscopy. For the Rh complexes, we observed S(n) <-- S(2) and S(n) <-- S(1) absorption bands similar to those of organic azobenzenes. For the Ru complexes, we observed very fast bleaching of the MLCT band of the Ru complex, which indicated that the energy transfer pathway to the MLCT was the primary cause of the depressed photoisomerization. The electronic structures, which were estimated from ZINDO molecular orbital calculation, supported the different photochemical reaction behavior between the Ru and Rh complexes.