To examine the impact of metal moieties that have different triplet energies on the photoisomerization of B(ppy)Mes2 compounds (ppy=2-phenyl pyridine, Mes=mesityl), three metal-functionalized B(ppy)Mes2 compounds, Re-B, Au-B, and Pt-B, have been synthesized and fully characterized. The metal moieties in these three compounds are Re(CO)3(tert-Bu2bpy)(CC), Au(PPh3)(CC), and trans-Pt(PPh3)2(CC)2, respectively, which are connected to the ppy chelate through the alkyne linker. Our investigation has established that the ReI unit completely quenches the photoisomerization of the boron unit because of a low-lying intraligand charge transfer/MLCT triplet state. The AuI unit, albeit with a triplet energy that is much higher than that of B(ppy)Mes2, upon conjugation with the ppy chelate unit, substantially increases the contribution of the π→π* transition, localized on the conjugated chelate backbone in the lowest triplet state, thereby leading to a decrease in the photoisomerization quantum efficiency (QE) of the boron chromophore when excited at 365 nm. At higher excitation energies, the photoisomerization QE of Au-B is comparable to that of the silyl–alkyne-functionalized B(ppy)Mes2 (TIPS-B), which was attributable to a triplet-state-sensitization effect by the AuI unit. The PtII unit links two B(ppy)Mes2 together in Pt-B, thereby extending the π-conjugation through both chelate backbones and leading to a very low QE of the photoisomerization. In addition, only one boron unit in Pt-B undergoes photoisomerization. The isomerization of the second boron unit is quenched by an intramolecular energy transfer of the excitation energy to the low-energy absorption band of the isomerized boron unit. TD-DFT computations and spectroscopic studies of the three metal-containing boron compounds confirm that the photoisomerization of the B(ppy)Mes2 chromophore proceeds through a triplet photoactive state and that metal units with suitable triplet energies can be used to tune this system.
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