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[Ru(bpy)3]2+, [ReCl(CO)3], and naphthalimde moieties can be incorporated into palladium cages via triazole linkers. The emissive properties of these units are virtually unchanged from the uncaged species, with the [Ru(bpy)3]2+ lifetime shortening from 943 to 659 ns and the naphthalimde quantum yield reducing from 0.72 to 0.59. This opens the possibility of aggregating photophysically and redox active moieties, via cage assembly, without compromising their properties.
The photophysics of a family of exo-functionalized [Pd2L4]4+ metallo-supramolecular cage architectures constructed from a tripyridyl 1,2,3-triazole backbone are reported. Several spectroscopic techniques are employed including both electronic (steady-state and transient absorption and emission) and vibrational (resonant and nonresonant Raman) methods. These experimental results are interpreted alongside simulated results from density functional theory calculations of the system’s vibrational and electronic properties. The ligands and cages are shown to be essentially insulated from the exo-functionalization. They exhibit electronic transitions in the UV region and excited-state properties that are little affected by formation of the cage. Upon functionalization, characteristic Raman bands, electronic transitions, and emission bands associated with, and confined to, the substituent are observed.
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