Abstract
Energy and electron transfer reactions are central to many different processes and research fields, from photosynthesis and solar energy harvesting to biological and medical applications. Herein we report a comprehensive study of the singlet and triplet energy transfer dynamics in porphyrin-anthracene coordination complexes. Seven newly synthesized pyridine functionalized anthracene ligands, five with various bridge lengths and two dendrimer structures containing three and seven anthracene units, were prepared. We found that triplet energy transfer from ruthenium octaethylporphyrin to an axially coordinated anthracene is possible, and is in some cases followed by back triplet energy transfer to the porphyrin. The triplet energy transfer follows an exponential distance dependence with an attenuation factor, β, of 0.64 Å-1. Further, singlet energy transfer from anthracene to the ruthenium porphyrin appears to follow a R6 Förster distance dependence. Porphyrin-anthracene complexes are also used as triplet sensitizers for triplet-triplet annihilation (TTA) based photon upconversion, demonstrating their potential for photophysical and photochemical applications. The triplet lifetime of the complex is extended by the anthracene ligands, resulting in a threefold increase in the upconversion efficiency, ΦUC to 4.5%, compared to the corresponding ruthenium porphyrin-pyridine complex. Based on the results herein we discuss the future design of supra-molecular structures for TTA upconversion.
Highlights
Energy and electron transfer reactions are central to many different processes and research fields, from photosynthesis and solar energy harvesting to biological and medical applications
The dendrimer ligands were synthesized by repeating a sequence of three high yielding and simple reactions; bromination followed by borylation followed by a Suzuki-coupling, similar to our previously established route for DPA dendrons and dendrimers.[45]
We report a comprehensive study of the energy transfer processes of seven new ruthenium porphyrin–anthracene coordination complexes, RuOEP(CO)L
Summary
1.1 Ligand design and synthesis Ligand design is based on our previous work with 9,10-diphenylanthracene (DPA) based ligands and dendrimeric structures.[25,45] Fig. 1 shows the structures of the ligands: ligand 1 has a metapyridine substitution, ligands 2–5 have para-pyridine substitutions with increasing bridge lengths and dendrimeric ligands 6 and 7 have an increasing number of DPA monomer units. By borylation followed by a Suzuki-coupling, similar to our previously established route for DPA dendrons and dendrimers.[45] The synthetic route is illustrated in Fig. S1 and described in more detail in the ESI.† Similar to what was reported previously RuOEP(CO) was obtained by refluxing the corresponding freebase porphyrin with Ru3CO12.46–48 ‡
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