Abstract
The photophysics of triplet excitons in a series of electronically asymmetric “push−pull” π-conjugated meso-to-meso ethyne-bridged (porphinato)metal oligomers, along with electronically symmetric analogues, were studied by X-band electron paramagnetic resonance (EPR) spectroscopy under continuous-wave (CW) optical pumping conditions in the 4−100 K temperature range. In all of the systems studied, the spatial extent of the triplet wave function, as inferred from the |D| zero-field splitting (ZFS) parameter, never exceeds the dimensions of a single porphyryl moiety and its meso-pendant ethynyl groups. The |D| values determined for an oligomeric series of these electronically asymmetric species that span one through four porphyryl units are respectively 0.0301, 0.0303, 0.0300, and 0.0301 cm-1, indicating a common triplet wave function spatial delocalization of approximately 0.4−0.45 nm. Electron spin−spin and spin−lattice relaxation times were determined over the 4−30 K temperature range using progressive mi...
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