1. Room-temperature optical spin polarization of an electron spin qudit in a vanadyl -- free base porphyrin dimer
- Author
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Privitera, Alberto, Chiesa, Alessandro, Santanni, Fabio, Carella, Angelo, Ranieri, Davide, Caneschi, Andrea, Krzyaniak, Matthew D., Young, Ryan M., Wasielewski, Michael R., Carretta, Stefano, and Sessoli, Roberta
- Subjects
Quantum Physics ,Physics - Chemical Physics - Abstract
Photoexcited organic chromophores appended to molecular qubits can serve as a source of spin initialization or multi-level qudit generation for quantum information applications. So far, this approach has been primarily investigated in chromophore/stable radical systems. Here, we extend this concept to a meso-meso linked oxovanadium(IV) porphyrin - free base porphyrin dimer. Femtosecond transient absorption experiments reveal that photoexcitation of the free base porphyrin leads to picosecond triplet state formation via enhanced intersystem crossing. Time-resolved electron paramagnetic resonance (TREPR) experiments carried out at both 85 K and room temperature reveal the formation of a long-lived spin-polarized quartet state through triplet-doublet spin mixing. Notably, a distinct hyperfine structure arising from the interaction between the electron spin quartet state and the vanadyl nucleus (51V, I=7/2) is evident, with the quartet state exhibiting long-lived spin polarization even at room temperature. Theoretical simulations of the TREPR spectra confirm the photogenerated quartet state and provide insights into the non-Boltzmann spin populations. Exploit-ing this phenomenon affords the possibility of using photoinduced triplet states in porphyrins for quantum information as a resource to polarize and magnetically couple molecular electronic or nuclear spin qubits and qudits.
- Published
- 2024