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Optical-spin interfaces that enable the photoinitialization, coherent microwave manipulation, and optical read-out of ground state spins have been studied extensively in solid-state defects such as diamond nitrogen vacancy (NV) centers and are promising for quantum information science applications. Molecular quantum bits (qubits) offer many advantages over solid-state spin centers through synthetic control of their optical and spin properties and their scalability into well-defined multiqubit arrays. In this work, we report an optical-spin interface in an organic molecular qubit consisting of two luminescent tris(2,4,6-trichlorophenyl)methyl (TTM) radicals connected via the meta -positions of a phenyl linker. The triplet ground state of this system can be photoinitialized in its | T 0 ⟩ state by shelving triplet populations as singlets through spin-selective excited-state intersystem crossing with 80% selectivity from | T + ⟩ and | T - ⟩. The fluorescence intensity in the triplet manifold is determined by the ground-state polarization, and we show successful optical read-out of the ground-state spin following microwave manipulations by fluorescence-detected magnetic resonance spectroscopy. At 85 K, the lifetime of the polarized ground state is 45 ± 3 μs, and the ground state phase memory time is T m = 5.9 ± 0.1 μs, which increases to 26.8 ± 1.6 μs at 5 K. These results show that luminescent diradicals with triplet ground states can serve as optically addressable molecular qubits with long spin coherence times, which marks an important step toward the rational design of spin-optical interfaces in organic materials.

Electrolysis integrates renewable energy into chemical manufacturing and is key to sustainable chemistry. Controlling the waveform beyond direct current (DC) addresses the long-standing obstacle of chemoselectivity, yet it also expands the parameter set to optimize, creating a demand for theoretical predictions. Here, we report the first analytical theory for predicting chemoselectivity in an alternating current (AC) electrosynthesis. The mechanism is a selective reversal of the unwanted redox reaction during periods of opposite polarity, reflected in the final reaction outcome as a time-averaged effect. In the ideal scenario of all redox reactions being reversible, square AC waveform biases the outcome toward more overoxidation/over-reduction, whereas sine AC waveform exhibits the opposite effect. However, in a more realistic scenario of some redox reactions being quasi-reversible, sine AC may behave mostly like square AC. These predictions are in numerical agreement with model experiments employing acetophenone and align qualitatively with the literature precedent. Collectively, this study provides theoretical proof for a growing trend that promotes changing waveforms to overcome limitations challenging to address by varying canonical electrochemical parameters.

High-spin molecules allow for bottom-up qubit design and are promising platforms for magnetic sensing and quantum information science. Optical addressability of molecular electron spins has also been proposed in first-row transition-metal complexes via optically detected magnetic resonance (ODMR) mechanisms analogous to the diamond-nitrogen-vacancy color center. However, significantly less progress has been made on the front of metal-free molecules, which can deliver lower costs and milder environmental impacts. At present, most luminescent open-shell organic molecules are π-diradicals, but such systems often suffer from poor ground-state open-shell characters necessary to realize a stable ground-state molecular qubit. In this work, we use alternancy symmetry to selectively minimize radical-radical interactions in the ground state, generating π-systems with high diradical characters. We call them m -dimers, referencing the need to covalently link two benzylic radicals at their meta carbon atoms for the desired symmetry. Through a detailed electronic structure analysis, we find that the excited states of alternant hydrocarbon m -diradicals contain important symmetries that can be used to construct ODMR mechanisms leading to ground-state spin polarization. The molecular parameters are set in the context of a tris(2,4,6-trichlorophenyl)methyl (TTM) radical dimer covalently tethered at the meta position, demonstrating the feasibility of alternant m -diradicals as molecular color centers.

Most photochemistry occurs in the regime of weak light-matter coupling, in which a molecule absorbs a photon and then performs photochemistry from its excited state. In the strong coupling regime, enhanced light-matter interactions between an optical field and multiple molecules lead to collective hybrid light-matter states called polaritons. This strong coupling leads to fundamental changes in the nature of the excited states including multi-molecule delocalized excitations, modified potential energy surfaces, and dramatically altered energy levels relative to non-coupled molecules. The effect of strong light-matter coupling on covalent photochemistry has not been well explored. Photoswitches undergo reversible intramolecular photoreactions that can be readily monitored spectroscopically. In this work, we study the effect of strong light-matter coupling on the kinetics of photoswitching within optical cavities. Reproducing prior experiments, photoswitching of spiropyran/merocyanine photoswitches is decelerated in a cavity. Fulgide photoswitches, however, show the opposite effect, with strong coupling accelerating photoswitching. While modified merocyanine switching can be explained by changes in radiative decay rates or the amount of light in the cavity, modified fulgide switching kinetics suggest direct changes to excited-state reaction kinetics.