Brian T. Phelan

The Jahn–Teller distortion (JTD) is a defining structural response to electronic excitation in Cu(I)-based transition metal complexes, yet its role in photoinduced electron transfer (PET) remains largely unexplored. Here, we demonstrate that the JTD governs charge separation (CS) through a vibronically controlled conical intersection in heteroleptic Cu(I) bisphenanthroline–naphthalene diimide (CuHETPHEN-NDI) donor–acceptor dyads. Using 20-fs broadband transient absorption spectroscopy combined with coherent vibrational wavepacket (CVWP) analysis and quantum chemical calculations, we directly track nuclear motions that steer the system from the metal-to-ligand charge-transfer (¹MLCT) state to the CS state. Steric bulkiness of the pendant groups at the 2,9-positions of the phenanthroline ligand systematically slows both JTD and CS. Short-time Fourier transformation and Fourier filtering analyses identify two key vibrational signatures: a low-frequency breathing mode (∼100 cm⁻¹) via a bond distance change between Cu and ligated Ns (Cu–N) that modulates the NDI anion absorption and acts as a vibronic coupling coordinate, and a higher-frequency mode (∼313 cm⁻¹) that evolves along the PET trajectory. Normal mode analysis and potential energy surface calculations show that the JTD brings the ¹MLCT and CS states into degeneracy, while the Cu–N breathing motion dynamically modulates donor–acceptor electronic coupling to enable ultrafast nonadiabatic electron transfer. Steric hindrance exerted by the groups at the 2,9 positions of the phenanthroline ligands suppresses this vibronic coupling, leading to faster CVWP decoherence for the 313 cm⁻¹ mode and slower CS. These findings unravel JTD-controlled vibronic coupling at conical intersection as a governing factor for CS and provide insight into designing Cu-based photosensitizers by harnessing structural dynamics to control PET.

Cu(I)-bisdiimine complexes, [Cu(NN)₂]⁺ (where NN represents a diimine such as phenanthroline or bipyridine derivatives), are considered promising photosensitizers for various photochemical applications. However, their effectiveness is subject to several key challenges. In particular, controlling steric strain around the copper(I) center by introducing appropriate substituents (R) at the α-position of the nitrogen atoms is crucial for optimizing the excited-state properties of the complex. In brief, increasing the size of R leads to longer emission lifetimes and higher quantum yields. Additionally, the energy of the singlet excited state rises with increasing steric bulk, enhancing photoinduced reactivity. However, excessive steric strain from bulky substituents can significantly destabilize the coordination sphere. To balance complex stability with increased steric bulk around the metal center, we have developed two novel nonsymmetrical ligands featuring branched alkyl chains and benzyl groups at the α-position of the nitrogen atoms. Our findings demonstrate that intramolecular π-stacking interactions between the benzyl group and the opposing phenanthroline ligand contribute to stabilizing the coordination sphere. Furthermore, the flexibility of the benzyl group reinforces the tetrahedral geometry around copper(I), resulting in an increased singlet excited-state energy compared to benchmark complexes. Notably, we show that this enhancement in excited-state energy translates into greater excited-state reactivity.

Luminescent tris(2,4,6-trichlorophenyl)methyl (TTM) radicals are promising doublet emitters that have been used to generate spin-optical interfaces in molecular electron spin qudits. In particular, photoexcitation of covalent TTM-chromophore dyads can generate quartet spin states that can be detected via photoluminescence. However, the mechanism of quartet spin initialization is complicated by competing charge-transfer (CT) and energy-transfer (EnT) pathways between the radical and the chromophore. Here, we demonstrate the role of CT intermediates by engineering a covalent dyad of TTM and naphthalene-(1,4:5,8)-bis(dicarboximide) (NDI), a well-known electron acceptor chromophore. Transient absorption spectroscopy indicates that photoexcitation of TTM results in ultrafast electron transfer from ^2*TTM to NDI, which kinetically outcompetes EnT. Electron paramagnetic resonance spectroscopy reveals that charge recombination proceeds via spin-orbit charge-transfer intersystem crossing to generate ^3*NDI, followed by spin mixing with ²TTM to form the quartet state. This process uniquely spin-polarizes the quartet state, providing fundamental design principles to purify the initial wave function for quantum information processing.

Molecular optical-spin interfaces are emerging as promising alternatives to solid-state defects, such as diamond nitrogen vacancy centers for quantum information science applications. In this work, we report a new organic molecular color center consisting of two luminescent tris(2,4,6-trichlorophenyl)methyl (TTM) radicals connected at the 2,6-positions of a toluene bridge. Optical polarization of the |T₀⟩ sublevel of the triplet ground state is achieved by spin-selective excited-state intersystem crossing from the |T₊⟩ and |T_-⟩ sublevels of the triplet excited state. Steric hindrance between the toluene methyl group and the phenyls of the TTM radicals results in a structure that increases the excited-state intersystem crossing spin selectivity while reducing the electronic coupling between the TTM subunits. This results in an order of magnitude increase in the optically detected magnetic resonance contrast and longer excited-state lifetimes relative to the sterically unencumbered analogue. We demonstrate coherent microwave manipulation of the spin-polarized ground-state populations and coherences using optical detection of Rabi nutations, Hahn echo formation, and echo decay measurements at 85 K in a nuclear-spin-rich solvent matrix. This marks a crucial step toward leveraging the favorable spin relaxation times of organic molecules for applications as quantum sensors at temperatures that heretofore have been difficult to achieve by molecular color centers.

Singlet exciton fission (SF) and symmetry-breaking charge separation (SB-CS) are both photophysical processes that can occur between two organic chromophores and are both of interest to improve solar energy conversion. Here, we tuned the photophysics of a 9,9'-bianthracene (BA) single crystal between SF and SB-CS using solvent intercalation to change the electric field within the crystal. Crystals of BA were grown in o-xylene, chlorobenzene, o-dichlorobenzene, and benzonitrile, as well as solvent-free from a melt. The crystals were studied by X-ray diffraction, steady-state optical spectroscopy, and transient absorption microscopy to elucidate the role of the intercalated solvent molecules. The crystals with no solvent in the structure undergo fast SF (o-xylene, chlorobenzene, and o-dichlorobenzene show evidence of charge-transfer-mediated SF. Finally, the crystals containing highly polar benzonitrile undergo SB-CS instead of SF. These results demonstrate that controlling solvation of BA in the crystal structure can tune its photophysics between SF and SB-CS.

We report on new donor-chromophore-acceptor triads BDX-ANI-NDI and BDX-ANI-xy-NDI where the BDX donor is 2,2,6,6-tetramethylbenzo[1,2-d;4,5-d]bis[1,3]dioxole, the ANI chromophore is 4-(N-piperidinyl)naphthalene-1,8-dicarboximide, the NDI acceptor is naphthalene-1,8:4,5-bis(dicarboximide), and xy is a 2,5-xylyl spacer. The results on these compounds are compared to the analogous derivatives having a p-methoxyaniline (MeOAn) as the donor. BDX^•+ has no nitrogen atoms and only a single hydrogen atom coupled to its unpaired electron spin, and therefore has significantly decreased hyperfine interactions compared to MeOAn^•+. We use femtosecond transient absorption (fsTA) and nanosecond TA (nsTA) spectroscopies, the latter with an applied static magnetic field, to study the charge transfer dynamics and determine the spin-spin exchange interaction (J) for BDX^•+-ANI-NDI^•- and BDX^•+-ANI-xy-NDI^•- at both ambient and cryogenic temperatures. Time-resolved electron paramagnetic resonance (EPR) and pulse-EPR measurements on these spin-correlated radical pairs (SCRPs) were used to probe their spin dynamics. We demonstrate that BDX^•+-ANI-xy-NDI^•- has an unusually long lifetime of ∼550 μs in glassy butyronitrile (PrCN) at 85 K, which makes it useful for pulse-EPR studies that target quantum information science (QIS) applications. We also show that rotation of the BDX group about the single bond linking it to the neighboring phenyl group has a significant impact on the spin dynamics, and in particular the magnitude of J. By comparing the results on these compounds to the analogous MeOAn series, insights into design principles for creating improved spin-correlated radical pair systems for QIS studies are obtained.

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 |T₀⟩ 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.

Copper(I) bis-diimine complexes have played important roles in light-activated processes that can lead to their potential applications in photocatalysis and chemical sensing. Their metal-to-ligand charge-transfer (MLCT) excited-state properties are tunable by various structural factors. Dimeric Cu(I) complexes with connecting diimine derivative ligands offer another structural tuning platform for the excited-state properties. Here, we investigate excited-state properties in two covalently connected dimeric Cu(I)'s with varying structural constraints exerted by the number of carbons in the polyethylene bridge (C0 and C4) connecting the two copper(I) diimine moieties. An interesting feature of Cu(I) diimine complexes is their ability to flatten following a photoinduced structural change. Herein, we observe larger structural constraints and more structural rearrangement required upon excitation of the longer bridged complex C4 to achieve a conformation toward a more flattened tetrahedral coordination geometry compared to the shorter bridged C0. Vibrational wavepacket analysis of these complexes further supports the effect of these structural constraints where we observe a more rapid dephasing of the C0 complex, as opposed to the C4 complex, despite similar normal mode vibrations. The experimental results were supplemented by TDDFT calculations. The studies provide insight into using metal-metal interactions through constraints to tune excited-state dynamics and pathways.