Solid-state photochemically induced dynamic nuclear polarization (photo-CIDNP) is a nuclear magnetic resonance spectroscopy technique in which nuclear spin hyperpolarization is generated upon optical irradiation of an appropriate donor-acceptor system. Until now, solid-state photo-CIDNP at high magnetic fields has been observed only in photosynthetic reaction centers and flavoproteins. In the present work, we show that the effect is not limited to such biomolecular samples, and solid-state 13C photo-CIDNP can be observed at 9.4 T under magic angle spinning using a frozen solution of a synthetic molecular system dissolved in an organic solvent. Signal enhancements for the source molecule larger than a factor of 2300 are obtained. In addition, we show that bulk 13C hyperpolarization of the solvent can be generated via spontaneous 13C-13C spin diffusion at natural abundance.
Nitrenium ions are important reactive intermediates participating in the synthetic chemistry and biological processes. Little is known about triplet phenyl nitrenium ions regarding their reactivity, lifetimes, spectroscopic features, and electronic configurations, and no ground state triplet nitrenium ion has been directly detected. In this work, m-pyrrolidinyl-phenyl hydrazine hydrochloride (1) is synthesized as the photoprecursor to photochemically generate the corresponding m-pyrrolidinyl-phenyl nitrenium ion (2), which is computed to adopt a π, π* triplet ground state. A combination of femtosecond (fs) and nanosecond (ns) transient absorption (TA) spectroscopy, cryogenic continuous-wave electronic paramagnetic resonance (CW-EPR) spectroscopy, computational analysis, and photoproduct studies was performed to elucidate the photolysis pathway of 1 and offers the first direct experimental detection of a ground state triplet phenyl nitrenium ion. Upon photoexcitation, 1 forms S1, where bond heterolysis occurs and the NH3 leaving group is extruded in 1.8 ps, generating a vibrationally hot, spin-conserving closed-shell singlet phenyl nitrenium ion (12) that undergoes vibrational cooling in 19 ps. Subsequent intersystem crossing takes place in 0.5 ns, yielding the ground state triplet phenyl nitrenium ion (32), with a lifetime of 0.8 µs. Unlike electrophilic singlet phenyl nitrenium ions, which react rapidly with nucleophiles, this triplet phenyl nitrenium reacts through sequential H atom abstractions, resulting in the eventual formation of the reduced m-pyrrolidinyl-aniline as the predominant stable photoproduct. Supporting the triplet ground state, continuous irradiation of 1 in a glassy matrix at 80 K in an EPR spectrometer forms a paramagnetic triplet species, consistent with a triplet nitrenium ion.
An important criterion for quantum operations is long qubit coherence times. To elucidate the influence of molecular structure on the coherence times of molecular spin qubits and qudits, a series of molecules featuring perylenediimide (PDI) chromophores covalently linked to stable nitroxide radicals were synthesized and investigated by pulse electron paramagnetic resonance spectroscopy. Photoexcitation of PDI in these systems creates an excited quartet state (Q) followed by a spin-polarized doublet ground state (D0), which hold promise as spin qudits and qubits, respectively. By tailoring the molecular structure of these spin qudit/qubit candidates by selective deuteration and eliminating intramolecular motion, coherence times of Tm = 9.1 ± 0.3 and 4.2 ± 0.3 µs at 85 K for D0 and Q, respectively, are achieved. These coherence times represent a nearly 3-fold enhancement compared to those of the initial molecular design. This approach offers a rational structural design protocol for effectively extending coherence times in molecular spin qudits/qubits.
Photoexcited organic chromophores appended to stable radicals can serve as qubit and/or qudit candidates for quantum information applications. 1,6,7,12-Tetra-(4-tert-butylphenoxy)-perylene-3,4 : 9,10-bis(dicarboximide) (tpPDI) linked to a partially deuterated α,γ-bisdiphenylene-ß-phenylallyl radical (BDPA-d16 ) was synthesized and characterized by time-resolved optical and electron paramagnetic resonance (EPR) spectroscopies. Photoexcitation of tpPDI-BDPA-d16 results in ultrafast radical-enhanced intersystem crossing to produce a quartet state (Q) followed by formation of a spin-polarized doublet ground state (D0 ). Pulse-EPR experiments confirmed the spin multiplicity of Q and yielded coherence times of Tm =2.1±0.1â µs and 2.8±0.2â µs for Q and D0 , respectively. BDPA-d16 eliminates the dominant 1 H hyperfine couplings, resulting in a single narrow line for both the Q and D0 states, which enhances the spectral resolution needed for good qubit addressability.
Owing to their exceptional photophysical properties and high photostability, perylene diimide (PDI) chromophores have found various applications as building blocks of materials for organic electronics. In many light-induced processes in PDI derivatives, chromophore excited states with high spin multiplicities, such as triplet or quintet states, have been revealed as key intermediates. The exploration of their properties and formation conditions is thus expected to provide invaluable insight into their underlying photophysics and promises to reveal strategies for increasing the performance of optoelectronic devices. However, accessing these high-multiplicity excited states of PDI to increase our mechanistic understanding remains a difficult task, due to the fact that the lowest excited singlet state of PDI decays with near-unity quantum yield to its ground state. Here we make use of radical-enhanced intersystem crossing (EISC) to generate the PDI triplet state in high yield. One or two 2,2,6,6-tetramethylpiperidinyloxyl (TEMPO) stable radicals were covalently attached to the imide position of PDI chromophores with and without p-tert-butylphenoxy core substituents. By combining femtosecond UV-vis transient absorption and transient electron paramagnetic resonance spectroscopies, we demonstrate strong magnetic exchange coupling between the PDI triplet state and TEMPO, resulting in the formation of excited quartet or quintet states. Important differences in the S1 state deactivation rate constants and triplet yields are observed for compounds bearing PDI moieties with different core substitution patterns. We show that these differences can be rationalized by considering the varying importance of competitive excited state decay processes, such as electron and excitation energy transfer. The comparison of the results obtained for different PDI-TEMPO derivatives leads us to propose design guidelines for optimizing the efficiency of triplet sensitization in molecular assemblies by EISC.
Nitrenium ions are important reactive intermediates in both chemistry and biology. Although singlet nitrenium ions are well-characterized by direct methods, the triplet states of nitrenium ions have never been directly detected. Here, we find that the excited state of the photoprecursor partitions between heterolysis to generate the singlet nitrenium ion and intersystem crossing (ISC) followed by a spontaneous heterolysis process to generate the triplet p-iodophenylnitrenium ion (np). The triplet nitrenium ion undergoes ISC to generate the ground singlet state, which ultimately undergoes proton and electron transfer to generate a long-lived radical cation that further generates the reduced p-iodoaniline. Ab Initio calculations were performed to map out the potential energy surfaces to better understand the excited state reactivity channels show that an energetically-accessible singlet-triplet crossing lies along the N-N stretch coordinate and that the excited triplet state is unbound and spontaneously eliminates ammonia to generate the triplet nitrenium ion. These results give a clearer picture of the photophysical properties and reactivity of two different spin states of a phenylnitrenium ion and provide the first direct glimpse of a triplet nitrenium ion.
Ions , Electron Transport
Multiexciton quintet states, 5(TT), photogenerated in organic semiconductors using singlet fission (SF), consist of four quantum entangled spins, promising to enable new applications in quantum information science. However, the factors that determine the spin coherence of these states remain underexplored. Here, we engineer the packing of tetracene molecules within single crystals of 5,12-bis(tricyclohexylsilylethynyl)tetracene (TCHS-tetracene) to demonstrate a 5(TT) state that exhibits promising spin qubit properties, including a coherence time, T2, = 3 µs at 10 K, a population lifetime, Tpop, = 130 µs at 5 K, and stability even at room temperature. The single-crystal platform also enables global alignment of the spins and, consequently, individual addressability of the spin-sublevel transitions. Decoherence mechanisms, including exciton diffusion, electronic dipolar coupling, and nuclear hyperfine interactions, are elucidated, providing design principles for increasing T2 and the operational temperature of 5(TT). By dynamically decoupling 5(TT) from the surrounding spin bath, T2 = 10 µs is achieved. These results demonstrate the viability of harnessing singlet fission to initiate multiple electron spins in a well-defined quantum state for next-generation molecular-based quantum technologies.
We recently demonstrated photodriven quantum teleportation of an electron spin state in a covalent donor-acceptor-radical (D-A-Râ¢) system. Following specific spin state preparation on R⢠with a microwave pulse, photoexcitation of A results in two-step electron transfer producing Dâ¢+-A-R-, where the spin state on R⢠is teleported to Dâ¢+. This study examines the effects of varying the time (τD) between spin state preparation and photoinitiated teleportation. Using pulse electron paramagnetic resonance spectroscopy, the spin echo of Dâ¢+ resulting from teleportation shows a damped oscillation as a function of τD that is simulated using a density matrix model, which provides a fundamental understanding of the echo behavior. Teleportation fidelity calculations also show oscillatory behavior as a function of τD due to the accumulation of a phase factor between ⟨Sx⟩ and ⟨Sy⟩. Understanding experimental parameters intrinsic to quantum teleportation in molecular systems is crucial to leveraging this phenomenon for quantum information applications.
Manipulating frontier orbital energies of aromatic molecules with substituents is key to a variety of chemical and material applications. Here, we investigate a simple strategy for achieving high-energy in-plane orbitals for aromatics simply by positioning iodine atoms next to each other. The lone pair orbitals on the iodines mix to give a high-energy in-plane σ-antibonding orbital as the highest occupied molecular orbital (HOMO). We show that this effect can be used to manipulate orbital gaps, the symmetry of the highest occupied orbital, and the adopted electronic state for reactive intermediates. This electronic effect is not limited to reactive intermediates, and we demonstrate that this iodine buttressing strategy also can be used to achieve small HOMO-lowest unoccupied molecular orbital (HOMO-LUMO) gaps in organic electronic materials. Iodinated oligomers of several of the most popular conducting polymers are computed to have smaller HOMO-LUMO gaps than the unsubstituted materials. This iodine buttressing approach for generating high-energy in-plane HOMOs is anticipated to be highly general. While the unusual properties of fluorous materials are well established, at the other extreme on the periodic table novel properties of iodous materials may await discovery.
Nitrenium and oxenium ions are important reactive intermediates in synthetic and biological processes, and their ground electronic configurations are of great interest due to having distinct reactivities and properties. In general, the closed-shell singlet state of these intermediates usually react as electrophiles, while reactions of the triplet states of these ions react like typical diradicals (e.g., H atom abstractions). Nonsubstituted phenyl nitrenium ions (Ph-NH+) and phenyl oxenium ions (Ph-O+) have closed-shell singlet ground states with large singlet-triplet gaps resulting from a strong break in the degeneracy of the p orbitals on the formal nitrenium/oxenium center. Remarkably, we find computationally (CBS-QB3 and G4MP2) that azulenyl nitrenium and oxenium ions can have triplet ground states depending upon the attachment position on the azulene core. For instance, CBS-QB3 predicts that 1-azulenyl nitrenium ion and 1-azulenyl oxenium ion are singlet ground-state species with considerable singlet-triplet gaps of -47 and -45 kcal/mol to the lowest-energy triplet state, respectively. In contrast, 6-azulenyl nitrenium ion and 6-azulenyl oxenium ion have triplet ground states with a singlet-triplet gap of +7 and +10 kcal/mol, respectively. Moreover, the triplet states are π,π* states, rather than the typical n,π* states seen for many aryl nitrenium or oxenium ions. This dramatic switch in favored electronic states can be ascribed to changes in ring aromaticity/antiaromaticity, with the switch from ground-state singlet ions to triplet-favored ions resulting from both a destabilized singlet state (Hückel antiaromatic) and a stabilized triplet (Baird aromatic) state. Density functional theory (UB3LYP/6-31+G(d,p)) was used to determine substituent effects on the singlet-triplet energy gap for azulenyl nitrenium and oxenium ions, and we find that the unusual ground triplet states can be further tuned by employing electron-donating or -withdrawing groups on the azulene ring. This work demonstrates that azulenyl nitrenium and oxenium ions can have triplet π,π* ground states and provides a simple recipe for making ionic intermediates with distinct electronic configurations and consequent prediction of unique reactivity and magnetic properties from these species.
A new photoprecursor to the phenyloxenium ion, 4-methoxyphenoxypyridinium tetrafluoroborate, was investigated using trapping studies, product analysis, computational investigations, and laser flash photolysis experiments ranging from the femtosecond to the millisecond time scale. These experiments allowed us to trace the complete arc of the photophysics and photochemistry of this photoprecursor beginning with the initially populated excited states to its sequential formation of transient intermediates and ultimate formation of stable photoproducts. We find that the excited state of the photoprecursor undergoes heterolysis to generate the phenyloxenium ion in â¼2 ps but surprisingly generates the ion in its open-shell singlet diradical configuration (1A2), permitting an unexpected look at the reactivity of an atom-centered open-shell singlet diradical. The open-shell phenyloxenium ion (1A2) has a much shorter lifetime (τ â¼ 0.2 ns) in acetonitrile than the previously observed closed-shell singlet (1A1) phenyloxenium ion (τ â¼ 5 ns). Remarkably, despite possessing no empty valence orbitals, this open-shell singlet oxenium ion behaves as an even more powerful electrophile than the closed-shell singlet oxenium ion, undergoing solvent trapping by weakly nucleophilic solvents such as water and acetonitrile or externally added nucleophiles (e.g., azide) rather than engaging in typical diradical chemistry, such as H atom abstraction, which we have previously observed for a triplet oxenium ion. In acetonitrile, the open-shell singlet oxenium ion is trapped to generate ortho and para Ritter intermediates, one of which (para) is directly observed as a longer-lived species (τ â¼ 0.1 ms) in time-resolved resonance Raman experiments. The Ritter intermediates are ultimately trapped by either the 4-methoxypyridine leaving group (in the case of para addition) or trapped internally via an essentially barrierless rearrangement (in the case of ortho addition) to generate a cyclized product. The expectation that singlet diradicals react similarly to triplet or uncoupled diradicals needs to be reconsidered, as a recent study by Perrin and Reyes-Rodríguez (J. Am. Chem. Soc. 2014, 136, 15263) suggested the unsettling possibility that singlet p-benzyne could suffer nucleophilic attack to generate a naked phenyl anion. Now, this study provides direct spectroscopic observation of this phenomenon, with an atom-centered open-shell singlet diradical reacting as a powerful electrophile. To the question of whether a nucleophile can attack a singly occupied molecular orbital, the answer is apparently yes, at least if another partially occupied orbital is available to avoid violation of the rules of valence.
The combination of theoretical calculations and laser flash photolysis experiments has aided in understanding the reactivity and properties of oxenium ions. Direct observation of the reactivity, spin configurations, and lifetimes of short-lived oxenium ions via laser flash photolysis (LFP) techniques is now possible due to the discovery of new photoprecursors to these species. These new precursors allowed the direct observation of the parent phenyloxenium ion in solution by using protonated hydroxylamine tetrafluoroborate salt. Computations suggest that the singlet-triplet gap (ΔEST) of aryloxenium ions can be tuned by substituents, and predicted a ground state triplet oxenium ion, which was confirmed by experimental studies. The interplay of theory and experiment in understanding these species is discussed.
Three-electron σ-bonding that was proposed by Linus Pauling in 1931 has been recognized as important in intermediates encountered in many areas. A number of three-electron bonding systems have been spectroscopically investigated in the gas phase, solution and solid matrix. However, X-ray diffraction studies have only been possible on simple noble gas dimer Xeâ´Xe and cyclic framework-constrained Nâ´N radical cations. Here, we show that a diselena species modified with a naphthalene scaffold can undergo one-electron oxidation using a large and weakly coordinating anion, to afford a room-temperature-stable radical cation containing a Seâ´Se three-electron σ-bond. When a small anion is used, a reversible dimerization with phase and marked colour changes is observed: radical cation in solution (blue) but diamagnetic dimer in the solid state (brown). These findings suggest that more examples of three-electron σ-bonds may be stabilized and isolated by using naphthalene scaffolds together with large and weakly coordinating anions.
The methylene-bridged triphenylamine 2 has been oxidized to planar radical cation 2(â¢+) by B(C6F5)3 or Ag(+). Further reaction of 2(â¢+)[Al(ORF)4](-) and 2 with trace amounts of silver salt resulted in dication 3(2+), providing a rare example of structurally characterized bis(triarylamine) "bipolarons". 3(2+) can be directly prepared by the reaction of 3 with 2 equiv of Ag(+). X-ray structural analysis together with theoretical calculation shows that 3(2+) has singlet diradical character and is analogous to Chichibabin's hydrocarbons.
