Jordan N. Nelson

Synchrotron Photoionization Study of Mesitylene Oxidation Initiated by Reaction with Cl(2P) or O(3P) Radicals

This work studies the oxidation of mesitylene (1,3,5-trimethylbenzene) initiated by O(3P) or Cl(2P) atoms. The O(3P) initiated mesitylene oxidation was investigated at room temperature and 823 K, whereas the Cl-initiated reaction was carried out at room temperature only. Products were probed by a multiplexed chemical kinetics photoionization mass spectrometer using the synchrotron radiation produced at the Advanced Light Source (ALS) of Lawrence Berkeley National Laboratory. Reaction products and intermediates are identified on the basis of their time behavior, mass-to-charge ratio, ionization energies, and photoionization spectra. Branching yields are derived for the O-initiated reaction at 823 K and the Cl-initiated reaction at room temperature. Reaction schematics are proposed and presented.

Picosecond Control of Photogenerated Radical Pair Lifetimes Using a Stable Third Radical

Photoinduced electron transfer reactions in organic donor-acceptor systems leading to long-lived radical ion pairs (RPs) have attracted broad interest for their potential applications in fields as diverse as solar energy conversion and spintronics. We present the photophysics and spin dynamics of an electron donor - electron acceptor - stable radical system consisting of a meta-phenylenediamine (mPD) donor covalently linked to a 4-aminonaphthalene-1,8-dicarboximide (ANI) electron-accepting chromophore as well as an α,γ-bisdiphenylene-β-phenylallyl (BDPA) stable radical. Selective photoexcitation of ANI produces the BDPA-mPD(+•)-ANI(-•) triradical in which the mPD(+•)-ANI(-•) RP spins are strongly exchange coupled. The presence of BDPA is found to greatly increase the RP intersystem crossing rate from the initially photogenerated BDPA-(1)(mPD(+•)-ANI(-•)) to BDPA-(3)(mPD(+•)-ANI(-•)), resulting in accelerated RP recombination via the triplet channel to produce BDPA-mPD-(3*)ANI as compared to a reference molecule lacking the BDPA radical. The RP recombination rates observed are much faster than those previously reported for weakly coupled triradical systems. Time-resolved EPR spectroscopy shows that this process is also associated with strong spin polarization of the stable radical. Overall, these results show that RP intersystem crossing rates can be strongly influenced by stable radicals nearby strongly coupled RP systems, making it possible to use a third spin to control RP lifetimes down to a picosecond time scale.

Study of tert-Amyl Methyl Ether Low Temperature Oxidation Using Synchrotron Photoionization Mass Spectrometry.

This paper examines the oxidation reaction of tert-amyl methyl ether (TAME), an oxygenated fuel additive, with chlorine radical initiators in the presence of oxygen. Data are collected at 298, 550, and 700 K. Reaction intermediates and products are probed by a multiplexed chemical kinetics synchrotron photoionization mass spectrometer (SPIMS) and characterized on the basis of the mass-to-charge ratio, ionization energy, and photoionization spectra. Branching fractions of primary products are obtained at the different reaction temperatures. CBS-QB3 computations are also carried out to study the potential energy surface of the investigated reactions to validate detected primary products.

Fast photo-driven electron spin coherence transfer: The effect of electron-nuclear hyperfine coupling on coherence dephasing

Selective photoexcitation of the donor in an electron donor–acceptor1–acceptor2 (D–A1–A2) molecule, in which D = perylene and both A1 and A2 = naphthalene-1,8:4,5-bis(dicarboximide), results in sub-nanosecond formation of a spin-correlated singlet radical pair 1(D+˙–A1−˙–A2) having a large electron spin–spin exchange interaction, 2J, which precludes its observation by transient EPR spectroscopy. Subsequent selective photoexcitation of A1−˙ rapidly produces 1(D+˙–A1–A2−˙), resulting in a dramatic decrease in 2J, which allows coherent spin evolution to mix the singlet (S) radical pair state 1(D+˙–A1–A2−˙) with the T0 triplet sublevel of 3(D+˙–A1–A2−˙) in an applied magnetic field, where B ≫ 2J. A spin-polarized transient EPR spectrum characteristic of the spin-correlated radical pair D+˙–A1–A2−˙ is then observed. The time delay between the two laser pulses was incremented to measure the rate of decoherence in 1(D+˙–A1−˙–A2) in toluene at 295 K, which was found to be 8.1 × 107 s−1. Deuteration of the perylene donor or the toluene solvent decreases the decoherence rate constant of 1(D+˙–A1−˙–A2) to 4.3 × 107 s−1 and 4.6 × 107 s−1, respectively, while deuteration of both the perylene donor and the toluene solvent reduced the decoherence rate constant by more than half to 3.4 × 107 s−1. The data show that decreasing electron-nuclear hyperfine interactions significantly increases the zero quantum coherence lifetime of the spin-correlated radical pair.

Covalent Radical Pairs as Spin Qubits: Influence of Rapid Electron Motion between Two Equivalent Sites on Spin Coherence

Ultrafast photodriven electron transfer reactions starting from an excited singlet state in an organic donor-acceptor molecule generate a radical pair (RP) in which the two spins are initially entangled and, in principle, can serve as coupled spin qubits in quantum information science (QIS) applications, provided that spin coherence lifetimes in these RPs are long. Here we investigate the effects of electron transfer between two equivalent sites comprising the reduced acceptor of the RP. A covalent electron donor-acceptor molecule (D-C-A24+) including a p-methoxyaniline donor (D), a 4-aminonaphthalene-1,8-imide chromophoric primary acceptor (C), and a m-xylene bridged cyclophane having two equivalent phenyl-extended viologens (A24+) as a secondary acceptor was synthesized along with the analogous molecule having one phenyl-extended viologen acceptor and a second, more difficult to reduce 2,5-dimethoxyphenyl-extended viologen in a very similar cyclophane structure (D-C-A4+). Photoexcitation of C within each molecule results in subnanosecond formation of D+•-C-A23+• and D+•-C-A3+•. The spin dynamics of these RPs were characterized by time-resolved EPR spectroscopy and magnetic field effects on the RP yield in both CH3CN and CD3CN. The data show that rapid electron hopping within A23+• promotes spin decoherence in D+•-C-A23+• relative to D+•-C-A3+• having a monomeric acceptor, while the interaction of the RP electron spins with the nuclear spins of the solvent have little or no effect on the spin dynamics. These observations provide important information for designing and understanding novel molecular assemblies of spin qubits with long coherence times for QIS applications.

Tunable Crystallinity and Charge Transfer in Two‐Dimensional G‐Quadruplex Organic Frameworks

DNA G-quadruplex structures were recently discovered to provide reliable scaffolding for two-dimensional organic frameworks due to the strong hydrogen-bonding ability of guanine. Herein, 2,7-diaryl pyrene building blocks with high HOMO energies and large optical gaps are incorporated into G-quadruplex organic frameworks. The adjustable substitution on the aryl groups provides an opportunity to elucidate the framework formation mechanism; molecular non-planarity is found to be beneficial for restricting interlayer slippage, and the framework crystallinity is highest when intermolecular interaction and non-planarity strike a fine balance. When guanine-functionalized pyrenes are co-crystallized with naphthalene diimide, charge-transfer (CT) complexes are obtained. The photophysical properties of the pyrene-only and CT frameworks are characterized by UV/Vis and steady-state and time-resolved photoluminescence spectroscopies, and by EPR spectroscopy for the CT complex frameworks.

Zero Quantum Coherence in a Series of Covalent Spin-Correlated Radical Pairs

Photoinitiated subnanosecond electron transfer within covalently linked electron donor-acceptor molecules can result in the formation of a spin-correlated radical pair (SCRP) with a well-defined initial singlet spin configuration. Subsequent coherent mixing between the SCRP singlet and triplet ms = 0 spin states, the so-called zero quantum coherence (ZQC), is of potential interest in quantum information processing applications because the ZQC can be probed using pulse electron paramagnetic resonance (pulse-EPR) techniques. Here, pulse-EPR spectroscopy is utilized to examine the ZQC oscillation frequencies and ZQC dephasing in three structurally well-defined D-A systems. While transitions between the singlet and triplet ms = 0 spin states are formally forbidden (Δms = 0), they can be addressed using specific microwave pulse turning angles to map information from the ZQC onto observable single quantum coherences. In addition, by using structural variations to tune the singlet-triplet energy gap, the ZQC frequencies determined for this series of molecules indicate a stronger dependence on the electronic g-factor than on electron-nuclear hyperfine interactions.

Spin Polarization Transfer from a Photogenerated Radical Ion Pair to a Stable Radical Controlled by Charge Recombination

Photoexcitation of electron donor-acceptor molecules frequently produces radical ion pairs with well-defined initial spin-polarized states that have attracted significant interest for spintronics. Transfer of this initial spin polarization to a stable radical is predicted to depend on the rates of the radical ion pair recombination reactions, but this prediction has not been tested experimentally. In this study, a stable radical/electron donor/chromophore/electron acceptor molecule, BDPA•-mPD-ANI-NDI, where BDPA• is α,γ-bisdiphenylene-β-phenylallyl, mPD is m-phenylenediamine, ANI is 4-aminonaphthalene-1,8-dicarboximide, and NDI is naphthalene-1,4:5,8-bis(dicarboximide), was synthesized. Photoexcitation of ANI produces the triradical BDPA•-mPD+•-ANI-NDI-• in which the mPD+•-ANI-NDI-• radical ion pair is spin coupled to the BDPA• stable radical. BDPA•-mPD+•-ANI-NDI-• and its counterpart lacking the stable radical are found to exhibit spin-selective charge recombination in which the triplet radical ion pair 3(mPD+•-ANI-NDI-•) is in equilibrium with the 3*NDI charge recombination product. Time-resolved EPR measurements show that this process is associated with an inversion of the sign of the polarization transferred to BDPA• over time. The polarization transfer rates are found to be strongly solvent dependent, as shifts in this equilibrium affect the spin dynamics. These results demonstrate that even small changes in electron transfer dynamics can have a large effect on the spin dynamics of photogenerated multispin systems.

Charge Separation Mechanisms in Ordered Films of Self-Assembled Donor–Acceptor Dyad Ribbons

Orthogonal attachment of polar and nonpolar side-chains to a zinc porphyrin-perylenediimide dyad (ZnP-PDI, 1a) is shown to result in self-assembly of ordered supramolecular ribbons in which the ZnP and PDI molecules form segregated π-stacked columns. Following photoexcitation of the ordered ribbons, ZnP+•-PDI-• radical ion pairs form in <200 fs and subsequently produce a 30 ± 3% yield of free charge carriers that live for about 100 μs. Elongating the side chains on ZnP and PDI in 1b enhances the order of the films, but does not result in an increase in free charge carrier yield. In addition, this yield is independent of temperature, free energy of reaction, and the ZnP-PDI distance in the covalent dyad. These results suggest that the free charge carrier yield in this system is not limited by a bound charge transfer (CT) state or promoted by a vibronically hot CT state. Instead, it is likely that π-stacking of the segregated donors and acceptors within the ribbons results in delocalization of the charges following photoexcitation, allowing them to overcome Coulombic attraction and generate free charge carriers.