Control of excitation selectivity in pulse EPR on spin-correlated radical pairs with shaped pulses.

Spin-correlated radical pairs generated by photoinduced electron transfer are characterised by a distinctive spin polarisation and a unique behaviour in pulse electron paramagnetic resonance (EPR) spectroscopy. Under non-selective excitation, an out-of-phase echo signal modulated by the dipolar and exchange coupling interactions characterising the radical pair is observed and allows extraction of geometric information in the two-pulse out-of-phase electron spin echo envelope modulation (ESEEM) experiment. The investigation of the role of spin-correlated radical pairs in a variety of biological processes and in the fundamental mechanisms underlying device function in optoelectronics, as well as their potential use in quantum information science, relies on the ability to precisely address and manipulate the spins using microwave pulses. Here, we explore the use of shaped pulses for controlled narrowband selective and broadband non-selective excitation of spin-correlated radical pairs in two model donor-bridge-acceptor triads, characterised by different spectral widths, at X- and Q-band frequencies. We demonstrate selective excitation with close to rectangular excitation profiles using BURP (band-selective, uniform response, pure-phase) pulses and complete non-selective excitation of both spins of the radical pair using frequency-swept chirp pulses. The use of frequency-swept pulses in out-of-phase ESEEM experiments enables increased modulation depths and, combined with echo transient detection and Fourier transformation, correlation of the dipolar frequencies with the EPR spectrum and therefore the potential to extract additional information on the donor-acceptor pair geometry.

High-efficiency BODIPY-based organic photovoltaics.

A benzannulated boron dipyrromethene (BODIPY, bDIP) molecule exhibiting strong absorption at 640 nm was synthesized. The organic dye was used in an organic solar cell as the electron donor with C60 as the acceptor. The BODIPY dye demonstrated the best performance in lamellar architecture (indium tin oxide (ITO)/bDIP/C60/bathocuproine/Al), giving power conversion efficiency up to 4.5% with short-circuit current (JSC) of 8.7 mA/cm(2) and an open-circuit voltage (VOC) of 0.81 V. Neutron reflectivity experiments were performed on the bilayer film to investigate the thickness dependence of JSC. A 13 nm mixed layer was found to be present at the donor/acceptor interface in the bilayer device, formed when the C60 was deposited onto a room temperature bDIP film. Planar-mixed heterojunction devices were fabricated to understand the extent of spontaneous mixing between the donor and acceptor materials. The native mixed region in the bilayer device was shown to most resemble 1:3 bDIP:C60 layer in the structure: (ITO/bDIP/bDIP:C60 blend/C60/bathocuproine/Al).

Electron spin polarization transfer from photogenerated spin-correlated radical pairs to a stable radical observer spin.

A series of donor-chromophore-acceptor-stable radical (D-C-A-R(•)) molecules having well-defined molecular structures were synthesized to study the factors affecting electron spin polarization transfer from the photogenerated D(+•)-C-A(-•) spin-correlated radical pair (RP) to the stable radical R(•). Theory suggests that the magnitude of this transfer depends on the spin-spin exchange interaction (2JDA) of D(+•)-C-A(-•). Yet, the generality of this prediction has never been demonstrated. In the D-C-A-R(•) molecules described herein, D is 4-methoxyaniline (MeOAn), 2,3-dihydro-1,4-benzodioxin-6-amine (DioxAn), or benzobisdioxole aniline (BDXAn), C is 4-aminonaphthalene-1,8-dicarboximide, and A is naphthalene-1,8:4,5-bis(dicarboximide) (1A,B-3A,B) or pyromellitimide (4A,B-6A,B). The terminal imide of the acceptors is functionalized with either a hydrocarbon (1A-6A) or a 2,2,6,6-tetramethyl-1-piperidinyloxyl radical (R(•)) (1B-6B). Photoexcitation of C with 416-nm laser pulses results in two-step charge separation to yield D(+•)-C-A(-•)-(R(•)). Time-resolved electron paramagnetic resonance (TREPR) spectroscopy using continuous-wave (CW) microwaves at both 295 and 85 K and pulsed microwaves at 85 K (electron spin-echo detection) was used to probe the initial formation of the spin-polarized RP and the subsequent polarization of the attached R(•) radical. The TREPR spectra show that |2JDA| for D(+•)-C-A(-•) decreases in the order MeOAn(+•) > DioxAn(+•) > BDXAn(+•) as a result of their spin density distributions, whereas the spin-spin dipolar interaction (dDA) remains nearly constant. Given this systematic variation in |2JDA|, electron spin-echo-detected EPR spectra of 1B-6B at 85 K show that the magnitude of the spin polarization transferred from the RP to R(•) depends on |2JDA|.

Photoinitiated electron transfer in zinc porphyrin-perylenediimide cruciforms and their self-assembled oligomers.

Two X-shaped, cruciform electron donor(2)-acceptor-acceptor'(2) (D(2)-A-A'(2)) molecules, 1 and 2, in which D = zinc 5-phenyl-10,15,20-tripentylporphyrin (ZnTPnP) or zinc 5,10,15,20-tetraphenylporphyrin (ZnTPP), respectively, A = pyromellitimide (PI), and A' = perylene-3,4:9,10-bis(dicarboximide) (PDI), were prepared to study self-assembly motifs that promote photoinitiated charge separation followed by electron and hole transport through π-stacked donors and acceptors. PDI secondary electron acceptors were chosen because of their propensity to form self-ordered, π-stacked assemblies in solution, while the ZnTPnP and ZnTPP donors were selected to test the effect of peripheral substituent steric interactions on the π-stacking characteristics of the cruciforms. Small- and wide-angle X-ray scattering measurements in toluene solution reveal that 1 assembles into a π-stacked structure having an average of 5 ± 1 molecules, when [1] =/~ 10(-5) M, while 2 remains monomeric. Photoexcitation of the π-stacked structure of 1 results in formation of ZnTPnP(•+)-PI-PDI(•-) in τ(CS1) = 0.3 ps, which is nearly 100-fold faster than the formation of ZnTPnP(•+)-PI(•-) in a model system lacking the PDI acceptor. The data are consistent with a self-assembled structure for 1 in which the majority of the intermolecular interactions have the ZnTPnP donor of one monomer cofacially π-stacked with the PDI acceptor of a neighboring monomer in a crisscrossed fashion. In contrast, 2 remains monomeric in toluene, so that photoexcitation of ZnTPP results in the charge separation reaction sequence: (1*)ZnTPP-PI-PDI → ZnTPP(•+)-PI(•-)-PDI → ZnTPP(•+)-PI-PDI(•-), where τ(CS1) = 33 ps and τ(CS2) = 239 ps. The perpendicular orientation of ZnTPnP and ZnTPP relative to PDI in 1 and 2 is designed to decrease the porphyrin-PDI distance without greatly decreasing the overall number of bonds linking them. This serves to decrease the Coulomb energy penalty required to produce D(•+)-PI-PDI(•-) relative to the corresponding linear D-PI-PDI array, while retaining the weak electronic coupling necessary to achieve long-lived charge separation, as evidenced by τ(CR) = 24 ns for ZnTPP(•+)-PI-PDI(•-).

Structure and dynamics of photogenerated triplet radical ion pairs in DNA hairpin conjugates with anthraquinone end caps.

A series of DNA hairpins (AqGn) possessing a tethered anthraquinone (Aq) end-capping group were synthesized in which the distance between the Aq and a guanine-cytosine (G-C) base pair was systematically varied by changing the number (n - 1) of adenine-thymine (A-T) base pairs between them. The photophysics and photochemistry of these hairpins were investigated using nanosecond transient absorption and time-resolved electron paramagnetic resonance (TREPR) spectroscopy. Upon photoexcitation, (1*)Aq undergoes rapid intersystem crossing to yield (3*)Aq, which is capable of oxidizing purine nucleobases resulting in the formation of (3)(Aq(-•)Gn(+•)). All (3)(Aq(-•)Gn(+•)) radical ion pairs exhibit asymmetric TREPR spectra with an electron spin polarization phase pattern of absorption and enhanced emission (A/E) due to their different triplet spin sublevel populations, which are derived from the corresponding non-Boltzmann spin sublevel populations of the (3*)Aq precursor. The TREPR spectra of the (3)(Aq(-•)Gn(+•)) radical ion pairs depend strongly on their spin-spin dipolar interaction and weakly on their spin-spin exchange coupling. The anisotropy of (3)(Aq(-•)Gn(+•)) makes it possible to determine that the π systems of Aq(-•) and G(+•) within the radical ion pair are parallel to one another. Charge recombination of the long-lived (3)(Aq(-•)Gn(+•)) radical ion pair displays an unusual bimodal distance dependence that results from a change in the rate-determining step for charge recombination from radical pair intersystem crossing for n < 4 to coherent superexchange for n > 4.

Ultrafast intersystem crossing and spin dynamics of zinc meso-tetraphenylporphyrin covalently bound to stable radicals.

tert-Butylphenylnitroxide (BPNO(•)) and α,γ-bisdiphenylene-ß-phenylallyl (BDPA(•)) stable radicals are each attached to zinc meso-tetraphenylporphyrin (ZnTPP) at a fixed distance using one of the ZnTPP phenyl groups. BPNO(•) and BDPA(•) are oriented para (1 and 3, respectively) or meta (2 and 4, respectively) relative to the porphyrin macrocycle. Following photoexcitation of 1-4, transient optical absorption spectroscopy is used to observe excited state quenching of (1)*ZnTPP by the radicals and time-resolved electron paramagnetic resonance (TREPR) spectroscopy is used to monitor the spin dynamics of the paramagnetic product states. The presence of BPNO(•) or BDPA(•) accelerates the intersystem crossing rate of (1)*ZnTPP about 10- to 500-fold in 1-4 depending on the structure compared to that of (1)*ZnTPP itself. In addition, the lifetime of (3)*ZnTPP in 1 is shorter than that of (3)*ZnTPP itself as a result of enhanced intersystem crossing (EISC) from (3)*ZnTPP to the ground state. The TREPR spectra of the three unpaired spins produced within 1 and 2 show spin-polarized excited doublet (D(1)) and quartet (Q) states and subsequent formation of a spin-polarized ground state radical (D(0)). All three signals are absorptive for 1 and emissive for 2. Polarization inversion of the Q state is observed on a tens of nanoseconds time scale in 2, while no polarization inversion is observed for 1. The lack of polarization inversion in 1 is attributed to the short lifetime of the doublet-quartet manifold as a result of the very large exchange interaction. The TREPR spectra of 3 and 4 show ground state radical polarization at X-band (9.5 GHz) at room temperature, but not at 85 K, and similarly no polarization is observed at W-band (94 GHz). No evidence of excited doublet or quartet states is observed, indicating that the exchange interaction is both weak and temperature dependent. These results show that although ultrafast EISC produces (3)*ZnTPP within 1-4, the magnitude of the exchange interactions between the three relevant spins in the resulting (3)*ZnTPP-BPNO(•) and (3)*ZnTPP-BDPA(•) systems dramatically alters their spin dynamics.

Direct measurement of the dynamics of hole hopping in extended DNA G-tracts. An unbiased random walk.

We report the measurement of distance- and temperature-dependent rate constants for charge separation in capped hairpins in which a stilbene hole acceptor and hole donor are separated by A(3)G(n) diblock polypurine sequences consisting of 3 adenines and 1-19 guanines. The longer diblock systems obey the simplest model for an unbiased random walk, providing a direct measurement of k(hop) = 4.3 × 10(9) s(-1) for a single reversible G-to-G hole hopping step, somewhat faster than the value of 1.2 × 10(9) s(-1) calculated for A-tract hole hopping. The temperature dependence for hopping in A(3)G(13) provides values of E(act) = 2.8 kcal/mol and A = 7 × 10(9) s(-1), consistent with a weakly activated, conformationally gated process.

Self-assembly of a hexagonal supramolecular light-harvesting array from chlorophyll a trefoil building blocks.

Small- and wide-angle X-ray scattering in solution reveals that chlorophyll (Chl) trefoils self-assemble in the presence of 1,4-diazabicyclo[2.2.2]octane (DABCO) to yield supramolecular cyclic trimers. Two Chls of each trefoil coordinate to DABCO to form the vertices of the hexagonal structure, while the remaining Chl acts like a substituent on the benzene-like assembly.