Detection of magnetic field effects by confocal microscopy.

Certain pairs of paramagnetic species generated under conservation of total spin angular momentum are known to undergo magnetosensitive processes. Two prominent examples of systems exhibiting these so-called magnetic field effects (MFEs) are photogenerated radical pairs created from either singlet or triplet molecular precursors, and pairs of triplet states generated by singlet fission. Here, we showcase confocal microscopy as a powerful technique for the investigation of such phenomena. We first characterise the instrument by studying the field-sensitive chemistry of two systems in solution: radical pairs formed in a cryptochrome protein and the flavin mononucleotide/hen egg-white lysozyme model system. We then extend these studies to single crystals. Firstly, we report temporally and spatially resolved MFEs in flavin-doped lysozyme single crystals. Anisotropic magnetic field effects are then reported in tetracene single crystals. Finally, we discuss the future applications of confocal microscopy for the study of magnetosensitive processes with a particular focus on the cryptochrome-based chemical compass believed to lie at the heart of animal magnetoreception.

Nanosecond time-resolved characterization of a pentacene-based room-temperature MASER.

The performance of a room temperature, zero-field MASER operating at 1.45 GHz has been examined. Nanosecond laser pulses, which are essentially instantaneous on the timescale of the spin dynamics, allow the visible-to-microwave conversion efficiency and temporal response of the MASER to be measured as a function of excitation energy. It is observed that the timing and amplitude of the MASER output pulse are correlated with the laser excitation energy: at higher laser energy, the microwave pulses have larger amplitude and appear after shorter delay than those recorded at lower laser energy. Seeding experiments demonstrate that the output variation may be stabilized by an external source and establish the minimum seeding power required. The dynamics of the MASER emission may be modeled by a pair of first order, non-linear differential equations, derived from the Lotka-Volterra model (Predator-Prey), where by the microwave mode of the resonator is the predator and the spin polarization in the triplet state of pentacene is the prey. Simulations allowed the Einstein coefficient of stimulated emission, the spin-lattice relaxation and the number of triplets contributing to the MASER emission to be estimated. These are essential parameters for the rational improvement of a MASER based on a spin-polarized triplet molecule.

Enhanced magnetic Purcell effect in room-temperature masers.

Recently, the world's first room-temperature maser was demonstrated. The maser consisted of a sapphire ring housing a crystal of pentacene-doped p-terphenyl, pumped by a pulsed rhodamine-dye laser. Stimulated emission of microwaves was aided by the high quality factor and small magnetic mode volume of the maser cavity yet the peak optical pumping power was 1.4 kW. Here we report dramatic miniaturization and 2 orders of magnitude reduction in optical pumping power for a room-temperature maser by coupling a strontium titanate resonator with the spin-polarized population inversion provided by triplet states in an optically excited pentacene-doped p-terphenyl crystal. We observe maser emission in a thimble-sized resonator using a xenon flash lamp as an optical pump source with peak optical power of 70 W. This is a significant step towards the goal of continuous maser operation.

Excited-state dynamics in an α-perylene single crystal: two-photon- and consecutive two-quantum-induced singlet fission.

Excited-state dynamics in α-perylene single crystals is studied by time-resolved fluorescence and transient absorption techniques under different excitation conditions. The ultrafast lifetimes of the "hot" excimer (Y) state were resolved. Three competing excited-states decay channels are observed: excimer formation, dimer cation generation, and singlet fission. The singlet fission induced by two-photon and consecutive two-quantum absorption is reported for the first time in an α-perylene crystal.

Revealing surface oxidation on the organic semi-conducting single crystal rubrene with time of flight secondary ion mass spectroscopy.

To address the question of surface oxidation in organic electronics the chemical composition at the surface of single crystalline rubrene is spatially profiled and analyzed using Time of Flight - Secondary Ion Mass Spectroscopy (ToF-SIMS). It is seen that a uniform oxide (C42H28O) covers the surface while there is an increased concentration of peroxide (C42H28O2) located at crystallographic defects. By analyzing the effects of different primary ions, temperature and sputtering agents the technique of ToF-SIMS is developed as a valuable tool for the study of chemical composition variance both at and below the surface of organic single crystals. The primary ion beams C60(3+) and Bi3(+) are found to be most appropriate for mass spectroscopy and spatial profiling respectively. Depth profiling of the material is successfully undertaken maintaining the molecular integrity to a depth of ~5 µm using an Ar cluster ion source as the sputtering agent.

Crystal structure and phototransistor behavior of N-substituted heptacence.

6,8,15,17-Tetraaza-1.18,4.5,9.10,13.14-tetrabenzoheptacene (TTH, 1) has been prepared and characterized by single-crystal X-ray structure analysis. A phototransistor device based on TTH single crystal demonstrated that TTH showed a good performance in signal amplification under the photoconductive effect as well as photocontrolled switches.

Synthesis, characterization, self-assembly, and physical properties of 11-methylbenzo[d]pyreno[4,5-b]furan.

Synthesis, structure, and physical properties of a novel 11-methylbenzo[d]pyreno[4,5-b]furan (BPF) and its self-assembly in water have been reported. The performance of nanowire-based films in organic light-emitting diodes is much better than that of the thin film deposited by directly drop-coating BPF molecules in THF solution. SEM study indicates that the well-organized structure (nanowires) is an important factor in enhancing the performance of OLED devices.

Influence of vibronic coupling on band structure and exciton self-trapping in α-perylene.

Exciton sizes influence transport processes and spectroscopic phenomena in molecular aggregates and crystals. Thermally driven nuclear motion generally localizes electronic states in equilibrium systems. Exciton sizes also undergo dynamic changes caused by nonequilibrium relaxation in the lattice structure local to the photoexcitations (i.e., self-trapping). The α-phase of crystalline perylene is particularly well-suited for fundamental studies of exciton self-trapping mechanisms. It is generally agreed that a subpicosecond self-trapping process in α-perylene localizes photoexcited excitons onto pairs of closely spaced molecules (i.e., dimers), which then relax through excimer emission. Here, electronic relaxation dynamics in α-perylene single crystals are investigated using a variety of nonlinear optical spectroscopies in conjunction with a Frenkel exciton model. Linear absorption and photon echo spectroscopies suggest that excitons are delocalized over less than four unit cells (16 molecules) at 78 K prior to self-trapping. Stimulated Raman spectroscopies conducted on and off electronic resonance reveal significant vibronic coupling in a mode at 104 cm(-1), which corresponds to the displacement between perylene molecules comprising a dimer. Strong vibronic coupling in this mode suggests that motion along the interdimer axis is instrumental in driving the self-trapping process. The results are discussed in the context of our recent study of tetracene and rubrene single crystals in which similar experiments and models were employed.

One-pot synthesis of 4,8-dibromobenzo[1,2-c;4,5-c']bis[1,2,5]thiadiazole.

A one-step synthesis of 4,8-dibromobenzo[1,2-c;4,5-c']bis[1,2,5]thiadiazole with use of 1,2,4,5-tetraaminobenzene tetrahydrobromide and thionyl bromide in good yield is reported. This unit can then be used in the synthesis of low bandgap materials via palladium-catalyzed coupling reactions. The approach offers a quick and easy way to prepare low bandgap materials as compared to the current literature methods.