Photophysics of Azobenzene Constrained in a UiO Metal–Organic Framework: Effects of Pressure,Solvation and Dynamic Disorder

Photophysical studies of chromophoric linkers in metal–organic frameworks (MOFs) are undertaken commonly in the context of sensing applications, in search of readily observable changes of optical properties in response to external stimuli. The advantages of the MOF construct as a platform for investigating fundamental photophysical behaviour have been somewhat overlooked. The linker framework offers a unique environment in which the chromophore is geometrically constrained and its structure can be determined crystallographically, but it exists in spatial isolation, unperturbed by inter-chromophore interactions. Furthermore, high-pressure studies enable the photophysical consequences of controlled, incremental changes in local environment or conformation to be observed and correlated with structural data. This approach is demonstrated in the present study of the trans-azobenzene chromophore, constrained in the form of the 4,4’-azobenzenedicarboxylate (abdc) linker, in a UiO topology framework. Previously unobserved effects of pressure-induced solvation and conformational distortion on the lowest energy, nπ* transition are reported, and interpreted the light of crystallographic data. It was found that trans-azobenzene remains non-fluorescent (with a quantum yield less than 10⁻⁴) despite the prevention of trans-cis isomerization by the constraining MOF structure. We propose that efficient non-radiative decay is mediated by the local, pedal-like twisting of the azo group that is evident as dynamic disorder in the crystal structure.     

Synthesis,Structure, and Reactivity of a Gold Carbenoid Complex That Lacks Heteroatom Stabilization

Hydride abstraction from the neutral gold cycloheptatrienyl complex [( P )Au(η¹‐C₇H₇)] ( P =P(tBu)₂(o‐biphenyl)) with triphenylcarbenium tetrafluoroborate at ?80 °C led to the isolation of the cationic gold cycloheptatrienylidene complex [( P )Au(η¹‐C₇H₆)]⁺ BF₄^? in 52 % yield, which was characterized in solution and by single‐crystal X‐ray diffraction. This cycloheptatrienylidene complex represents the first example of a gold carbenoid complex that lacks conjugated heteroatom stabilization of the electron‐deficient C1 carbon atom. The cycloheptatrienylidene ligand of this complex is reactive; it can be reduced by mild hydride donors, and converted to tropone in the presence of pyridine N‐oxide.     

Biimidazol-2-yl–BF2 complexes

Nonfluorescent 4,4′,5,5′-tetramethyl- and 4,5,4′,5′-bistetramethylene biimidazol-2-yls 5 and 6 combined with boron trifluoride to give the tetramethyl and bistetramethylenebiimidazol-2-yl–BF₂ complexes 9 and 10 isolated as strongly fluorescent BF₃ salts, λ_f (dichloromethane): 377 nm Φ 0.93 and 386 nm Φ 0.90. Similarly, fluorescent bibenzimidazol-2-yl 7 , λ_f (ethanol), 370 nm Φ 0.14, gave a BF₂ complex 11 isolated as a BF₃ salt λ_f (ethanol), 417 nm Φ 0.68.     

Selection of solvent load and first-stage pressure to reduce interference effects in inductively coupled plasma-mass spectrometry

In inductively coupled plasma-mass spectrometry the first-stage pressure and solvent characteristics can strongly influence spectral and nonspectroscopic interference effects. By manipulating the pressure and solvent load, one can regulate the degree of analyte signal suppression observed in the presence of high concentrations (> 10 mM) of concomitants. Importantly, the same operating conditions that eliminate the matrix effects maintain the analytical utility of the system. However, for some interferent-analyte combinations, the identity of the concomitant anion and subsequent pH of the solution determine whether the interference effects can be eliminated entirely. The first-stage pressure does not appear to significantly affect the oxide-ion and doubly charged ion ratios; the solvent characteristics are the dominant factors that dictate these ratios.     

Ideal laser-beam propagation through high-temperature ignition Hohlraum plasmas

We demonstrate that a blue (3omega, 351 nm) laser beam with an intensity of 2 x 10(15) W cm(-2) propagates nearly within the original beam cone through a millimeter scale, T(e)=3.5 keV high density (n(e)=5 x 10(20) cm(-3)) plasma. The beam produced less than 1% total backscatter at these high temperatures and densities; the resulting transmission is greater than 90%. Scaling of the electron temperature in the plasma shows that the plasma becomes transparent for uniform electron temperatures above 3 keV. These results are consistent with linear theory thresholds for both filamentation and backscatter instabilities inferred from detailed hydrodynamic simulations. This provides a strong justification for current inertial confinement fusion designs to remain below these thresholds.     

Anomalous optical constants of thin films

The explanation of anomalous optical constants in thin chemically distinct layers on substrates offered by Plumb is re-examined and extended. The model invokes the concept of the space charged boundary layer and treats the charge carrier population as a free-electron gas to derive the optical behaviour of thin surface films. The implication of the space charge means that the optical constants of a dielectric film on a metal will vary over a distance directly proportional to the dielectric constant of the film and inversly proportional to the concentration of the electrons at the metal/film interface. Similarly as the temperature increases this space charge region should extend to larger distances from the interface.     

The First in Vivo Observation of C–N Coupling in Mammalian Brain

[5-¹³C,¹⁵N]Glutamine, with ¹J(¹³C–¹⁵N) of 16 Hz, was observed in vivo in the brain of spontaneously breathing rats by ¹³C MRS at 4.7 T. The brain [5-¹³C]glutamine peak consisted of the doublet from [5-¹³C,¹⁵N]glutamine and the center [5-¹³C,¹⁴N]glutamine peak, resulting in an apparent triplet with a separation of 8 Hz. The time course of formation of brain [5-¹³C,¹⁵N]glutamine was monitored in vivo with a time resolution of 20–35 min. This [5-¹³C,¹⁵N]glutamine was formed by glial uptake of released neurotransmitter [5-¹³C]glutamate and its reaction with ¹⁵NH₃ catalyzed by the glia-specific glutamine synthetase. The neurotransmitter glutamate C5 was selectively¹³C-enriched by intravenous [2,5-¹³C]glucose infusion to ¹³C-label whole-brain glutamate C5, followed by [¹²C]glucose infusion to chase ¹³C from the small and rapidly turning-over glial glutamate pool, leaving ¹³C mainly in the neurotransmitter [5-¹³C]glutamate pool, which is sequestered in vesicles until release. Hence, the observed [5-¹³C,¹⁵N]glutamine arises from a coupling between ¹³C of neuronal origin and ¹⁵N of glial origin. Measurement of the rate of brain [5-¹³C,¹⁵N]glutamine formation provides a novel noninvasive method of studying the kinetics of neurotransmitter uptake into glia in vivo, a process that is crucial for protecting the brain from glutamate excitotoxicity.     

High dynamic range measurement of temporal shape and contrast of ultrashort UV pulses

This paper presents an experimental technique for measurement of the contrast ratio of ultrashort UV pulses. As a multiple-shot device based on the scheme of difference frequency generation this is, to our knowledge, the only cross correlator in the UV so far, which offers a dynamic range of 10⁷ and operates with input pulse energies as low as 5 μJ. By changing the cross correlator into single-shot mode, the temporal shape of the UV pulse can be measured. Received: 26 October 1998 / Revised version: 13 January 1998 / Published online: 28 April 1999     

Probing the structure of the pomeron

We suggest that the pseudo-rapidity cut dependence of diffractive deep-inelastic scattering events at HERA may provide a sensitive test of models of diffraction. A comparison with the experimental cross section shows that the Donnachie-Landshoff model and a simple two-gluon exchange model of the pomeron model are disfavoured. However a model with a direct coupling of the pomeron to quarks is viable for a harder quark–pomeron form factor, as is a model based on the leading-twist operator contribution. We also consider a direct-coupling scalar pomeron model. We comment on the implications of these results for the determination of the partonic structure of the pomeron. Received: 5 March 1999 / Published online: 3 August 1999