Locking down the electronic structure of (monopyrrolo)tetrathiafulvalene in [2]rotaxanes

[reaction: see text] The redox potentials of a highly constrained [2]rotaxane have been measured and used to model the energy of the HOMO of tetrathiafulvalene-based bistable [2]rotaxanes in their two co-conformationally isomeric states. Restrained from co-conformational movements, the measured oxidation and reduction potentials provide insights into the orbital energies and electronic structure of a (monopyrrolo)tetrathiafulvalene unit when encircled by a tetracationic cyclobis(paraquat-p-phenylene) ring.     

Discovery of the shape coexisting 0+ state in 32 Mg by a two neutron transfer reaction

The "island of inversion" nucleus 32 Mg has been studied by a (t, p) two neutron transfer reaction in inverse kinematics at REX-ISOLDE. The shape coexistent excited 0+ state in 32 Mg has been identified by the characteristic angular distribution of the protons of the Δ L=0 transfer. The excitation energy of 1058 keV is much lower than predicted by any theoretical model. The low γ-ray intensity observed for the decay of this 0+ state indicates a lifetime of more than 10 ns. Deduced spectroscopic amplitudes are compared with occupation numbers from shell-model calculations.     

Ground-state equilibrium thermodynamics and switching kinetics of bistable [2]rotaxanes switched in solution, polymer gels, and molecular electronic devices

We report on the kinetics and ground-state thermodynamics associated with electrochemically driven molecular mechanical switching of three bistable [2]rotaxanes in acetonitrile solution, polymer electrolyte gels, and molecular-switch tunnel junctions (MSTJs). For all rotaxanes a pi-electron-deficient cyclobis(paraquat-p-phenylene) (CBPQT4+) ring component encircles one of two recognition sites within a dumbbell component. Two rotaxanes (RATTF4+ and RTTF4+) contain tetrathiafulvalene (TTF) and 1,5-dioxynaphthalene (DNP) recognition units, but different hydrophilic stoppers. For these rotaxanes, the CBPQT4+ ring encircles predominantly (>90 %) the TTF unit at equilibrium, and this equilibrium is relatively temperature independent. In the third rotaxane (RBPTTF4+), the TTF unit is replaced by a pi-extended analogue (a bispyrrolotetrathiafulvalene (BPTTF) unit), and the CBPQT4+ ring encircles almost equally both recognition sites at equilibrium. This equilibrium exhibits strong temperature dependence. These thermodynamic differences were rationalized by reference to binding constants obtained by isothermal titration calorimetry for the complexation of model guests by the CBPQT4+ host in acetonitrile. For all bistable rotaxanes, oxidation of the TTF (BPTTF) unit is accompanied by movement of the CBPQT4+ ring to the DNP site. Reduction back to TTF0 (BPTTF0) is followed by relaxation to the equilibrium distribution of translational isomers. The relaxation kinetics are strongly environmentally dependent, yet consistent with a single electromechanical-switching mechanism in acetonitrile, polymer electrolyte gels, and MSTJs. The ground-state equilibrium properties of all three bistable [2]rotaxanes were reflective of molecular structure in all environments. These results provide direct evidence for the control by molecular structure of the electronic properties exhibited by the MSTJs.     

Molecular logic gates using surface-enhanced Raman-scattered light

A voltage-activated molecular-plasmonics device was created to demonstrate molecular logic based on resonant surface-enhanced Raman scattering (SERS). SERS output was achieved by a combination of chromophore-plasmon coupling and surface adsorption at the interface between a solution and a gold nanodisc array. The chromophore was created by the self-assembly of a supramolecular complex with a redox-active guest molecule. The guest was reversibly oxidized at the gold surface to the +1 and +2 oxidation states, revealing spectra that were reproduced by calculations. State-specific SERS features enabled the demonstration of a multigate logic device with electronic input and optical output.     

Optical switching and detection of 640 Gbits/s optical time-division multiplexed data packets transmitted over 50 km of fiber

We demonstrate 1×4 optical-packet switching with error-free transmission of 640?Gbits/s single-wavelength optical time-division multiplexed data packets including clock distribution and short pulse generation for optical time demultiplexing based on a cavityless pulse source.     

Blue five-level frequency-upconversion system in rubidium

We demonstrate production of continuous coherent blue laser light by using a five-level system in rubidium vapor. Two low-power lasers, at 780 and 776 nm, induce strong atomic coherence in the 5S-5P-5D states. The atoms decay to the 6P excited state, from which stimulated emission produces a coherent blue (420 nm) beam. We have coupled both ground-state hyperfine levels, effecting coherence between four levels. The coherent blue output is enhanced by several mechanisms, including stronger coupling to a larger fraction of the atomic population, operation at a detuning such that the vapor is nominally transparent to the 780 nm pump field, reduced losses owing to optical pumping, and optimal phase matching. We report experimental findings and compare them with results from a semiclassical Maxwell-Bloch model.     

Search for oscillation of the electron-capture decay probability of Pm

We have searched for time modulation of the electron capture decay probability of ¹⁴²Pm in an attempt to confirm a recent claim from a group at the Gesellschaft für Schwerionenforschung (GSI). We produced ¹⁴²Pm via the ¹²⁴Sn(²³Na, 5n)¹⁴²Pm reaction at the Berkeley 88-Inch Cyclotron with a bombardment time short compared to the reported modulation period. Isotope selection by the Berkeley Gas-filled Separator is followed by implantation and a long period of monitoring the ¹⁴²Nd Kα${\text{K}}_{\alpha }$ x-rays from the daughter. The decay time spectrum of the x-rays is well-described by a simple exponential and the measured half-life of 40.68(53) seconds is consistent with the accepted value. We observed no oscillatory modulation at the proposed frequency at a level 31 times smaller than that reported by Litvinov et al. [Y.A. Litvinov, et al., Phys. Lett. B 664 (2008) 162]. A literature search for previous experiments that might have been sensitive to the reported modulation uncovered another example in ¹⁴²Eu electron-capture decay. A reanalysis of the published data shows no oscillatory behavior.     

Effects of pressure and temperature on RD detected growth oscillations

We report on the vacuum chemical epitaxy (VCE) growth of GaAs from triethylgallium and arsine at varying partial pressures of arsine and hydrogen. In situ, monolayer growth oscillations were, for the first time, detected in a hydrogen environment using reflectance difference (RD). These results offer the possibility to link surface mechanisms occuring during chemical beam epitaxy (CBE) with those taking place in metalorganic vapour phase epitaxy (MOVPE) and may lead to the observation of growth oscillations also during MOVPE. Finally, the behaviour of the RD signal as a function of substrate temperature is studied over a wider temperature interval than has previously been reported, giving further information about surface processes.     

Acid/base controllable molecular recognition

The study of controllable molecular recognition in supramolecular receptors is important for elucidating design strategies that can lead to external control of molecular recognition applications. In this work, we present the design and synthesis of an asymmetric (TTF) tetrathiafulvalene-calix[4]pyrrole receptor and show that its recognition of 1,3,5-trinitrobenzene (TNB) can be controlled by an acid/base input. The new receptor is composed of three identical TTF units and a fourth TTF unit appended with a phenol moiety. Investigation of the host-guest complexation taking place between the TTF-calix[4]pyrrole receptor and the TNB guests was studied by means of absorption and (1)H NMR spectroscopy; this revealed that the conformation of the molecular receptor can be switched between locked and unlocked states by using base and acid as the input. In the unlocked state, the receptor is able to accommodate two TNB guest molecules, whereas the guests are not able to bind to the receptor in the locked state. This work serves to illustrate how external control (acid/base) of a receptor may be used to direct the molecular recognition of guests (TNBs). It has led to a new controllable molecular recognition system that functions as an acid/base switch.