No abstract

As part of our efforts to discover simple routes to room-temperature phosphors, we have investigated the interaction of bis(pentafluorophenyl)mercury (1) or trimeric perfluoro-o-phenylene mercury (2) with selected arenes (naphthalene, biphenyl, and fluorene). Solution studies indicate that 2, unlike 1, quenches the fluorescence of naphthalene. When compared to 1, the high quenching efficiency of 2 may be correlated to the higher affinity that 2 displays for arenes as well as to more acute external heavy-atom effects caused by the three mercury atoms. In the crystal, the adducts [1.naphthalene], [1.biphenyl], [1.fluorene], and [2.fluorene] form supramolecular binary stacks in which the arene approaches the mercury centers of 1 or 2 to form Hg-C pi-interactions. Analysis of the electrostatic potential surfaces of the individual components supports the involvement of electrostatic interactions. The luminescence spectra of the adducts show complete quenching of the fluorescence and display heavy-atom-induced emission whose energies and vibronic progressions correspond to the phosphorescence of the respective pure arene. The phosphorescence lifetimes are shortened by 3 or 4 orders of magnitude when compared with those of the free arenes. Taken collectively, the structural, photophysical, and computational results herein suggest that the proximity of the three mercury centers serves to enhance the Lewis acidity of 2, which becomes a better acceptor and a more effective heavy-atom effect inducer than 1.

No abstract

We demonstrate frequency-comb-based optical two-way time-frequency transfer across a three-node clock network. A fielded, bidirectional relay node connects laboratory-based master and end nodes, allowing the network to span 28 km of turbulent outdoor air while keeping optical transmit powers below 5 mW. Despite the comparatively high instability of the free-running local oscillator at the relay node, the network transfers frequency with fractional precision below 10−18 at averaging times above 200 s and transfers time with a time deviation below 1 fs at averaging times between 1 s and 1 h. The successful operation of this network represents a promising step toward the operation of future free-space networks of optical atomic clocks.