Expanding luminescence horizons in macropolyhedral heteroboranes

Luminescence is observed in three novel macropolyhedral nineteen- and eighteen-vertex chalcogenaboranes: Se2B17H17 (1), SeB17H19 (3) and SeB18H20 (4). This led us to the recognition that previously published macropolyhedral heteroborane species might also exhibit luminescence. Thus, the known nineteen- and eighteen-vertex dithiaboranes S2B17H17 (2), n-S2B16H16 (5) and i-S2B16H16 (6) were synthesised and also found to exhibit a range of luminescent properties. These macropolyhedral species are very different from the previously unique fluorescent binary borane B18H22 in terms of their structural architectures, by the presence of borane cluster hetero atoms, and, as in the cases of 5 and 6, that their synthetic origins are not derived simply through the modification of B18H22 itself. They consequently greatly expand the possibilities of finding new luminescent inorganic borane species

Zn-Al Layered Double Hydroxide Film Functionalized by a Luminescent Octahedral Molybdenum Cluster: Ultraviolet-Visible Photoconductivity Response

International audienceA novel UV-Vis photodetector consisting of an octahedral molybdenum cluster-functionalized ZnAl layered double hydroxide (LDH) has been successfully synthesized by co-precipitation and delamination methods under ambient conditions. The electrophoretic deposition process has been used as a low-cost, fast, and effective method to fabricate thin and transparent nanocomposite films containing a dense and regular layered structure. The study provided evidence that the presence of the Mo cluster units between the LDH does not affect the ionic conduction mechanism of the LDH, which linearly depends on the relative humidity and temperature. Moreover, the photocurrent response is remarkably extended to the visible domain. The reproducibility and stabilization of the photocurrent response caused by the Mo cluster-functionalized LDH have been verified upon light excitation at 540 nm. Additionally, it was demonstrated that the films show advantageously strong adherence properties for application requirements

A Series of Ultra-Efficient Blue Borane Fluorophores

13 pags., 14 figs., 5 tabs.We present the first examples of alkylated derivatives of the macropolyhedral boron hydride, anti-B18H22, which is the gain medium in the first borane laser. This new series of ten highly stable and colorless organic-inorganic hybrid clusters are capable of the conversion of UVA irradiation to blue light with fluorescence quantum yields of unity. This study gives a comprehensive description of their synthesis, isolation, and structural characterization together with a delineation of their photophysical properties using a combined theoretical and experimental approach. Treatment of anti-B18H22 1 with RI (where R = Me or Et) in the presence of AlCl3 gives a series of alkylated derivatives, Rx-anti-B18H22-x (where x = 2 to 6), compounds 2-6, in which the 18-vertex octadecaborane cluster architectures are preserved and yet undergo a linear "polyhedral swelling", depending on the number of cluster alkyl substituents. The use of dichloromethane solvent in the synthetic procedure leads to dichlorination of the borane cluster and increased alkylation to give Me11-anti-B18H9Cl2 11, Me12-anti-B18H8Cl2 12, and Me13-anti-B18H7Cl2 13. All new alkyl derivatives are highly stable, extremely efficient (φF = 0.76-1.0) blue fluorophores (λems = 423-427 nm) and are soluble in a wide range of organic solvents and also a polystyrene matrix. The Et4-anti-B18H18 derivative 4b crystallizes from pentane solution in two phases with consequent multiabsorption and multiemission photophysical properties. An ultrafast transient UV-vis absorption spectroscopic study of compounds 4a and 4b reveals that an efficient excited-state absorption at the emission wavelength inhibits the laser performance of these otherwise remarkable luminescent molecules. All these new compounds add to the growing portfolio of octadecaborane-based luminescent species, and in an effort to broaden the perspective on their highly emissive photophysical properties, we highlight emerging patterns that successive substitutions have on the molecular size of the 18-vertex borane cluster structure and the distribution of the electron density within.This work was supported by the Czech Science Foundation (Project No. 18-20286S). We also acknowledge the working group Interactions of Inorganic Clusters, Cages, and Containers with Light within the AV21 Strategy, Czech Academy of Sciences. W.C. and P.G.W. thank Diamond Light Source for access to beamline I19 in remote-access mode (beam-time award CY22240). A.F.-M. is grateful to Generalitat Valenciana and the European Social Fund (postdoctoral contract APOSTD/2019/149 and project GV/2020/226) for financial support. A.F.-M. and D.R.-S. also acknowledge support from the Ministerio de Ciencia e Innovacioń (project CTQ2017- 87054-C2-2-P)