On the basis of the
unique chaotropic supramolecular assembly of cucurbit[5]uril (CB5)
and dodecahydro-closo-dodecaborate anion [closo-B12H12]2–,
we have developed an efficient and universal platform to fabricate
shape-controlled dodecaborate-based supramolecular organic frameworks
(BOFs) decorated with ultrafine monodispersed trimetallic alloys.
Simply by regulating the molar ratio of CB5 and [closo-B12H12]2–, a series of fascinating
morphologies, such as flowerlike structures, nanorods, nanocubes,
and nanosheets, were successfully constructed. These obtained BOFs
were proved to be good substrate supports for in situ synthesis of
trimetallic PtCoNi nanoalloys, where the final PtCoNi–BOFs
materials were obtained efficiently as a precipitate from aqueous
solutions, and showed excellent catalytic performance in ammonia borane
hydrolysis with a high turnover frequency of 1490 molH2
molPt
–1 min–1 and a low activation energy of 15.79 kJ mol–1.
To
address a long-standing issue of building molecular electrical
circuits heavily relying on anchoring chemistry, we propose an alternative
method to immobilize anchor-free molecules in a molecular cavity between
metal electrodes. In such a scheme, well-defined conductance distribution
of anchor-free molecules was obtained by means of a scanning tunneling
microscopy break-junction technique. Density functional theory calculations
suggest that effective electronic coupling at the molecule-electrode
interface can be achieved through well-defined van der Waals (vdW)
interactions when the molecule is confined in a cavity with a defined
geometry. This work offers a new paradigm to achieve reliable conductance
measurements of molecules via vdW interaction without metal-binding
groups.
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