Sulfur functionalized diamondoid phosphines enable building nanocomposites interfacing sp3-carbon and gold nanolayers†

Interfacing metal frameworks with carbon-based materials is attractive for the bottom-up construction of nanocomposite functional materials. The stepwise layering of difunctionalized diamantanes and gold metal from physical and chemical vapor deposition for the preparation of nanocomposites inverts the conventional preparation of metal–organic frameworks (MOFs) and self-assemblies, where the metal is introduced first, and this method delivers metal surfaces with modified properties originating from the sp³-carbon core. However, appropriate diamondoid candidates for such an approach are rare. By the mild chemical vapor deposition of the organometallic complex MeAuPMe₃, gold coating is achieved on a diamantane SP^(V) sulfide primary phosphine diamantanol 2. This later leads to sulfide and polysulfide surface rearrangement and provides a suitable substrate for metal–organic nanocomposite formation through a fully-dry vapor process, with the advantage, in contrast to the P^(III) primary phosphine phosphinodiamantanol 1, of being resistant to uncontrolled oxidation at phosphorus during physical vapor deposition (PVD) and chemical vapor deposition (CVD) processing.