A nonporous molecular
crystal (NMC) has been developed for use
as a host material. The NMC comprises a platinum dibromide complex
with coordinating 9-phenyl-9-arsafluorene ligands. The NMC also contains
chlorobenzene (PhCl) molecules, which quench emissions from the platinum
complex. On exposure to the vapors of several volatile organic compounds
(VOC), the encapsulated PhCl was released. With the loss of PhCl,
the crystal once again showed the intrinsic luminescence of the platinum
complex. Furthermore, the NMC can recognize the molecular shape of
VOCs; consequently, VOCs having small minimum diameters turn on emission,
but large VOCs do not cause the release of the included PhCl quencher,
and emission remains switched off. Interestingly, a wide range of
VOCs (e.g., alcohol, ether, haloalkane, and alkane) could be used,
implying that the shape recognition ability of the present NMC system
is polarity independent. This is the first example of NMCs having
widespread molecular shape recognition properties.