Resolving Molecular Size and Homologues with a Self-Assembled Metal–Organic Framework Photonic Crystal Detector

Traditional environmental photonic sensing based on the balanced reflection of a photonic structure can hardly be applied to distinguish molecular size and homologues, since the refractive index change introduced by these analytes can be too similar to be unambiguously distinguished. Here, a sensing method based on the pore size selectivity and organics adsorption–desorption capacity of self-assembled ZIF-8 photonics crystal is demonstrated, which can tell apart different molecular sizes, homologues, and organics with similar structures and physical properties. Specificity is improved by the inherent relationships between the pore size of ZIF-8 metal–organic frameworks and the associated molecular diffusion rates in the pores, so that the combination of the observed peak shift and recovery time are unique to each analyte. Using this method, selective detection of molecular size is also demonstrated in the case of linear vs cyclic molecules, since only the former can penetrate inside the ZIF-8 pores to induce a large wavelength shift. The reflection peak shift caused by the linear molecules was found to be about 30–40 nm, an order of magnitude larger compared to those for the cyclic molecules. A relationship between the diffusion rate of linear molecules in ZIF-8 pore and the recovery time of photonic crystal reflective peak is further established, linking the recovery time and the linear molecular diffusion coefficient. Finally, different linear molecules are identified by their associated recovery time to detect homologues or organics with similar refractive index.