Ultrasonic exfoliation of hydrophobic and hydrophilic metal-organic frameworks to form nanosheets

The modular structure of metal-organic nanosheets (MONs) provides a convenient route to creating two-dimensional materials with readily tunable surface properties. Here we report the liquid exfoliation of two closely related layered metal-organic frameworks functionalised with either methoxy-propyl (1) or pentyl (2) pendent groups intended to bestow either hydrophilic or hydrophobic character to the resulting nanosheets. Exfoliation of the two materials in a range of different solvents highlighted significant differences in their dispersion properties and molecular and nanoscopic structure. Exchange or loss of solvent was found to occur at the labile axial position of the paddle-wheel based MONs and DFT calculations indicated that intramolecular coordination by the oxygen of the methoxy-propyl pendant groups may take place. The nanoscopic dimensions of the MONs were further tuned by varying the exfoliation conditions and through "cascade centrifugation". Aqueous suspensions of the nanosheets were used as sensors to detect aromatic heterocycles and with clear differences in binding behaviour observed and quantified.