Role of Host-Guest Interaction in Understanding Polymerisation in Metal Organic Frameworks

Metal-organic frameworks, MOFs, offer an effective templet for polymerisation of polymers with precisely controlled structures within the sub-nanometre scales. However, synthetic difficulties such as monomer infiltration, detailed understanding of polymerisation mechanisms within the MOF nano-channels and the mechanism for removing the MOF template post polymerisation have prevented wide scale implementation of polymerisation in MOFs. This is partly due to the significant lack in understanding of the energetic and atomic-scale intermolecular interactions between the monomers and the MOFs. Consequently in this study, we explore the interaction of varied concentration of styrene, and EDOT, at the surface and in the nano-channel of Zn2(1,4- ndc)2(dabco), where 1,4-ndc = 1,4-naphthalenedicarboxylate and dabco = 1,4-diazabicyclo[2.2.2]octane. Our results showed that the interactions between monomers are stronger in the nano-channels than at the surfaces of the MOF. Moreover, the MOF-monomer interactions are strongest in the nano-channels and increases with increase in the number of monomers. However, as the number of monomer increases, the monomers turn to bind more strongly at the surface leading to a potential agglomeration of the monomers at the surface.