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

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