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.

Abstract