Wonanke A D Dinga, Bennett Poppy, Caldwell Lewis, Addicoat Matthew A
Department of Chemistry and Forensics, Nottingham Trent University, Nottingham, United Kingdom.
Front Chem. 2021 Jul 21;9:716294. doi: 10.3389/fchem.2021.716294. eCollection 2021.
Metal-organic frameworks, MOFs, offer an effective template 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 nanochannels 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 3,4-ethylenedioxythiophene (EDOT), at the surface and in the nanochannel of Zn(1,4-ndc) (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 nanochannels than at the surfaces of the MOF. Moreover, the MOF-monomer interactions are strongest in the nanochannels and increase with the number of monomers. However, as the number of monomers increases, the monomers turn to bind more strongly at the surface leading to a potential agglomeration of the monomers at the surface.
金属有机框架材料（MOFs）为在亚纳米尺度内精确控制结构的聚合物聚合提供了一种有效的模板。然而，诸如单体渗透、对MOF纳米通道内聚合机制的详细理解以及聚合后去除MOF模板的机制等合成难题阻碍了MOF中聚合反应的大规模应用。部分原因是对单体与MOFs之间的能量和原子尺度分子间相互作用缺乏深入了解。因此，在本研究中，我们探究了不同浓度的苯乙烯和3,4-乙撑二氧噻吩（EDOT）在Zn(1,4-ndc)(dabco)的表面和纳米通道中的相互作用，其中1,4-ndc = 1,4-萘二甲酸酯，dabco = 1,4-二氮杂双环[2.2.2]辛烷。我们的结果表明，单体之间在纳米通道中的相互作用比在MOF表面更强。此外，MOF与单体之间的相互作用在纳米通道中最强，并且随着单体数量的增加而增强。然而，随着单体数量的增加，单体在表面的结合变得更强，导致单体在表面可能发生团聚。
