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Multivariate Stratified Metal–Organic Frameworks: Diversification Using Domain Building Blocks
journal contribution
posted on 2019-01-12, 00:00 authored by Tian-Yi Luo, Chong Liu, Xing Yee Gan, Patrick F. Muldoon, Nathan A. Diemler, Jill E. Millstone, Nathaniel L. RosiWe introduce the
concept of domain building blocks (DBBs) as an
effective approach to increasing the diversity and complexity of metal–organic
frameworks (MOFs). DBBs are defined as distinct structural or compositional
regions within a MOF material. Using the DBB approach, we illustrate
how an immense number of multivariate MOF materials can be prepared
from a small collection of molecular building blocks comprising the
distinct domains. The multivariate nature of the MOFs is determined
by the sequence of DBBs within the MOF. We then apply this approach
to the construction of a rich library of UiO-67 stratified MOF (sMOF)
particles consisting of multiple concentric DBBs. We discuss and highlight
the negative consequences of linker exchange reactions on the compositional
integrity of DBBs in the UiO-67 sMOFs and propose and demonstrate
mitigation strategies. We also demonstrate that individual strata
can be specifically postsynthetically addressed and manipulated. Finally,
we demonstrate the versatility of these synthetic strategies through
the preparation of sMOF–nanoparticle composite materials.