ja9b12408_si_001.pdf (3.59 MB)
Download fileModular Total Synthesis in Reticular Chemistry
journal contribution
posted on 28.01.2020, 15:35 authored by Liang Feng, Kun-Yu Wang, Xiu-Liang Lv, Tian-Hao Yan, Jian-Rong Li, Hong-Cai ZhouThe
idea of modularity in organic total synthesis has promoted
the construction of diverse targeted natural products by varying the
building blocks and assembly sequences. Yet its utilization has been
mainly limited to the synthesis of molecular compounds based on covalent
bonds. In this work, we expand the conceptual scope of modular synthesis
into framework materials, which bridges metal- and covalent organic
frameworks (MOFs and COFs) hierarchically in reticular chemistry.
While the assembly sequences are determined by the coordination or
the covalent bond strengths, a modular synthesis strategy which progressively
links simple building blocks into increasingly sophisticated superstructures
was reported. As a result, a series of hierarchical COF-on-MOF structures
with architectural intricacy were obtained through sequence-defined
reactions of diverse building blocks. The tunability of spatial apportionment,
compositions, and functionality was successfully managed in these
framework materials. To the best of our knowledge, this is the first
report on the synthesis of COF@MOF composites and also the first discovery
of controlled COF alignment. This generalizable modularity strategy
will not only accelerate the discovery of multicomponent framework
materials by the hierarchical assembly of MOFs and COFs but also offer
a predictable retrosynthetic route to smart materials with unusual
tunability owing to the diverse inorganic or organic building units.