In terms of recently documented references,
the introduction of
VO units into porous MOF/COF frameworks can greatly improve
their original performance and expand their application prospects
due to a change in their electronegativity. In this work, by a cation-exchange
strategy, a consummate combination of separate 4f [Tm2(CO2)8] SBUs and 3d [VIVO(H2O)2] units generated the functionalized porous metal–organic
framework {(Me2NH2)2[VO(H2O)][Tm2(BDCP)2]·3DMF·3H2O}
n
(NUC-11), in which [Tm2(CO2)8] SBUs constitute the fundamental
3D host framework of {[Tm2](BDCP)2}
n
along with [VIVO(H2O)2] units being further docked on the inner wall of channels
by covalent bonds. Significantly, NUC-11 represents the
first example of VO modified porous MOFs, in which uncoordinated
carboxylic groups (−CO2H) further grasp the functional
[VIVO(H2O)2] units on the initial
basic skeleton along with the formation of covalent bonds as fixed
ropes. Furthermore, activated samples of NUC-11 displayed
a good catalytic performance for the chemical synthesis of carbonates
from related epoxides and CO2 with high conversion rate.
Moreover, by employing NUC-11 as a catalyst, a simulator
of mustard gas, 2-chloroethyl ethyl sulfide, could be quickly and
efficiently oxidized into low-toxicity products of oxidized sulfoxide
(CEESO). Thus, this study offers a brand new view for the design and
synthesis of functional-units-modified porous MOFs, which could be
potentially applied as an excellent candidate in the growing field
of efficient catalysis.