Abstract:
A 3D MnII-porphyrin metal–organic framework
(MOF), [{Mn2(TCPP)·2H2O}·DMF]n (MOF1) (TCPP=5,10,15,20-
tetrakis(4-benzoate)porphyrin), was constructed; it exhibits
an interesting 3D framework structure with two types of 1D
channels of dimensions of 3.94V8.37 a2 and 4.66V4.93 a2
running along the crystallographic a axis. Owing to the presence
of a nonmetallated porphyrin cavity, MOF1 exhibits selective
storage of CO2 with an isosteric heat of adsorption
value of 32.1 kJmol@1, which is further supported by theoretical
calculations with the calculated binding energy (BE) of
29.78 kJmol@1. Interestingly, the nonmetallated nature of the
porphyrin ligand was exploited for implantation of coordinatively
unsaturated FeIII ions to generate a FeIII@MOF1 framework,
which acts as an efficient recyclable catalyst for the oxidation
of styrenes to the corresponding epoxides in the
presence of PhIO as an oxidant at room temperature. Moreover,
the one-pot synthesis of styrene carbonates from styrenes
and CO2 was also achieved using FeIII@MOF1 as a catalyst.
The rational design of a porous MnII-porphyrin MOF for
the selective capture of CO2 and the one-pot synthesis of
styrene carbonates at mild conditions is reported.
