10.1021/jacs.6b05626.s004
Jacob
A. Johnson
Jacob
A.
Johnson
Brenna M. Petersen
Brenna M.
Petersen
Attila Kormos
Attila
Kormos
Elena Echeverría
Elena
Echeverría
Yu-Sheng Chen
Yu-Sheng
Chen
Jian Zhang
Jian
Zhang
A New
Approach to Non-Coordinating Anions: Lewis Acid
Enhancement of Porphyrin Metal Centers in a Zwitterionic Metal–Organic
Framework
American Chemical Society
2016
Porphyrin Metal Centers
cationic metal center
cycloaddition
III
representative electrocyclization reactions
tunable chemical catalysis
zwitterionic MOFs
SBU
Lewis
2016-07-20 00:00:00
Dataset
https://acs.figshare.com/articles/dataset/A_New_Approach_to_Non-Coordinating_Anions_Lewis_Acid_Enhancement_of_Porphyrin_Metal_Centers_in_a_Zwitterionic_Metal_Organic_Framework/3515945
We
describe a new strategy to generate non-coordinating anions
using zwitterionic metal–organic frameworks (MOFs). By assembly
of anionic inorganic secondary building blocks (SBUs) ([In(CO<sub>2</sub>)<sub>4</sub>]<sup>−</sup>) with cationic metalloporphyrin-based
organic linkers, we prepared zwitterionic MOFs in which the complete
internal charge separation effectively prevents the potential binding
of the counteranion to the cationic metal center. We demonstrate the
enhanced Lewis acidity of Mn<sup>III</sup>- and Fe<sup>III</sup>-porphyrins
in the zwitterionic MOFs in three representative electrocyclization
reactions: [2 + 1] cycloisomerization of enynes, [3 + 2] cycloaddition
of aziridines and alkenes, and [4 + 2] hetero-Diels–Alder cycloaddition
of aldehydes with dienes. This work paves a new way to design functional
MOFs for tunable chemical catalysis.