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.