Outstanding Enhancement in the Axial Coordination Ability of the Highly Rigid Cofacial Cyclic Metalloporphyrin Dimer

09 February 2021, Version 1
This content is a preprint and has not undergone peer review at the time of posting.


Copper- and nickel-porphyrin complexes show extremely weak axial coordination ability without any electron-withdrawing groups. Herein, we report axial ligation on CuII- and NiII-porphyrins in a highly rigid cofacial porphyrin dimer with a bidentate ligand, 1,4-diazabicyclo[2.2.2]octane (DABCO). To the best of our knowledge, this is the first report on the use of CuII- and NiII-porphyrins for coordination-induced guest binding of porphyrin-based host molecules without the help of other metal ions. The high rigidity of the dimer induces guest binding through the cooperative effect of weak axial ligation. The results showed that CuII- and ZnII-complexes bind one DABCO molecule inside their cavities, whereas the NiII-complex binds two additional DABCO molecules outside to form a stable 6-coordinate paramagnetic NiII-complexes.


host-guest complexation
nickel ions
copper ion

Supplementary materials



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