title: Facile Conversion of Ni(II) Cyclopropylchlorins into Novel β-Substituted Porphyrins through Acid-Catalyzed Ring-Opening Reaction.
abstract: The conversion of cyclopropylchlorins into porphyrins represents a key step in the synthetic manipulation of macrocycles with tunable physical and chemical properties. Herein, we report a facile method for the synthesis of novel β-substituted porphyrins from cyclopropylchlorins. A series of Ni(II) cyclopropylchlorins was converted into the corresponding Ni(II) and free base porphyrins using TFA and H2SO4under mild reaction conditions in good yields (75-86%). The new chlorins and porphyrins were characterized by various spectroscopic techniques and the single-crystal X-ray diffraction method. The reaction proceeds very fast (<5 min.) with complete conversion of chlorin into porphyrin with distinct color change. Facile conversion, shorter reaction time scale, and good yield (75-86%) without any side products are the significant features of this new protocol. These porphyrinoids exhibited red-shifted electronic spectral features with varying degrees nonplanar conformation, tunable redox properties, and porphyrin core basicity.
authors.affiliation: Department of Chemistry, Indian Institute of Technology Roorkee , Roorkee 247667, India.
authors.forename: Nitika
authors.initials: N
authors.lastname: Grover
authors.affiliation: Department of Chemistry, Indian Institute of Technology Roorkee , Roorkee 247667, India.
authors.forename: Nivedita
authors.initials: N
authors.lastname: Chaudhri
authors.affiliation: Department of Chemistry, Indian Institute of Technology Roorkee , Roorkee 247667, India.
authors.forename: Muniappan
authors.identifier: http://orcid.org/0000-0001-6667-3759
authors.initials: M
authors.lastname: Sankar