Assembly of positively charged porphyrins driven by metal ions: A novel polymeric arrangement of cationic metalloporphyrin

Silvano Geremia, Luigi Di Costanzo, Giorgio Nardin, Lucio Randaccio, Roberto Purrello, Domenico Sciotto, Rosaria Lauceri, Fabio Pichierri

Research output: Contribution to journalArticlepeer-review

15 Citations (Scopus)

Abstract

Crystallization and crystal structure analysis of chlorohydrates of either tri- or tetracationic copper porphyrins, namely copper(5,-10,15-tris(N-methyl- pyridinium-4-yl)-20-pyridine-porphyrinato) (1) and copper(5,10,15,20-tetrakis(N- methyl-pyridinium-4-yl)-porphyrinato), respectively, have been performed. Two crystalline forms, 2 and 3, of the latter have been obtained under different preparation conditions. A novel kind of slipped stack chains of these cationic porphyrins has been detected. The pronounced saddle conformation of the porphyrin reveals π-like interactions between the peripheral pyrrole C b-Cb "double bond" and the metal center. DFT calculations on the isolated porphyrins clearly show the HOMO orbitals with the correct topology to yield a bonding interaction among the stacked porphyrin units. To our knowledge, a slipped stack chain of positively charged porphyrins has never been previously reported, if the arrangement of faced units of monocationic metalloporphyrins or phthalocyanins is excluded.

Original languageEnglish
Pages (from-to)7579-7581
Number of pages3
JournalInorganic Chemistry
Volume43
Issue number24
DOIs
Publication statusPublished - 2004 Nov 29

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

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