Self-assembly of 1D metalloporphyrin array within pseudo-hexagonal channels of polyoxometalates

Amanda M. Smelser, Yan Fen Li, Christopher N. Carmichael, Hou Yin Zhao, Wei Ping Pan, Sean Parkin, Bangbo Yan

Research output: Contribution to journalArticlepeer-review

12 Scopus citations


Self-assembly of the robust Keggin cluster [SiW12O 40]4- and metalloporphyrin building blocks [M(TpyPH n)]n+ under hydrothermal conditions gives two new organic-inorganic hybrid solid compounds. The hydrothermal reactions of H4SiO4·12WO3·xH2O, Cu(NO3)2·2.5H2O, meso-tetra(4-pyridyl) porphine (H2TpyP) and H2O at 200 °C for 72 h yield a solid compound [Cu(TpyPH3)]2[Cu(TpyPH2)] [SiW12O40]2·8H2O (1). Using ZnCl2 instead of Cu(NO3)2·2.5H 2O in the syntheses leads to the crystallization of a compound [Zn(TpyPH4)(H2O)][SiW12O40] ·3H2O (2). Both compounds consist of discrete anionic α-[SiW12O40]4- clusters, cationic metalloporphyrins and crystalline water molecules. Hydrogen bonds, π-π aromatic interactions and CH···π interactions in these two new hybrid solids lead to the formation of 3D framework structures. Pseudo-hexagonal channels are formed by polyoxometalates and are occupied by one-dimensional metalloporphyrin arrays. Both compounds were characterized by single crystal X-ray, UV-Vis, IR spectroscopy and thermogravimetric analysis.

Original languageEnglish
Pages (from-to)122-127
Number of pages6
JournalInorganica Chimica Acta
Issue number1
StatePublished - Sep 1 2011

Bibliographical note

Funding Information:
We are grateful for financial support from internal grant of WKU, NSF EPSCoR ( 4800001974 ), and KY EPSCoR ( RSF-030-06 ).


  • Copper complexes
  • H-aggregation
  • Keggin cluster
  • Metalloporphyrin
  • X-ray crystal structure
  • Zinc complexes

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry
  • Materials Chemistry


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