Morphology controlled self-assembled nanostructures of sandwich mixed (phthalocyaninato)(porphyrinato) europium triple-deckers. Effect of hydrogen bonding on tuning the intermolecular interaction

Guifen Lu, Yanli Chen, Yuexing Zhang, Meng Bao, Yongzhong Bian, Xiyou Li, Jianzhuang Jiang*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

140 Scopus citations

Abstract

A series of five novel sandwich-type mixed (phthalocyaninato)(porphyrinato) europium triple-decker complexes with different numbers of hydroxyl groups at the meso-substituted phenyl groups of porphyrin ligand 1-5 have been designed, synthesized, and characterized. Their self-assembly properties, in particular the effects of the number and positions of hydroxyl groups on the morphology of self-assembled nanostructures of these triple-decker complexes, have been comparatively and systematically studied. Competition and cooperation between the intermolecular π-π interaction and hydrogen bonding in the direction perpendicular to the π-π interaction direction for different compounds were revealed to result in nanostructures with a different morphology from nanoleafs for 1, nanoribbons for 2, nanosheets for 3, and curved nanosheets for 4 and to spherical shapes for 5. The IR and X-ray diffraction (XRD) results reveal that, in the nanostructures of triple-decker 2 as well as 3-5, a dimeric supramolecular structure was formed through an intermolecular hydrogen bond between two triple-decker molecules, which as the building block self-assembles into the target nanostructures. Electronic absorption spectroscopic results on the self-assembled nanostructures reveal the H-aggregate nature in the nanoleafs and nanoribbons formed from triple-deckers 1 and 2 due to the dominant π-π intermolecular interaction between triple-decker molecules, but the J-aggregate nature in the curved nanosheets and spherical shapes of 4 and 5 depending on the dominant hydrogen bonding interaction in cooperation with π-π interaction among the triple-decker molecules. Electronic absorption and XRD investigation clearly reveal the decrease in the π-π interaction and increase in the hydrogen bonding interaction among triple-decker molecules in the nanostructures along with the increase of hydroxyl number in the order of 1-5. The present result appears to represent the first effort toward realization of controlling and tuning the morphology of self-assembled nanostructures of sandwich tetrapyrrole rare earth complexes through molecular design and synthesis.

Original languageEnglish (US)
Pages (from-to)11623-11630
Number of pages8
JournalJournal of the American Chemical Society
Volume130
Issue number35
DOIs
StatePublished - Sep 3 2008

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

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