Directed assembly of transition-metal-coordinated molecular loops and squares from salen-type components. Examples of metalation-controlled structural conversion

Shih Sheng Sun, Charlotte L. Stern, SonBinh T. Nguyen, Joseph T Hupp

Research output: Contribution to journalArticle

214 Citations (Scopus)

Abstract

A series of transition-metal-containing molecular "loops" and "squares" has been prepared via a directed-assembly approach and characterized. The molecular loops were prepared from the reaction of cis-(PEt3)2Pt(OTf)2 with bis(4-pyridyl)-functionalized free-base salen-type ligands. Zn(II)-metalation of the salen-type ligands in the molecular loops converts the loops to molecular squares. Alternatively, the squares can be obtained by the directed assembly of cis-(PEt3)2Pt(OTf)2 and bis(4-pyridyl)-functionalized Zn(II)-salen-type ligands. A concentration-dependent dynamic equilibrium between cyclic species was observed when bis(3-pyridyl)-functionalized free-base salen-type ligand was employed in the reaction. Zn(II) or Cr(III) metalation of the free-base ligand shifted the equilibrium to the single dimeric species. The incorporation of multiple reactive metal sites into a single, cavity-containing supramolecular structure points toward catalytic applications for these new assemblies.

Original languageEnglish
Pages (from-to)6314-6326
Number of pages13
JournalJournal of the American Chemical Society
Volume126
Issue number20
DOIs
Publication statusPublished - May 26 2004

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Transition metals
Metals
Ligands
Catalytic Domain
disalicylaldehyde ethylenediamine

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Directed assembly of transition-metal-coordinated molecular loops and squares from salen-type components. Examples of metalation-controlled structural conversion. / Sun, Shih Sheng; Stern, Charlotte L.; Nguyen, SonBinh T.; Hupp, Joseph T.

In: Journal of the American Chemical Society, Vol. 126, No. 20, 26.05.2004, p. 6314-6326.

Research output: Contribution to journalArticle

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AU - Hupp, Joseph T

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AB - A series of transition-metal-containing molecular "loops" and "squares" has been prepared via a directed-assembly approach and characterized. The molecular loops were prepared from the reaction of cis-(PEt3)2Pt(OTf)2 with bis(4-pyridyl)-functionalized free-base salen-type ligands. Zn(II)-metalation of the salen-type ligands in the molecular loops converts the loops to molecular squares. Alternatively, the squares can be obtained by the directed assembly of cis-(PEt3)2Pt(OTf)2 and bis(4-pyridyl)-functionalized Zn(II)-salen-type ligands. A concentration-dependent dynamic equilibrium between cyclic species was observed when bis(3-pyridyl)-functionalized free-base salen-type ligand was employed in the reaction. Zn(II) or Cr(III) metalation of the free-base ligand shifted the equilibrium to the single dimeric species. The incorporation of multiple reactive metal sites into a single, cavity-containing supramolecular structure points toward catalytic applications for these new assemblies.

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