Self-assembly of triangular metallomacrocycles using unsymmetrical bisterpyridine ligands: isomer differentiation via TWIM mass spectrometry

Dalton Trans. 2015 Mar 21;44(11):5139-45. doi: 10.1039/c4dt03055a.

Abstract

Three unsymmetrical, 60°-bended bisterpyridine ligands with varying phenylene spacer lengths have been synthesized via the Suzuki-Miyaura coupling reactions. Their self-assembly processes were found to be strongly dependent on the ligand geometry. Upon complexation with Zn(II) ions, only 2,4''-di(4'-terpyridinyl)-1,1':4',1''-terphenyl underwent self-selection to give a trinuclear metallomacrocycle with perfect heteroleptic connectivity and the other two afforded a mixture of constitutional isomers. The metallosupramolecular assemblies were characterized by NMR spectroscopy, electrospray mass spectrometry (ESI MS), and single-crystal X-ray diffraction. In particular, the identification of isomeric architecture was accomplished using tandem mass spectrometry (MS(2)) coupled with traveling wave ion mobility mass spectrometry (TWIM MS).

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Isomerism
  • Ligands
  • Macrocyclic Compounds / chemistry*
  • Macrocyclic Compounds / isolation & purification
  • Models, Molecular
  • Molecular Conformation
  • Pyridines / chemistry*
  • Spectrometry, Mass, Electrospray Ionization*

Substances

  • Ligands
  • Macrocyclic Compounds
  • Pyridines
  • pyridine