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

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 (MS²) coupled with traveling wave ion mobility mass spectrometry (TWIM MS).