From trigonal bipyramidal to platonic solids: self-assembly and self-sorting study of terpyridine-based 3D architectures

J Am Chem Soc. 2014 Jul 23;136(29):10499-507. doi: 10.1021/ja505414x. Epub 2014 Jul 9.

Abstract

Using a series of tritopic 2,2':6',2″-terpyridine (tpy) ligands constructed on adamantane, three discrete 3D metallo-supramolecular architectures were assembled, i.e., trigonal bipyramidal, tetrahedron, and cube. The self-assembly used tritopic ligands as corner directing units and metal ions as glue units at the edge. The angles of the linkers between adamantane and tpy head play a critical role in guiding the assembled structures, which have the general formula of M3nL2n, where M denotes metal ion and L denotes ligand. All complexes were fully characterized by (1)H, (13)C NMR, diffusion-ordered NMR spectroscopy, ESI-MS, and traveling-wave ion mobility-mass spectrometry. The binary mixtures of LA and LC or LB and LC underwent a self-sorting process that led to the self-assembly of discrete 3D structures. The self-sorting behavior is solely based on the angles precoded within the arm of tritopic ligands. Moreover, kinetic study of preassembled cube and tetrahedron demonstrated a slow ligand exchange process toward a statistical mixture of hetero tetrahedrons with LA and LB.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Adamantane / chemistry*
  • Ligands
  • Magnetic Resonance Spectroscopy
  • Models, Molecular
  • Molecular Conformation
  • Organometallic Compounds / chemical synthesis*
  • Organometallic Compounds / chemistry*
  • Photochemical Processes
  • Pyridines / chemical synthesis*
  • Pyridines / chemistry*
  • Spectrometry, Mass, Electrospray Ionization
  • Surface Properties

Substances

  • Ligands
  • Organometallic Compounds
  • Pyridines
  • Adamantane