Dendrimer Disassembly in the Gas Phase: A Cascade Fragmentation Reaction of Frechet Dendrons


Baytekin B., Baytekin H. T. , Hahn U., Reckien W., Kirchner B., Schalley C. A.

CHEMISTRY-A EUROPEAN JOURNAL, vol.15, no.29, pp.7139-7149, 2009 (Journal Indexed in SCI) identifier identifier identifier

  • Publication Type: Article / Review
  • Volume: 15 Issue: 29
  • Publication Date: 2009
  • Doi Number: 10.1002/chem.200900403
  • Title of Journal : CHEMISTRY-A EUROPEAN JOURNAL
  • Page Numbers: pp.7139-7149
  • Keywords: dendrimers, fragmentation mechanisms, gas-phase reactions, mass spectrometry, MASS-SPECTROMETRIC CHARACTERIZATION, POLY(PROPYLENE IMINE) DENDRIMERS, METASTABLE ION CHARACTERISTICS, SUPRAMOLECULAR CHEMISTRY, PHOTOCHEMICAL PROPERTIES, CONVERGENT APPROACH, POLYMERS, EXCHANGE, TOLUENE, DISSOCIATION

Abstract

The mass spectrometric characterization of Frechet-type dendrons is reported. In order to provide the charges necessary for electrospray ionization, dendrons bearing an OH group at the focal point can be deprotonated and observed in the negative ion mode. Alternatively, the corresponding bromides can be converted to quaternary ammonium ions that can easily be detected in the positive mode. If the latter ions are subjected to collision-induced dissociation experiments, a fragmentation cascade begins with the dissociation of the focal amine. The focal benzyl cation quickly decomposes in a fragmentation cascade from the focal point to the periphery until the peripheral benzyl (or naphthylmethyl) cations are formed. Five different mechanisms are discussed in detail, three of which can be excluded based on experimental evidence. The cascade fragmentation is reminiscent of self-immolative dendrimers.