Dendrimer disassembly in the gas phase: a cascade fragmentation reaction of Fréchet dendrons.
The mass spectrometric characterization of Fréchet-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.
Baytekin
Bilge
B
Institut für Chemie und Biochemie, Freie Universität, Takustr. 3, 14195 Berlin, Germany.
Baytekin
H Tarik
HT
Hahn
Uwe
U
Reckien
Werner
W
Kirchner
Barbara
B
Schalley
Christoph A
CA
D050091:Dendrimers / Q000737:chemistry*; D005740:Gases; D007477:Ions; D015394:Molecular Structure; D021241:Spectrometry, Mass, Electrospray Ionization; D053719:Tandem Mass Spectrometry
D050091:Dendrimers; D005740:Gases; D007477:Ions