2,2':3',2''-Terthiophene-based all-thiophene dendrons and dendrimers: synthesis, structural characterization, and properties.
The synthesis of generational dendritic oligothiophenes (DOTs) has been successfully achieved by a divergent/convergent approach that involves halogenation, boronation, and palladium-catalyzed Suzuki coupling reactions. The key point in the presented synthetic approach is the use of trimethylsilyl (TMS) protecting groups, which allow for the core-lithiation and subsequent boronation of the dendrons and for the peripheral ipso-substitution with iodine monochloride or N-bromosuccimide. In addition, the TMS protecting groups can be completely removed by using tetrabutylammonium fluoride, thus yielding only-thiophene-based dendrons and dendrimers. Due to their highly branched structure, all these synthesized DOTs are soluble in organic solvents. Chemical structures were confirmed by NMR spectroscopic, mass spectrometric, and elemental analysis. Concentration-dependent (1)H NMR spectroscopic investigations revealed that the higher generation compounds tend to aggregate in solution. Such an aggregation behavior was further confirmed by measuring with MALDI-TOF MS. Both MALDI-TOF MS and gel-permeation chromatography (GPC) analyses confirmed the monodispersity of the DOTs. Furthermore, GPC results revealed that these DOT molecules adopt a condensed globular molecular shape. Their optical and electronic properties were also investigated. The results indicated that these DOTs comprise various conjugated α-oligothiophenes with different chain lengths, which results in the higher generation compounds showing broad and featureless UV/Vis absorption spectra and ill-defined redox waves.
Institute of Organic Chemistry II and Advanced Materials, Ulm University, Germany. cqma2011@sinano.ac.cn
Chang-Qi
CQ
Ma
Elena
E
Mena-Osteritz
Markus
M
Wunderlin
Gisela
G
Schulz
Peter
P
Bäuerle