A Semiconducting Organic Radical Cationic Host鈥揋uest Complex
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- 作者：Albert C. Fahrenbach ; Srinivasan Sampath ; Dattatray J. Late ; Jonathan C. Barnes ; Samuel L. Kleinman ; Nicholas Valley ; Karel J. Hartlieb ; Zhichang Liu ; Vinayak P. Dravid ; George C. Schatz ; Richard P. Van Duyne ; J. Fraser Stoddart
- 刊名：ACS Nano
- 出版年：2012
- 出版时间：November 27, 2012
- 年：2012
- 卷：6
- 期：11
- 页码：9964-9971
- 全文大小：504K
- 年卷期：v.6,no.11(November 27, 2012)
- ISSN：1936-086X
文摘
The self-assembly and solid-state semiconducting properties of single crystals of a trisradical tricationic complex composed of the diradical dicationic cyclobis(paraquat-p-phenylene) (CBPQT2(鈥?)) ring and methyl viologen radical cation (MV鈥?) are reported. An organic field effect transistor incorporating single crystals of the CBPQT2(鈥?)MV鈥? complex was constructed using lithographic techniques on a silicon substrate and shown to exhibit p-type semiconductivity with a mobility of 0.05 cm2 V鈥? s鈥?. The morphology of the crystals on the silicon substrate was characterized using scanning electron microscopy which revealed that the complexes self-assemble into 鈥渕olecular wires鈥?observable by the naked-eye as millimeter long crystalline needles. The nature of the recognition processes driving this self-assembly, radical鈥搑adical interactions between bipyridinium radical cations (BIPY鈥?), was further investigated by resonance Raman spectroscopy in conjunction with theoretical investigations of the vibrational modes, and was supported by X-ray structural analyses of the complex and its free components in both their radical cationic and dicationic redox states. These spectroscopic investigations demonstrate that the bond order of the BIPY鈥? radical cationic units of host and guest components is not changed upon complexation, an observation which relates to its conductivity in the solid-state. We envision the modularity inherent in this kind of host鈥揼uest complexation could be harnessed to construct a library of custom-made electronic organic materials tailored to fit the specific needs of a given electronic application.