A semiconducting organic radical cationic host-guest complex

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

Research output: Contribution to journalArticle

29 Citations (Scopus)

Abstract

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(•+)) ring and methyl viologen radical cation (MV•+) are reported. An organic field effect transistor incorporating single crystals of the CBPQT 2(•+)⊂MV•+ 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-1 s -1. The morphology of the crystals on the silicon substrate was characterized using scanning electron microscopy which revealed that the complexes self-assemble into "molecular wires" observable by the naked-eye as millimeter long crystalline needles. The nature of the recognition processes driving this self-assembly, radical-radical interactions between bipyridinium radical cations (BIPY•+), 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•+ 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-guest 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.

Original languageEnglish
Pages (from-to)9964-9971
Number of pages8
JournalACS Nano
Volume6
Issue number11
DOIs
Publication statusPublished - Nov 27 2012

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Paraquat
Silicon
Complexation
Self assembly
Cations
Positive ions
Single crystals
Organic field effect transistors
Substrates
Needles
Raman spectroscopy
Wire
Crystalline materials
X rays
Crystals
Scanning electron microscopy
self assembly
solid state
cations
modularity

Keywords

  • electrochemistry
  • molecular electronics
  • organic field effect transistors
  • quantum mechanics
  • Raman spectroscopy

ASJC Scopus subject areas

  • Engineering(all)
  • Materials Science(all)
  • Physics and Astronomy(all)

Cite this

Fahrenbach, A. C., Sampath, S., Late, D. J., Barnes, J. C., Kleinman, S. L., Valley, N., ... Stoddart, J. F. (2012). A semiconducting organic radical cationic host-guest complex. ACS Nano, 6(11), 9964-9971. https://doi.org/10.1021/nn303553z

A semiconducting organic radical cationic host-guest complex. / Fahrenbach, Albert C.; Sampath, Srinivasan; Late, Dattatray J.; Barnes, Jonathan C.; Kleinman, Samuel L.; Valley, Nicholas; Hartlieb, Karel J.; Liu, Zhichang; Dravid, Vinayak P.; Schatz, George C; Van Duyne, Richard P.; Stoddart, J. Fraser.

In: ACS Nano, Vol. 6, No. 11, 27.11.2012, p. 9964-9971.

Research output: Contribution to journalArticle

Fahrenbach, AC, Sampath, S, Late, DJ, Barnes, JC, Kleinman, SL, Valley, N, Hartlieb, KJ, Liu, Z, Dravid, VP, Schatz, GC, Van Duyne, RP & Stoddart, JF 2012, 'A semiconducting organic radical cationic host-guest complex', ACS Nano, vol. 6, no. 11, pp. 9964-9971. https://doi.org/10.1021/nn303553z
Fahrenbach AC, Sampath S, Late DJ, Barnes JC, Kleinman SL, Valley N et al. A semiconducting organic radical cationic host-guest complex. ACS Nano. 2012 Nov 27;6(11):9964-9971. https://doi.org/10.1021/nn303553z
Fahrenbach, Albert C. ; Sampath, Srinivasan ; Late, Dattatray J. ; Barnes, Jonathan C. ; Kleinman, Samuel L. ; Valley, Nicholas ; Hartlieb, Karel J. ; Liu, Zhichang ; Dravid, Vinayak P. ; Schatz, George C ; Van Duyne, Richard P. ; Stoddart, J. Fraser. / A semiconducting organic radical cationic host-guest complex. In: ACS Nano. 2012 ; Vol. 6, No. 11. pp. 9964-9971.
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AU - Valley, Nicholas

AU - Hartlieb, Karel J.

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