Synthesis, Crystal Structure, and Transistor Performance of Tetracene Derivatives

Abstract

The substitution of chloro or bromo groups in tetracene gives rise to the change of crystal structure, having a substantial effect on carrier transport. Halogenated tetracene derivatives were synthesized and grown into single crystals. Monosubstituted 5-bromo- and 5-chlorotetracenes have the herringbone-type structure, while 5,11-dichlorotetracene has the slipped pi stacking structure. Mobility of 5,11-dichlorotetracene was measured to be as high as 1.6 cm2/V.s in single-crystal transistors. The pi stacking structure, which enhances pi orbital overlap and facilitates carrier transport, may thus be responsible for this high mobility.

Colloquium: Electronic transport in single-crystal organic transistors

“…This testing is essential for supporting the effort on synthesizing more soluble small organic molecules that are attractive for applications, such as soluble derivatives of linear acenes ͑Klare et al, 2003;Moon et al, 2004;Payne et al, 2005͒. Systematic efforts in this direction will require the investigation of a much broader variety of new molecular compounds.…”

Development of Conductive Organic Molecular Assemblies: Organic Metals, Superconductors, and Exotic Functional Materials

“…However, such high mobility might be caused by the presence of oxygen. High FET mobilities have also been reported for naphthacene derivatives, i.e., 1-3 cm 2 V À1 s À1 for single crystals of naphthacene and 5,11-dichloronaphthacene, 42 and thin films of tetrachalcogenonaphthacenes (naphthaceno [5,6- for a rubrene single crystal 44 and that on a flexible poly-(dimethylsiloxane), 45 respectively. An FET fabricated from TMTSF, which has been comprised in many quasi 1D organic superconductors (see 3.3.1), shows a relatively high FET mobility of 0.2 cm 2 V À1 s À1 .…”

Noncovalent Interactions in Organic Electronic Materials

“…For example, 5-chlorotetracene derivatives pack in a herringbone geometry whereas 5,11-dicholorotetracene and 5,6,11,12-tetracholorotetracene both arrange in face-to-face, slip-stacked configurations, with intermolecular distances of 3.48 and 3.56 Å, respectively. 80, 81 Anthony and co-workers synthesized fluorinated 6,13-triisopropylsilylethynyl (TIPS)-pentacene derivatives, where the number of fluorine atoms on the peripheral rings shifts the intermolecular stacking distance; this distance goes from 3.43 Å in the unsubstituted parent molecule to 3.36 Å for the tetrafluoro structure to 3.28 Å for the octafluoro structure. 82 Perfluorination can also take place on the solubilizing alkyl side chains, which not only alters material miscibility but also influences the preferential charge-carrier transport in the molecular semiconductor; for instance, perfluoroalkyl functionalized oligothiophenes are n-type materials, whereas their alkyl cousins are p-type.…”