Thiophene-diazine molecular semiconductors

Synthesis, structural, electrochemical, optical, and electronic structural properties; Implementation in organic field-effect transistors

Rocío Ponce Ortiz, Juan Casado, Víctor Hernández, Juan T López Navarrete, Joseph A. Letizia, Mark A Ratner, Antonio Facchetti, Tobin J Marks

Research output: Contribution to journalArticle

65 Citations (Scopus)

Abstract

The synthesis, structural, electrochemical, optical, and electronic structure properties of a new azinethiophene semiconductor family are reported and compared to those of analogous oligothiophenes. The new molecules are: 5,5′-bis(6-(thien-2-yl)pyrimid-4-yl)-2,2′-dithiophene (1), 5,5′-bis(6-(5-hexylthien-2-yl)pyrimid-4-yl)-2,2′-dithiophene (3), and 5,5′-bis(6-(thien-2-yl)pyridazin-3-yl))-2,2′-dithiophene (2). Electrochemical experiments demonstrate that introduction of electron-poor heteroaromatic rings into the oligothiophene core significantly enhances electron affinity. Thin-film transistors were fabricated with these materials and evaluated both in vacuum and in air. We find that although diazine substitution is important in tuning oligothiophene orbital energetics, these oligomers are p-channel semiconductors and the field-effect transistor (FET) charge transport properties are remarkably similar to these of unsubstituted oligothiophenes. The combined computational-experimental analysis of the molecular and thin film properties indicates that these diazine-containing oligothiophenes essentially behave as π-extended bithiophenes. Interestingly, despite strong intermolecular interactions, high solid-state fluorescence efficiencies are observed for these new derivatives. Such emission characteristics suggest that these materials behave as more extended π systems, which should be advantageous in light-emitting transistors.

Original languageEnglish
Pages (from-to)5023-5039
Number of pages17
JournalChemistry - A European Journal
Volume15
Issue number20
DOIs
Publication statusPublished - May 11 2009

Fingerprint

Organic field effect transistors
Thiophenes
Thiophene
Structural properties
Semiconductor materials
Electron affinity
Thin film transistors
Field effect transistors
Oligomers
Transport properties
Electronic structure
Charge transfer
Transistors
Substitution reactions
Tuning
Fluorescence
Vacuum
Derivatives
Thin films
Molecules

Keywords

  • Density functional calculations
  • Electrochemistry
  • P-type mobility
  • Semiconductors transistors

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

Thiophene-diazine molecular semiconductors : Synthesis, structural, electrochemical, optical, and electronic structural properties; Implementation in organic field-effect transistors. / Ortiz, Rocío Ponce; Casado, Juan; Hernández, Víctor; Navarrete, Juan T López; Letizia, Joseph A.; Ratner, Mark A; Facchetti, Antonio; Marks, Tobin J.

In: Chemistry - A European Journal, Vol. 15, No. 20, 11.05.2009, p. 5023-5039.

Research output: Contribution to journalArticle

Ortiz, Rocío Ponce ; Casado, Juan ; Hernández, Víctor ; Navarrete, Juan T López ; Letizia, Joseph A. ; Ratner, Mark A ; Facchetti, Antonio ; Marks, Tobin J. / Thiophene-diazine molecular semiconductors : Synthesis, structural, electrochemical, optical, and electronic structural properties; Implementation in organic field-effect transistors. In: Chemistry - A European Journal. 2009 ; Vol. 15, No. 20. pp. 5023-5039.
@article{e43e092746d94fefb52c536ed3f9b66d,
title = "Thiophene-diazine molecular semiconductors: Synthesis, structural, electrochemical, optical, and electronic structural properties; Implementation in organic field-effect transistors",
abstract = "The synthesis, structural, electrochemical, optical, and electronic structure properties of a new azinethiophene semiconductor family are reported and compared to those of analogous oligothiophenes. The new molecules are: 5,5′-bis(6-(thien-2-yl)pyrimid-4-yl)-2,2′-dithiophene (1), 5,5′-bis(6-(5-hexylthien-2-yl)pyrimid-4-yl)-2,2′-dithiophene (3), and 5,5′-bis(6-(thien-2-yl)pyridazin-3-yl))-2,2′-dithiophene (2). Electrochemical experiments demonstrate that introduction of electron-poor heteroaromatic rings into the oligothiophene core significantly enhances electron affinity. Thin-film transistors were fabricated with these materials and evaluated both in vacuum and in air. We find that although diazine substitution is important in tuning oligothiophene orbital energetics, these oligomers are p-channel semiconductors and the field-effect transistor (FET) charge transport properties are remarkably similar to these of unsubstituted oligothiophenes. The combined computational-experimental analysis of the molecular and thin film properties indicates that these diazine-containing oligothiophenes essentially behave as π-extended bithiophenes. Interestingly, despite strong intermolecular interactions, high solid-state fluorescence efficiencies are observed for these new derivatives. Such emission characteristics suggest that these materials behave as more extended π systems, which should be advantageous in light-emitting transistors.",
keywords = "Density functional calculations, Electrochemistry, P-type mobility, Semiconductors transistors",
author = "Ortiz, {Roc{\'i}o Ponce} and Juan Casado and V{\'i}ctor Hern{\'a}ndez and Navarrete, {Juan T L{\'o}pez} and Letizia, {Joseph A.} and Ratner, {Mark A} and Antonio Facchetti and Marks, {Tobin J}",
year = "2009",
month = "5",
day = "11",
doi = "10.1002/chem.200802424",
language = "English",
volume = "15",
pages = "5023--5039",
journal = "Chemistry - A European Journal",
issn = "0947-6539",
publisher = "Wiley-VCH Verlag",
number = "20",

}

TY - JOUR

T1 - Thiophene-diazine molecular semiconductors

T2 - Synthesis, structural, electrochemical, optical, and electronic structural properties; Implementation in organic field-effect transistors

AU - Ortiz, Rocío Ponce

AU - Casado, Juan

AU - Hernández, Víctor

AU - Navarrete, Juan T López

AU - Letizia, Joseph A.

AU - Ratner, Mark A

AU - Facchetti, Antonio

AU - Marks, Tobin J

PY - 2009/5/11

Y1 - 2009/5/11

N2 - The synthesis, structural, electrochemical, optical, and electronic structure properties of a new azinethiophene semiconductor family are reported and compared to those of analogous oligothiophenes. The new molecules are: 5,5′-bis(6-(thien-2-yl)pyrimid-4-yl)-2,2′-dithiophene (1), 5,5′-bis(6-(5-hexylthien-2-yl)pyrimid-4-yl)-2,2′-dithiophene (3), and 5,5′-bis(6-(thien-2-yl)pyridazin-3-yl))-2,2′-dithiophene (2). Electrochemical experiments demonstrate that introduction of electron-poor heteroaromatic rings into the oligothiophene core significantly enhances electron affinity. Thin-film transistors were fabricated with these materials and evaluated both in vacuum and in air. We find that although diazine substitution is important in tuning oligothiophene orbital energetics, these oligomers are p-channel semiconductors and the field-effect transistor (FET) charge transport properties are remarkably similar to these of unsubstituted oligothiophenes. The combined computational-experimental analysis of the molecular and thin film properties indicates that these diazine-containing oligothiophenes essentially behave as π-extended bithiophenes. Interestingly, despite strong intermolecular interactions, high solid-state fluorescence efficiencies are observed for these new derivatives. Such emission characteristics suggest that these materials behave as more extended π systems, which should be advantageous in light-emitting transistors.

AB - The synthesis, structural, electrochemical, optical, and electronic structure properties of a new azinethiophene semiconductor family are reported and compared to those of analogous oligothiophenes. The new molecules are: 5,5′-bis(6-(thien-2-yl)pyrimid-4-yl)-2,2′-dithiophene (1), 5,5′-bis(6-(5-hexylthien-2-yl)pyrimid-4-yl)-2,2′-dithiophene (3), and 5,5′-bis(6-(thien-2-yl)pyridazin-3-yl))-2,2′-dithiophene (2). Electrochemical experiments demonstrate that introduction of electron-poor heteroaromatic rings into the oligothiophene core significantly enhances electron affinity. Thin-film transistors were fabricated with these materials and evaluated both in vacuum and in air. We find that although diazine substitution is important in tuning oligothiophene orbital energetics, these oligomers are p-channel semiconductors and the field-effect transistor (FET) charge transport properties are remarkably similar to these of unsubstituted oligothiophenes. The combined computational-experimental analysis of the molecular and thin film properties indicates that these diazine-containing oligothiophenes essentially behave as π-extended bithiophenes. Interestingly, despite strong intermolecular interactions, high solid-state fluorescence efficiencies are observed for these new derivatives. Such emission characteristics suggest that these materials behave as more extended π systems, which should be advantageous in light-emitting transistors.

KW - Density functional calculations

KW - Electrochemistry

KW - P-type mobility

KW - Semiconductors transistors

UR - http://www.scopus.com/inward/record.url?scp=66149131417&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=66149131417&partnerID=8YFLogxK

U2 - 10.1002/chem.200802424

DO - 10.1002/chem.200802424

M3 - Article

VL - 15

SP - 5023

EP - 5039

JO - Chemistry - A European Journal

JF - Chemistry - A European Journal

SN - 0947-6539

IS - 20

ER -