Inter- and intramolecular interactions in some bromo- and tricyanovinyl-substituted thiophenes and ethylenedioxythiophenes

Phuong-truc Thi Pham, Mamoun M. Bader

Research output: Contribution to journalArticle

8 Citations (Scopus)

Abstract

We report herein on the competing inter- and intramolecular interactions in seven structurally related thiophene and ethyelenedioxythiophene (EDOT) molecules, substituted with bromine and/or tricyanovinyl (TCV) groups in various combinations, using single crystal structural analyses. Br·· ·Br Interactions of less than 3.5 Å appear to be dominant in the crystal structures of the dibromo EDOT molecules and yet are almost nonexistent in 5,5″-dibromoterthiophene (shortest Br···Br distances are >4.2 Å), indicating a cooperative role involving the Br and the ethylenedioxy moiety. Short Br···Br distances of 3.5 Å within stacks and between adjacent stacks of molecules in crystalline dibromo EDOT dimer (6) could be utilized for the preparation of highly ordered polymers with the perfectly planar EDOT dimer as repeating unit, similar to the work reported by Wudl.18 On the other hand, new dimeric motifs are formed in Br-EDOT-TCV as strong S···N (3.03 Å) intermolecular interactions in TCV-EDOT are replaced by competing N···Br (2.99 Å) interactions. Short intramolecular N···S distances ranging from 3.2 to 3.3 Å are associated with small dihedral angles between the TCV and thiophene planes ranging from 0.80 to 4.3 deg. A slight enhancement of molecular planarity apparently has a profound impact on the extent of conjugation as evident from the Cî - C bond lengths (1.34-1.40 Å) and C-C (1.37-1.44 Å) within the thiophene rings. These findings suggest that N·· ·S, N···Br, and Br···Br inter- and intramolecular interactions could be utilized as additional crystal engineering tools to promote molecular planarity and arrangement of higher oligomers in the solid state prior to polymerization of thiophene-based molecular materials. On the basis of the current study, these interactions appear to also enhance the stability of the structure and influence intramolecular charge transfer and π-stack formation patterns.

Original languageEnglish (US)
Pages (from-to)916-922
Number of pages7
JournalCrystal Growth and Design
Volume14
Issue number3
DOIs
StatePublished - Mar 5 2014

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Thiophenes
Thiophene
thiophenes
Dimers
Molecules
Crystal engineering
interactions
Bromine
Bond length
Dihedral angle
dimers
Oligomers
Charge transfer
molecules
Polymers
Crystal structure
Polymerization
Single crystals
bromine
Crystalline materials

All Science Journal Classification (ASJC) codes

  • Chemistry(all)
  • Materials Science(all)
  • Condensed Matter Physics

Cite this

@article{36571db1461a4990aba10b0e2085c703,
title = "Inter- and intramolecular interactions in some bromo- and tricyanovinyl-substituted thiophenes and ethylenedioxythiophenes",
abstract = "We report herein on the competing inter- and intramolecular interactions in seven structurally related thiophene and ethyelenedioxythiophene (EDOT) molecules, substituted with bromine and/or tricyanovinyl (TCV) groups in various combinations, using single crystal structural analyses. Br·· ·Br Interactions of less than 3.5 {\AA} appear to be dominant in the crystal structures of the dibromo EDOT molecules and yet are almost nonexistent in 5,5″-dibromoterthiophene (shortest Br···Br distances are >4.2 {\AA}), indicating a cooperative role involving the Br and the ethylenedioxy moiety. Short Br···Br distances of 3.5 {\AA} within stacks and between adjacent stacks of molecules in crystalline dibromo EDOT dimer (6) could be utilized for the preparation of highly ordered polymers with the perfectly planar EDOT dimer as repeating unit, similar to the work reported by Wudl.18 On the other hand, new dimeric motifs are formed in Br-EDOT-TCV as strong S···N (3.03 {\AA}) intermolecular interactions in TCV-EDOT are replaced by competing N···Br (2.99 {\AA}) interactions. Short intramolecular N···S distances ranging from 3.2 to 3.3 {\AA} are associated with small dihedral angles between the TCV and thiophene planes ranging from 0.80 to 4.3 deg. A slight enhancement of molecular planarity apparently has a profound impact on the extent of conjugation as evident from the C{\^i} - C bond lengths (1.34-1.40 {\AA}) and C-C (1.37-1.44 {\AA}) within the thiophene rings. These findings suggest that N·· ·S, N···Br, and Br···Br inter- and intramolecular interactions could be utilized as additional crystal engineering tools to promote molecular planarity and arrangement of higher oligomers in the solid state prior to polymerization of thiophene-based molecular materials. On the basis of the current study, these interactions appear to also enhance the stability of the structure and influence intramolecular charge transfer and π-stack formation patterns.",
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Inter- and intramolecular interactions in some bromo- and tricyanovinyl-substituted thiophenes and ethylenedioxythiophenes. / Pham, Phuong-truc Thi; Bader, Mamoun M.

In: Crystal Growth and Design, Vol. 14, No. 3, 05.03.2014, p. 916-922.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Inter- and intramolecular interactions in some bromo- and tricyanovinyl-substituted thiophenes and ethylenedioxythiophenes

AU - Pham, Phuong-truc Thi

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N2 - We report herein on the competing inter- and intramolecular interactions in seven structurally related thiophene and ethyelenedioxythiophene (EDOT) molecules, substituted with bromine and/or tricyanovinyl (TCV) groups in various combinations, using single crystal structural analyses. Br·· ·Br Interactions of less than 3.5 Å appear to be dominant in the crystal structures of the dibromo EDOT molecules and yet are almost nonexistent in 5,5″-dibromoterthiophene (shortest Br···Br distances are >4.2 Å), indicating a cooperative role involving the Br and the ethylenedioxy moiety. Short Br···Br distances of 3.5 Å within stacks and between adjacent stacks of molecules in crystalline dibromo EDOT dimer (6) could be utilized for the preparation of highly ordered polymers with the perfectly planar EDOT dimer as repeating unit, similar to the work reported by Wudl.18 On the other hand, new dimeric motifs are formed in Br-EDOT-TCV as strong S···N (3.03 Å) intermolecular interactions in TCV-EDOT are replaced by competing N···Br (2.99 Å) interactions. Short intramolecular N···S distances ranging from 3.2 to 3.3 Å are associated with small dihedral angles between the TCV and thiophene planes ranging from 0.80 to 4.3 deg. A slight enhancement of molecular planarity apparently has a profound impact on the extent of conjugation as evident from the Cî - C bond lengths (1.34-1.40 Å) and C-C (1.37-1.44 Å) within the thiophene rings. These findings suggest that N·· ·S, N···Br, and Br···Br inter- and intramolecular interactions could be utilized as additional crystal engineering tools to promote molecular planarity and arrangement of higher oligomers in the solid state prior to polymerization of thiophene-based molecular materials. On the basis of the current study, these interactions appear to also enhance the stability of the structure and influence intramolecular charge transfer and π-stack formation patterns.

AB - We report herein on the competing inter- and intramolecular interactions in seven structurally related thiophene and ethyelenedioxythiophene (EDOT) molecules, substituted with bromine and/or tricyanovinyl (TCV) groups in various combinations, using single crystal structural analyses. Br·· ·Br Interactions of less than 3.5 Å appear to be dominant in the crystal structures of the dibromo EDOT molecules and yet are almost nonexistent in 5,5″-dibromoterthiophene (shortest Br···Br distances are >4.2 Å), indicating a cooperative role involving the Br and the ethylenedioxy moiety. Short Br···Br distances of 3.5 Å within stacks and between adjacent stacks of molecules in crystalline dibromo EDOT dimer (6) could be utilized for the preparation of highly ordered polymers with the perfectly planar EDOT dimer as repeating unit, similar to the work reported by Wudl.18 On the other hand, new dimeric motifs are formed in Br-EDOT-TCV as strong S···N (3.03 Å) intermolecular interactions in TCV-EDOT are replaced by competing N···Br (2.99 Å) interactions. Short intramolecular N···S distances ranging from 3.2 to 3.3 Å are associated with small dihedral angles between the TCV and thiophene planes ranging from 0.80 to 4.3 deg. A slight enhancement of molecular planarity apparently has a profound impact on the extent of conjugation as evident from the Cî - C bond lengths (1.34-1.40 Å) and C-C (1.37-1.44 Å) within the thiophene rings. These findings suggest that N·· ·S, N···Br, and Br···Br inter- and intramolecular interactions could be utilized as additional crystal engineering tools to promote molecular planarity and arrangement of higher oligomers in the solid state prior to polymerization of thiophene-based molecular materials. On the basis of the current study, these interactions appear to also enhance the stability of the structure and influence intramolecular charge transfer and π-stack formation patterns.

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