The impact of vinylene bridges and side chain alkyl groups on the solid state structures of tricyanovinyl-substituted thiophenes

Phuong-truc Thi Pham, Victor G. Young, Mamoun M. Bader

Research output: Contribution to journalArticle

Abstract

The goal of this work is to examine the solid state structures of compounds that have been designed for increased conjugation and solubility, as these factors are important if these compounds are to be used in the solid state. The impact of three commonly employed molecular design strategies on the solid state structures of three thiophene derivatives is reported herein. These strategies include: (i) introduction of a strong electron accepting group (2T-TCV, 1); (ii) increase in conjugation by introducing a vinylene bridge in the presence of a strong electron accepting group (2T-TCV with both a TCV group and a CC bridge, 2); and (iii) enhancing the solubility by introducing n-butyl side chain groups in the presence of both a strong electron accepting group and a CC bridge (2T-TCV containing a strong electron accepting group, a CC bridge and four n-butyl groups, 3). Compounds 1 and 2 crystallize with four molecules in the unit cell while the unit cell of compound 3 contains only two molecules. The torsion between the two thiophene rings increases from 4.39° to 5.50° to 5.75° for 1, 2, and 3, respectively. The short distances between adjacent molecules within the unit cell also increase from 2.84 Å in 2 to 3.47 Å in 3. We also note that while the sulfur atoms assume a syn conformation in both 1 and 2, they favor the anti-conformation in 3. DFT calculations show a small energy difference between the syn and anti-conformation for 1 and 2, i.e. 3.18 kJ mol-1 and 3.19 kJ mol-1, respectively; this energy difference is found to be greater for compound 3 with the anti-conformation being 17.47 kJ mol-1 more stable than the syn conformation.

Original languageEnglish (US)
Pages (from-to)128-132
Number of pages5
JournalCrystEngComm
Volume20
Issue number1
DOIs
StatePublished - Jan 1 2018

Fingerprint

Thiophenes
Thiophene
thiophenes
Conformations
solid state
Electrons
Molecules
Solubility
conjugation
electrons
solubility
cells
Sulfur
Discrete Fourier transforms
Torsional stress
molecules
Derivatives
torsion
Atoms
sulfur

All Science Journal Classification (ASJC) codes

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

Cite this

@article{703ba99ee4ba475799f355a3098b9531,
title = "The impact of vinylene bridges and side chain alkyl groups on the solid state structures of tricyanovinyl-substituted thiophenes",
abstract = "The goal of this work is to examine the solid state structures of compounds that have been designed for increased conjugation and solubility, as these factors are important if these compounds are to be used in the solid state. The impact of three commonly employed molecular design strategies on the solid state structures of three thiophene derivatives is reported herein. These strategies include: (i) introduction of a strong electron accepting group (2T-TCV, 1); (ii) increase in conjugation by introducing a vinylene bridge in the presence of a strong electron accepting group (2T-TCV with both a TCV group and a CC bridge, 2); and (iii) enhancing the solubility by introducing n-butyl side chain groups in the presence of both a strong electron accepting group and a CC bridge (2T-TCV containing a strong electron accepting group, a CC bridge and four n-butyl groups, 3). Compounds 1 and 2 crystallize with four molecules in the unit cell while the unit cell of compound 3 contains only two molecules. The torsion between the two thiophene rings increases from 4.39° to 5.50° to 5.75° for 1, 2, and 3, respectively. The short distances between adjacent molecules within the unit cell also increase from 2.84 {\AA} in 2 to 3.47 {\AA} in 3. We also note that while the sulfur atoms assume a syn conformation in both 1 and 2, they favor the anti-conformation in 3. DFT calculations show a small energy difference between the syn and anti-conformation for 1 and 2, i.e. 3.18 kJ mol-1 and 3.19 kJ mol-1, respectively; this energy difference is found to be greater for compound 3 with the anti-conformation being 17.47 kJ mol-1 more stable than the syn conformation.",
author = "Pham, {Phuong-truc Thi} and Young, {Victor G.} and Bader, {Mamoun M.}",
year = "2018",
month = "1",
day = "1",
doi = "10.1039/c7ce01574g",
language = "English (US)",
volume = "20",
pages = "128--132",
journal = "CrystEngComm",
issn = "1466-8033",
publisher = "Royal Society of Chemistry",
number = "1",

}

The impact of vinylene bridges and side chain alkyl groups on the solid state structures of tricyanovinyl-substituted thiophenes. / Pham, Phuong-truc Thi; Young, Victor G.; Bader, Mamoun M.

In: CrystEngComm, Vol. 20, No. 1, 01.01.2018, p. 128-132.

Research output: Contribution to journalArticle

TY - JOUR

T1 - The impact of vinylene bridges and side chain alkyl groups on the solid state structures of tricyanovinyl-substituted thiophenes

AU - Pham, Phuong-truc Thi

AU - Young, Victor G.

AU - Bader, Mamoun M.

PY - 2018/1/1

Y1 - 2018/1/1

N2 - The goal of this work is to examine the solid state structures of compounds that have been designed for increased conjugation and solubility, as these factors are important if these compounds are to be used in the solid state. The impact of three commonly employed molecular design strategies on the solid state structures of three thiophene derivatives is reported herein. These strategies include: (i) introduction of a strong electron accepting group (2T-TCV, 1); (ii) increase in conjugation by introducing a vinylene bridge in the presence of a strong electron accepting group (2T-TCV with both a TCV group and a CC bridge, 2); and (iii) enhancing the solubility by introducing n-butyl side chain groups in the presence of both a strong electron accepting group and a CC bridge (2T-TCV containing a strong electron accepting group, a CC bridge and four n-butyl groups, 3). Compounds 1 and 2 crystallize with four molecules in the unit cell while the unit cell of compound 3 contains only two molecules. The torsion between the two thiophene rings increases from 4.39° to 5.50° to 5.75° for 1, 2, and 3, respectively. The short distances between adjacent molecules within the unit cell also increase from 2.84 Å in 2 to 3.47 Å in 3. We also note that while the sulfur atoms assume a syn conformation in both 1 and 2, they favor the anti-conformation in 3. DFT calculations show a small energy difference between the syn and anti-conformation for 1 and 2, i.e. 3.18 kJ mol-1 and 3.19 kJ mol-1, respectively; this energy difference is found to be greater for compound 3 with the anti-conformation being 17.47 kJ mol-1 more stable than the syn conformation.

AB - The goal of this work is to examine the solid state structures of compounds that have been designed for increased conjugation and solubility, as these factors are important if these compounds are to be used in the solid state. The impact of three commonly employed molecular design strategies on the solid state structures of three thiophene derivatives is reported herein. These strategies include: (i) introduction of a strong electron accepting group (2T-TCV, 1); (ii) increase in conjugation by introducing a vinylene bridge in the presence of a strong electron accepting group (2T-TCV with both a TCV group and a CC bridge, 2); and (iii) enhancing the solubility by introducing n-butyl side chain groups in the presence of both a strong electron accepting group and a CC bridge (2T-TCV containing a strong electron accepting group, a CC bridge and four n-butyl groups, 3). Compounds 1 and 2 crystallize with four molecules in the unit cell while the unit cell of compound 3 contains only two molecules. The torsion between the two thiophene rings increases from 4.39° to 5.50° to 5.75° for 1, 2, and 3, respectively. The short distances between adjacent molecules within the unit cell also increase from 2.84 Å in 2 to 3.47 Å in 3. We also note that while the sulfur atoms assume a syn conformation in both 1 and 2, they favor the anti-conformation in 3. DFT calculations show a small energy difference between the syn and anti-conformation for 1 and 2, i.e. 3.18 kJ mol-1 and 3.19 kJ mol-1, respectively; this energy difference is found to be greater for compound 3 with the anti-conformation being 17.47 kJ mol-1 more stable than the syn conformation.

UR - http://www.scopus.com/inward/record.url?scp=85038593850&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=85038593850&partnerID=8YFLogxK

U2 - 10.1039/c7ce01574g

DO - 10.1039/c7ce01574g

M3 - Article

VL - 20

SP - 128

EP - 132

JO - CrystEngComm

JF - CrystEngComm

SN - 1466-8033

IS - 1

ER -