Chiral tetrathienylene: Synthesis and X-ray structure

Shuzhang Xiao, Maren Pink, Hua Wang, Suchada Rajca, Andrzej Rajca

Research output: Contribution to journalArticle

4 Citations (Scopus)

Abstract

Tetrakis(4-bromo-5-trimethylsilyl-2,3-thienylene) 1 with highly functionalized tetrathienylene ring may provide a building block for double helical oligothiophenes. Also, the tetrakis(2,3-thienylene) ring with relatively well-defined conformation provides an interesting probe for cross-conjugation and conjugation between thiophenes. Synthesis and X-ray structure of chiral tetrathienylene, tetrakis(4-bromo-5-trimethylsilyl-2,3-thienylene) 1, are reported. Treatment of 5,5′-bis(trimethylsilyl)-4,4′-dibromo-3, 3′-bithienyl with LDA, followed by oxidative coupling provided 1. The compound crystallizes with one chloroform molecule per formula unit in the chiral space group P21212 and is merohedrally twinned. The presence of four bromine atoms in the two bay areas of 1 leads to increased out-of-plane twisting (∼ 60°) of the chiral π-system along the β, β-linkages (CC bonds between the β-positions of thiophenes) within 3,3′- bithienylene units, compared to out-of-plane twisting (∼46°) in the parent tetrakis(2,3-thienylene). UV-vis spectra reveal a hypsochromic shift of about 50 nm for the onset of electronic absorption in 1, compared to tetrakis(5-trimethylsilyl-2,3-thienylene). This hypsochromic shift is assigned to the decreased cross-conjugation in 1 due to the increased out-of-plane twisting along the β, β-linkages. A large bathochromic shift of about 100 nm for the onset of electronic absorption in 1, compared to the corresponding acyclic 3,3′-bithienyl, i.e., 5,5′- bis(trimethylsilane)-4,4′-dibromo-3,3′-bithienyl, is assigned to the increased conjugation due to the presence of the α, α-linkages (CC bonds between α-positions of thiophenes) in 1.

Original languageEnglish (US)
Pages (from-to)425-432
Number of pages8
JournalJournal of Sulfur Chemistry
Volume29
Issue number3-4
DOIs
StatePublished - Jun 1 2008

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Thiophenes
X rays
Bromine
Chloroform
Conformations
Atoms
Molecules

Keywords

  • Chirality
  • Cross-conjugation
  • Oligothiophene
  • Thiophene
  • UV-vis spectra

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

Chiral tetrathienylene : Synthesis and X-ray structure. / Xiao, Shuzhang; Pink, Maren; Wang, Hua; Rajca, Suchada; Rajca, Andrzej.

In: Journal of Sulfur Chemistry, Vol. 29, No. 3-4, 01.06.2008, p. 425-432.

Research output: Contribution to journalArticle

Xiao, Shuzhang ; Pink, Maren ; Wang, Hua ; Rajca, Suchada ; Rajca, Andrzej. / Chiral tetrathienylene : Synthesis and X-ray structure. In: Journal of Sulfur Chemistry. 2008 ; Vol. 29, No. 3-4. pp. 425-432.
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abstract = "Tetrakis(4-bromo-5-trimethylsilyl-2,3-thienylene) 1 with highly functionalized tetrathienylene ring may provide a building block for double helical oligothiophenes. Also, the tetrakis(2,3-thienylene) ring with relatively well-defined conformation provides an interesting probe for cross-conjugation and conjugation between thiophenes. Synthesis and X-ray structure of chiral tetrathienylene, tetrakis(4-bromo-5-trimethylsilyl-2,3-thienylene) 1, are reported. Treatment of 5,5′-bis(trimethylsilyl)-4,4′-dibromo-3, 3′-bithienyl with LDA, followed by oxidative coupling provided 1. The compound crystallizes with one chloroform molecule per formula unit in the chiral space group P21212 and is merohedrally twinned. The presence of four bromine atoms in the two bay areas of 1 leads to increased out-of-plane twisting (∼ 60°) of the chiral π-system along the β, β-linkages (CC bonds between the β-positions of thiophenes) within 3,3′- bithienylene units, compared to out-of-plane twisting (∼46°) in the parent tetrakis(2,3-thienylene). UV-vis spectra reveal a hypsochromic shift of about 50 nm for the onset of electronic absorption in 1, compared to tetrakis(5-trimethylsilyl-2,3-thienylene). This hypsochromic shift is assigned to the decreased cross-conjugation in 1 due to the increased out-of-plane twisting along the β, β-linkages. A large bathochromic shift of about 100 nm for the onset of electronic absorption in 1, compared to the corresponding acyclic 3,3′-bithienyl, i.e., 5,5′- bis(trimethylsilane)-4,4′-dibromo-3,3′-bithienyl, is assigned to the increased conjugation due to the presence of the α, α-linkages (CC bonds between α-positions of thiophenes) in 1.",
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AU - Rajca, Suchada

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PY - 2008/6/1

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N2 - Tetrakis(4-bromo-5-trimethylsilyl-2,3-thienylene) 1 with highly functionalized tetrathienylene ring may provide a building block for double helical oligothiophenes. Also, the tetrakis(2,3-thienylene) ring with relatively well-defined conformation provides an interesting probe for cross-conjugation and conjugation between thiophenes. Synthesis and X-ray structure of chiral tetrathienylene, tetrakis(4-bromo-5-trimethylsilyl-2,3-thienylene) 1, are reported. Treatment of 5,5′-bis(trimethylsilyl)-4,4′-dibromo-3, 3′-bithienyl with LDA, followed by oxidative coupling provided 1. The compound crystallizes with one chloroform molecule per formula unit in the chiral space group P21212 and is merohedrally twinned. The presence of four bromine atoms in the two bay areas of 1 leads to increased out-of-plane twisting (∼ 60°) of the chiral π-system along the β, β-linkages (CC bonds between the β-positions of thiophenes) within 3,3′- bithienylene units, compared to out-of-plane twisting (∼46°) in the parent tetrakis(2,3-thienylene). UV-vis spectra reveal a hypsochromic shift of about 50 nm for the onset of electronic absorption in 1, compared to tetrakis(5-trimethylsilyl-2,3-thienylene). This hypsochromic shift is assigned to the decreased cross-conjugation in 1 due to the increased out-of-plane twisting along the β, β-linkages. A large bathochromic shift of about 100 nm for the onset of electronic absorption in 1, compared to the corresponding acyclic 3,3′-bithienyl, i.e., 5,5′- bis(trimethylsilane)-4,4′-dibromo-3,3′-bithienyl, is assigned to the increased conjugation due to the presence of the α, α-linkages (CC bonds between α-positions of thiophenes) in 1.

AB - Tetrakis(4-bromo-5-trimethylsilyl-2,3-thienylene) 1 with highly functionalized tetrathienylene ring may provide a building block for double helical oligothiophenes. Also, the tetrakis(2,3-thienylene) ring with relatively well-defined conformation provides an interesting probe for cross-conjugation and conjugation between thiophenes. Synthesis and X-ray structure of chiral tetrathienylene, tetrakis(4-bromo-5-trimethylsilyl-2,3-thienylene) 1, are reported. Treatment of 5,5′-bis(trimethylsilyl)-4,4′-dibromo-3, 3′-bithienyl with LDA, followed by oxidative coupling provided 1. The compound crystallizes with one chloroform molecule per formula unit in the chiral space group P21212 and is merohedrally twinned. The presence of four bromine atoms in the two bay areas of 1 leads to increased out-of-plane twisting (∼ 60°) of the chiral π-system along the β, β-linkages (CC bonds between the β-positions of thiophenes) within 3,3′- bithienylene units, compared to out-of-plane twisting (∼46°) in the parent tetrakis(2,3-thienylene). UV-vis spectra reveal a hypsochromic shift of about 50 nm for the onset of electronic absorption in 1, compared to tetrakis(5-trimethylsilyl-2,3-thienylene). This hypsochromic shift is assigned to the decreased cross-conjugation in 1 due to the increased out-of-plane twisting along the β, β-linkages. A large bathochromic shift of about 100 nm for the onset of electronic absorption in 1, compared to the corresponding acyclic 3,3′-bithienyl, i.e., 5,5′- bis(trimethylsilane)-4,4′-dibromo-3,3′-bithienyl, is assigned to the increased conjugation due to the presence of the α, α-linkages (CC bonds between α-positions of thiophenes) in 1.

KW - Chirality

KW - Cross-conjugation

KW - Oligothiophene

KW - Thiophene

KW - UV-vis spectra

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