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. 2023 May 15:19:674-686.
doi: 10.3762/bjoc.19.49. eCollection 2023.

Synthesis, structure, and properties of switchable cross-conjugated 1,4-diaryl-1,3-butadiynes based on 1,8-bis(dimethylamino)naphthalene

Semyon V Tsybulin  1 , Ekaterina A Filatova  1 , Alexander F Pozharskii  1 , Valery A Ozeryanskii  1 , Anna V Gulevskaya  1
Affiliations

Synthesis, structure, and properties of switchable cross-conjugated 1,4-diaryl-1,3-butadiynes based on 1,8-bis(dimethylamino)naphthalene

Semyon V Tsybulin et al. Beilstein J Org Chem. .

Abstract

A set of novel 1,4-diaryl-1,3-butadiynes terminated by two 7-(arylethynyl)-1,8-bis(dimethylamino)naphthalene fragments was prepared via the Glaser-Hay oxidative dimerization of 2-ethynyl-7-(arylethynyl)-1,8-bis(dimethylamino)naphthalenes. The oligomers synthesized in this way are cross-conjugated systems, in which two conjugation pathways are possible: π-conjugation of 1,8-bis(dimethylamino)naphthalene (DMAN) fragments through a butadiyne linker and a donor-acceptor aryl-C≡C-DMAN conjugation path. The conjugation path can be "switched" simply by protonation of DMAN fragments. X-ray diffraction, UV-vis spectroscopy and cyclic voltammetry are applied to analyze the extent of π-conjugation and the efficiency of particular donor-acceptor conjugation path in these new compounds. X-ray structures and absorption spectra of doubly protonated tetrafluoroborate salts of the oligomers are also discussed.

Keywords: 1,4-diaryl-1,3-butadiynes; 1,8-bis(dimethylamino)naphthalene; Glaser–Hay reaction; cross-conjugated systems; donor–acceptor systems.

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Figures

Figure 1
Figure 1
Proton sponge-based 1,4-diaryl-1,3-butadiynes synthesized previously and in this study.
Figure 2
Figure 2
Target oligomers as push–pull and cross-conjugated π-systems.
Scheme 1
Scheme 1
Synthetic strategy for target oligomers 5.
Scheme 2
Scheme 2
Synthesis of 7-(arylethynyl)-2-ethynyl-DMAN 6.
Scheme 3
Scheme 3
Synthesis of 1,4-diaryl-1,3-butadiynes 5 and their salts 11.
Figure 3
Figure 3
Molecular structures of compounds 5b (top), 5d (middle), and 5e (bottom).
Figure 4
Figure 4
Views on the molecular backbone of compounds 5b (top), 5d (middle), and 5e (bottom) along the naphthalene rings plane (hydrogen atoms omitted).
Scheme 4
Scheme 4
Transformation of butadiyne 5c into benzo[g]indole 12.
Figure 5
Figure 5
Molecular structure of compound 11c: frontal (top; BF4− omitted) and side views (bottom; hydrogen atoms omitted).
Figure 6
Figure 6
Calculation of the qr parameter.
Figure 7
Figure 7
Two π-conjugation ways in oligomers 5.
Figure 8
Figure 8
UV–vis spectra of oligomers 5 (blue line), monomers 6 (red line), and butadiyne 1 (green line).
Figure 9
Figure 9
UV–vis spectra of salts 11 (left), 1·2HBF4 and 6b·HBF4 (right) in acetonitrile.
Figure 10
Figure 10
π-Conjugation pathway in salts 11b and 6b·HBF4.
Figure 11
Figure 11
Cyclic voltammograms of oligomers 5.
Scheme 5
Scheme 5
Possible ways of one- and two-electron oxidation of oligomers 5.
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