Utilizing Selective Chlorination to Synthesize New Triangulenium Dyes
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Utilizing Selective Chlorination to Synthesize New Triangulenium Dyes. / Jensen, Jesper Dahl; Bisballe, Niels; Kacenauskaite, Laura; Thomsen, Maria Storm; Chen, Junsheng; Hammerich, Ole; Laursen, Bo W.
In: Journal of Organic Chemistry, Vol. 86, No. 23, 2021, p. 17002–17010.Research output: Contribution to journal › Journal article › Research › peer-review
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TY - JOUR
T1 - Utilizing Selective Chlorination to Synthesize New Triangulenium Dyes
AU - Jensen, Jesper Dahl
AU - Bisballe, Niels
AU - Kacenauskaite, Laura
AU - Thomsen, Maria Storm
AU - Chen, Junsheng
AU - Hammerich, Ole
AU - Laursen, Bo W.
N1 - Publisher Copyright: © 2021 American Chemical Society.
PY - 2021
Y1 - 2021
N2 - Functionalization of new sites on the triangulenium structure has been achieved by early-stage chlorination with N-chlorosuccinimide (NCS), giving rise to two new triangulenium dyes (1 and 3). By introducing the chlorine functionalities in the acridinium precursor, positions complementary to those previously obtained by electrophilic aromatic substitution on the final dyes are accessed. The chlorination is selective, giving only one regioisomer for both mono- and dichlorination products. For the monochlorinated acridinium compound, a highly selective ring-closing reaction was discovered, generating a single regioisomer of the cationic [4]helicene product. Further investigations into the mechanism of the [4]helicene formation lead to the first isolation of the previously proposed intermediate of the two-step SNAr reaction, key to all aza-bridged triangulenium and helicenium systems. Late-stage functionalization of DAOTA+ with NCS gave rise to a different dichlorinated compound (2). The fully ring closed chlorinated triangulenium dyes 1, 2, and 3 show a redshift in absorption and emission, while maintaining relatively high fluorescence quantum yields of 36%, 26%, and 41% and long fluorescence lifetimes of 15, 12.5, and 16 ns, respectively. Cyclic voltammetry shows that chlorination of the triangulenium dyes significantly lowers reduction potentials and thus allows for efficient tuning of redox and photoredox properties.
AB - Functionalization of new sites on the triangulenium structure has been achieved by early-stage chlorination with N-chlorosuccinimide (NCS), giving rise to two new triangulenium dyes (1 and 3). By introducing the chlorine functionalities in the acridinium precursor, positions complementary to those previously obtained by electrophilic aromatic substitution on the final dyes are accessed. The chlorination is selective, giving only one regioisomer for both mono- and dichlorination products. For the monochlorinated acridinium compound, a highly selective ring-closing reaction was discovered, generating a single regioisomer of the cationic [4]helicene product. Further investigations into the mechanism of the [4]helicene formation lead to the first isolation of the previously proposed intermediate of the two-step SNAr reaction, key to all aza-bridged triangulenium and helicenium systems. Late-stage functionalization of DAOTA+ with NCS gave rise to a different dichlorinated compound (2). The fully ring closed chlorinated triangulenium dyes 1, 2, and 3 show a redshift in absorption and emission, while maintaining relatively high fluorescence quantum yields of 36%, 26%, and 41% and long fluorescence lifetimes of 15, 12.5, and 16 ns, respectively. Cyclic voltammetry shows that chlorination of the triangulenium dyes significantly lowers reduction potentials and thus allows for efficient tuning of redox and photoredox properties.
U2 - 10.1021/acs.joc.1c02148
DO - 10.1021/acs.joc.1c02148
M3 - Journal article
C2 - 34791879
AN - SCOPUS:85120086286
VL - 86
SP - 17002
EP - 17010
JO - Journal of Organic Chemistry
JF - Journal of Organic Chemistry
SN - 0022-3263
IS - 23
ER -
ID: 286858203