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Title: A Naphtho-p-quinodimethane Exhibiting Baird’s (Anti)Aromaticity, Broken Symmetry, and Attractive Photoluminescence

Journal Article · · Journal of Organic Chemistry
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  1. Illinois Inst. of Technology, Chicago, IL (United States). Department of Chemistry
  2. Argonne National Lab. (ANL), Argonne, IL (United States). Center for Nanoscale Materials
  3. North Dakota State Univ., Fargo, ND (United States). Department of Chemistry and Biochemistry
  4. Columbia Univ., New York, NY (United States). Department of Chemistry
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In this paper, we report a novel reductive desulfurization reaction involving π-acidic naphthalene diimides 1 (NDI) using thionating agents such as Lawesson’s reagent. Along with the expected thionated NDI derivatives 2-6, new heterocyclic naphtho-p-quinodimethane compounds 7 depicting broken/reduced symmetry were successfully isolated and fully characterized. Empirical studies and theoretical modeling suggest that was formed via a six-membered ring oxathiaphosphenine intermediate rather than the usual four-membered ring oxathiaphosphetane of 2-6. Aside from the reduced symmetry in 7 as confirmed by single-crystal XRD analysis, we established that the ground state UV-vis absorption of 7 is red-shifted in comparison to the parent NDI 1. This result was expected in the case of thionated polycyclic diimides. However, unusual low energy transitions originate from Baird 4nπ aromaticity of compounds 7 in lieu of the intrinsic Huckel (4n + 2)π aromaticity as encountered in NDI 1. Moreover, complementary theoretical modeling results also corroborate this change in aromaticity of 7. Consequently, photophysical investigations show that, compared to parent NDI 1, 7 can easily access and emit from its T1 state with a phosphorescence 3(7a)* lifetime of τP = 395 μs at 77 K indicative of the formation of the corresponding “aromatic triplet” species according to the Baird’s rule of aromaticity.

Research Organization:
Argonne National Laboratory (ANL), Argonne, IL (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities Division; Illinois Institute of Technology, Chicago, IL (United States)
Grant/Contract Number:
AC02-06CH11357
OSTI ID:
1427718
Journal Information:
Journal of Organic Chemistry, Vol. 82, Issue 19; ISSN 0022-3263
Publisher:
American Chemical SocietyCopyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 21 works
Citation information provided by
Web of Science

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Cited By (2)

Quinoidization of π-Expanded Aromatic Diimides: Photophysics, Aromaticity, and Stability of the Novel Quinoidal Acenes: Quinoidization of π-Expanded Aromatic Diimides: Photophysics, Aromaticity, and Stability of the Novel Quinoidal Acenes journal January 2020
New perspectives for triplet–triplet annihilation based photon upconversion using all-organic energy donor & acceptor chromophores journal January 2018

Linked Research (2)

Figures / Tables (7)

Scheme 1(p. 1)figure Scheme 1
Figure 1(p. 2)figure Figure 1
Scheme 3(p. 3)figure Scheme 3
Table 1(p. 3)table Table 1
Figure 2(p. 4)figure Figure 2
Figure 3(p. 4)figure Figure 3
Figure 4(p. 5)figure Figure 4

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