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. 2016;7(8):5547-5558.
doi: 10.1039/C6SC00950F. Epub 2016 May 13.

Indacenodibenzothiophenes: synthesis, optoelectronic properties and materials applications of molecules with strong antiaromatic character

Jonathan L Marshall  1 , Kazuyuki Uchida  2 , Conerd K Frederickson  1 , Christian Schütt  3 , Andrew M Zeidell  4 , Katelyn P Goetz  4 , Tristan W Finn  5 , Karol Jarolimek  5 , Lev N Zakharov  6 , Chad Risko  5 , Rainer Herges  3 , Oana D Jurchescu  4 , Michael M Haley  1
Affiliations

Indacenodibenzothiophenes: synthesis, optoelectronic properties and materials applications of molecules with strong antiaromatic character

Jonathan L Marshall et al. Chem Sci. 2016.

Abstract

Indeno[1,2-b]fluorenes (IFs), while containing 4n π-electrons, are best described as two aromatic benzene rings fused to a weakly paratropic s-indacene core. In this study, we find that replacement of the outer benzene rings of an IF with benzothiophenes allows the antiaromaticity of the central s-indacene to strongly reassert itself. Herein we report a combined synthetic, computational, structural, and materials study of anti- and syn-indacenodibenzothiophenes (IDBTs). We have developed an efficient and scalable synthesis for preparation of a series of aryl- and ethynyl-substituted IDBTs. NICS-XY scans and ACID calculations reveal an increasingly antiaromatic core from [1,2-b]IF to anti-IDBT, with syn-IDBT being nearly as antiaromatic as the parent s-indacene. As an initial evaluation, the intermolecular electronic couplings and electronic band structure of a diethynyl anti-IDBT derivative reveal the potential for hole and / or electron transport. OFETs constructed using this molecule show the highest hole mobilities yet achieved for a fully conjugated IF derivative.

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Figures

Fig. 1
Fig. 1. Indeno[1,2-b]fluorene ([1,2-b]IF) 1, indeno[2,1-c]fluorene ([2,1-c IF) 2, anti-indacenodithiophene (anti-IDT) 3a, indacenodiselenophene (IDS) 3b, syn-indacenodithiophene (syn-IDT) 4, diindenothiophene (DI1T) 5a, diindenoselenophene (DIS) 5b, anti-indacenodibenzothiophene (anti-IDBT) 6a, and syn-indacenodibenzothiophene (syn-IDBT) 7a.
Scheme 1
Scheme 1. Preparation of IDBTs 6a–f and 7a–fvia an improved synthesis of diesters 12 and 13.
Fig. 2
Fig. 2. Molecular structures highlighting the para-xylylene motif in [1,2-b]IF 1′ and the s-indacene motif in IDBTs 6′ and 7′.
Fig. 3
Fig. 3. Partial 1H NMR spectra (500 MHz, CD2Cl2, 20 °C) of compounds 1, 6a, and 7a.
Fig. 4
Fig. 4. NICS-XY scans and induced ring currents of s-indacene (black), [1,2-b]IF 1′ (blue), anti-IDBT 6′ (red), syn-IDBT 7′ (green), anti-IDN 8′ (purple) and syn-IDN 9′ (orange).
Fig. 5
Fig. 5. ACID plots of the induced ring currents of (a) s-indacene, (b) indeno[1,2-b]fluorene 1′, (c) anti-IDBT 6′, (d) syn-IDBT 7′, (e) anti-IDN 8′ and (f) syn-IDN 9′. Note that the magnetic field is chosen to be orthogonal to the ring planes and pointing towards the viewer.
Fig. 6
Fig. 6. Electronic absorption spectra of anti-IDBTs 6a–f (left) and syn-IDBTs 7a–f (right) in CH2Cl2.
Fig. 7
Fig. 7. CV data of anti-IDBTs 6b, 6e, and 6f (left) and syn-IDBT 7b, 7e, and 7f (right).
Fig. 8
Fig. 8. Molecular structures of 6f, 6d, 7d, and 7b; hydrogen atoms omitted for clarity. Ellipsoids drawn at 50% probability level.
Fig. 9
Fig. 9. Solid state crystal packing diagrams of (a) anti-IDBT 6d, (b) syn-IDBT 7d, (c) syn-IDBT 7b, and (d) anti-IDBT 6f. Hydrogen atoms omitted for clarity. Ellipsoids drawn at 50% probability level.
Fig. 10
Fig. 10. (Left) Electronic band structure for 6f in the triclinic lattice (TRI1a). The valence band [VB] and conduction band [CB] are labeled for clarity. The origin of the energy axis is set at the top of VB. (Right) Pictorial representations of the 6f dimer HOMO (bottom) and LUMO (top).
Fig. 11
Fig. 11. Transfer (a) and transport (b) characteristics of an OFET using anti-IDBT 6f. This device demonstrated a hole mobility of 0.44 cm2 V–1 s–1, and a threshold voltage of Vth = 1.33 V.
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