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

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.

SUBMITTER: Marshall JL

PROVIDER: S-EPMC5207214 | biostudies-literature | 2016

REPOSITORIES: biostudies-literature

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

Marshall Jonathan L JL Uchida Kazuyuki K Frederickson Conerd K CK Schütt Christian C Zeidell Andrew M AM Goetz Katelyn P KP Finn Tristan W TW Jarolimek Karol K Zakharov Lev N LN Risko Chad C Herges Rainer R Jurchescu Oana D OD Haley Michael M MM

Chemical science 20160513 8

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 ...[more]

PMID: 28066536

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Project description:In this study, we investigate a set of organic diradical structures in which two oxo-verdazyl radicals are selected as radical spin centers that are connected (coupled) via six coupler molecules (CM), resulting in various magnetic (ferromagnetic (FM) or antiferromagnetic (AFM)) characteristics, as reflected by their exchange coupling constants (J). We have designed 12 diradicals with 6-antiaromatic couplers coupled with bis-oxo-verdazyl diradicals with meta-meta (m-m) and para-meta (p-m) positional connectivities. The nature of the magnetic coupling (ferromagnetic, nonmagnetic, or antiferromagnetic) and the magnitude of the exchange constant J depend on the type of coupler, the connecting point between each radical center and CM, the degree of aromaticity of the coupler, and the length of the through-bond distance between radical centers. The computed magnetic exchange coupling constants J for these diradicals at the B3LYP/6-311++G(d,p) and MN12SX/6-311++G(d,p) levels of theory are large for many of these structures, indicating strong ferromagnetic coupling (with positive J values). In some cases, magnetic couplings are observed with J > 1000 cm-1 (B3LYP/6-311++G(d,p)) and strong antiferromagnetic coupling (with negative J values) with J < -1000 cm-1 (B3LYP/6-311++G(d,p)). Similarly, in some cases, magnetic couplings are observed with J > 289 cm-1 (MN12SX/6-311++G(d,p)) and strong antiferromagnetic coupling (with negative J values) with J < -568 cm-1 (MN12SX/6-311++G(d,p)). Furthermore, while numerous studies have reported that the degree of aromaticity of molecular couplers often favors strong ferromagnetic coupling, displaying the high-spin character of diradicals in their ground states, the couplers chosen in this study are characterized as antiaromatic or nonaromatic. The current investigation provides evidence that, remarkably, antiaromatic couplers are able to enhance stability by favoring electronic diradical structures with very strong ferromagnetic coupling when the length of the through-bond distance and connectivity pattern between radical centers are selected in such a way that the FM coupling is optimized. The findings in this study offer new strategies in the design of novel organic materials with interesting magnetic properties for practical applications.

Dataset Information

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

Publications

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

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