Naphthacenodithiophene Based Polymers—New Members of the Acenodithiophene Family Exhibiting High Mobility and Power Conversion Efficiency

Knall, Astrid‐Caroline; Ashraf, Raja Shahid; Nikolka, Mark; Nielsen, Christian B.; Purushothaman, Balaji; Sadhanala, Aditya; Hurhangee, Michael; Broch, Katharina; Harkin, David; Novák, Jiřı́; Neophytou, Marios; Hayoz, Pascal; Sirringhaus, Henning; McCulloch, Iain

doi:10.1002/adfm.201602285

Cited by 19 publications

(21 citation statements)

References 28 publications

(48 reference statements)

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“…The syntheses of the IDBFs and IIDBFs begin from dibromoterephthalate 10 and bistriflate 11 , [45] respectively (Scheme 1). Suzuki cross‐coupling with either 3‐benzofuran‐boronic acid ( 12 ) or 2‐benzofuranboronic acid ( 13 ) yielded diesters 14 – 17 .…”

Section: Resultsmentioning

confidence: 99%

A Tale of Two Isomers: Enhanced Antiaromaticity/Diradical Character versus Deleterious Ring‐Opening of Benzofuran‐fused s‐Indacenes and Dicyclopenta[b,g]naphthalenes

et al. 2021

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We examine the effects of fusing two benzofurans to s‐indacene (indacenodibenzofurans, IDBFs) and dicyclopenta[b,g]naphthalene (indenoindenodibenzofurans, IIDBFs) to control the strong antiaromaticity and diradical character of these core units. Synthesis via 3‐functionalized benzofuran yields syn‐IDBF and syn‐IIDBF. syn‐IDBF possesses a high degree of paratropicity, exceeding that of the parent hydrocarbon, which in turn results in strong diradical character for syn‐IIDBF. In the case of the anti‐isomers, synthesized via 2‐substituted benzofurans, these effects are decreased; however, both derivatives undergo an unexpected ring‐opening reaction during the final dearomatization step. All the results are compared to the benzothiophene‐fused analogues and show that the increased electronegativity of oxygen in the syn‐fused derivatives leads to enhancement of the antiaromatic core causing greater paratropicity. For syn‐IIDBF increased diradical character results from rearomati‐zation of the core naphthalene unit in order to relieve this paratropicity.

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Section: Resultsmentioning

confidence: 99%

A Tale of Two Isomers: Enhanced Antiaromaticity/Diradical Character versus Deleterious Ring‐Opening of Benzofuran‐fused s‐Indacenes and Dicyclopenta[b,g]naphthalenes

et al. 2021

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“…Expanding on the design motif of C 16 IDT‐BT, a series of structurally similar near‐amorphous D–A copolymers were also investigated. These polymers exhibit further extended and rigidified donor units, including naphthacenodithiophene (NDT), [ 69 ] thienobenzo [b]indacenodithiophene (TBIDT), [ 70 ] and dithiopheneindenofluorene (TIF). [ 71 ] The underlying electronic design motive for these polymers is to facilitate polaron delocalization along the extended backbone and thus, further improve on the overall charge transport properties.…”

Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Linking Glass‐Transition Behavior to Photophysical and Charge Transport Properties of High‐Mobility Conjugated Polymers

Xiao

Sadhanala

Abdi-Jalebi

et al. 2020

Adv Funct Materials

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The measurement of the mechanical properties of conjugated polymers can reveal highly relevant information linking optoelectronic properties to underlying microstructures and the knowledge of the glass transition temperature (Tg) is paramount for informing the choice of processing conditions and for interpreting the thermal stability of devices. In this work, we use dynamical mechanical analysis to determine the Tg of a range of state‐of‐the‐art conjugated polymers with different degrees of crystallinity that are widely studied for applications in organic field‐effect transistors. We compare our measured values for Tg to the theoretical value predicted by a recent work based on the concept of effective mobility ζ. The comparison shows that for conjugated polymers with a modest length of the monomer units, the Tg values agree well with theoretically predictions. However, for the near‐amorphous, indacenodithiophene–benzothiadiazole family of polymers with more extended backbone units, values for Tg appear to be significantly higher, predicted by theory. However, values for Tg are correlated with the sub‐bandgap optical absorption suggesting the possible role of the interchain short contacts within materials’ amorphous domains.

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“…Recently, aided by the disclosure of a key bistriflate intermediate by the McCulloch group, [ 32 ] graduate student Josh Barker recently returned to the FF arena and successfully prepared the linearly fused, π‐expanded [1,2‐ b ]IF analogue, fluoreno[3,2‐ b ]fluorene 8. [ 33 ] Despite the different mode of fusion of the indene units to the central naphthalene, this work led to the same conclusions experimentally and computationally as the [4,3‐ c ]FF study, more specifically, the observed structural and optical properties of [3,2‐ b ]FF 8 were consistent with a quinoidal core, that is, a closed‐shell molecule.…”

Section: First Steps At π‐Expansionmentioning

confidence: 99%

“…The synthesis of the IIDBT derivatives was fortunately a straightforward process (Scheme 2). Starting from dione 17 , itself prepared from the same bistriflate [ 32 ] that ultimately afforded [3,2‐ b ]FF 8, [ 33 ] addition of bulky aryllithiates followed by SnCl 2 ‐mediated reductive dearomatization gave IIDBTs 13a‐b . At this same time, it occurred to us that if the IIDBTs were truly open‐shell molecules with distinct radical centers, reducing the steric protection about the apical carbon atoms should allow the radical centers to behave like true radicals and thus scavenge hydrogen atoms.…”

Section: Diradical Derivatives With Naphthalene Coresmentioning

confidence: 99%

Learning how to fine‐tune diradical properties by structure refinement

Dressler

Haley

2020

J of Physical Organic Chem

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The literature has seen a large increase in the number of new carbon-based organic diradicals/diradicaloids in recent years. While a plethora of new and exciting structures have been created, there seemingly is a gap in knowledge of what fundamental electronic parameters are in play and thus how to rationally manipulate said parameters to "fine tune" the resultant diradical properties. Since 2014, the Haley group has been exploring methods to systematically alter the diradical character and the singlet-triplet energy gap in said class of molecules. Our entrance into organic diradicals began with the π-expansion of the benzene core of indeno[1,2-b]fluorene up to the anthracene core of diindenoanthracene (DIAn). DIAn possessed moderate diradical character (y = 0.62) with a surprising level of stability (more than 2 months in solution). From this molecular blueprint for producing stable diradicals, the Haley lab has investigated how to fine tune diradical properties via structural changes in two key positions: (a) the length of the acene core and (b) thoughtful exchange of the outer arenes. With this strategy at our disposal, we can make large scale changes to the diradical character index and singlet-triplet energy gap through changing the core length, and these properties can be further fine-tuned in a series of closely related diradicals by careful exchange of the outer arenes utilizing the straightforward methods described in this mini-review.

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Naphthacenodithiophene Based Polymers—New Members of the Acenodithiophene Family Exhibiting High Mobility and Power Conversion Efficiency

Cited by 19 publications

References 28 publications

A Tale of Two Isomers: Enhanced Antiaromaticity/Diradical Character versus Deleterious Ring‐Opening of Benzofuran‐fused s‐Indacenes and Dicyclopenta[b,g]naphthalenes

A Tale of Two Isomers: Enhanced Antiaromaticity/Diradical Character versus Deleterious Ring‐Opening of Benzofuran‐fused s‐Indacenes and Dicyclopenta[b,g]naphthalenes

Linking Glass‐Transition Behavior to Photophysical and Charge Transport Properties of High‐Mobility Conjugated Polymers

Learning how to fine‐tune diradical properties by structure refinement

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