Origins of the Indenofluorene Project: Serendipity and Other Surprises

Haley, Michael M.

doi:10.1002/tcr.201510004

Cited by 10 publications

(4 citation statements)

References 29 publications

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“…While redox-active biradical PCHs based on large acene cores are known, − this study represents a thorough experimental and theoretical investigation of the reduced and oxidized states of DIAn and the transformation of molecular structure along all four redox events. Our results provide a clearer understanding of the nature of charge carriers in ambipolar OFETs and serve as a platform for further modification of the diindenoacene family. ,,− …”

Section: Introductionmentioning

confidence: 79%

A Biradical Balancing Act: Redox Amphoterism in a Diindenoanthracene Derivative Results from Quinoidal Acceptor and Aromatic Donor Motifs

et al. 2016

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The reduced and oxidized states of an open-shell diindeno[b,i]anthracene (DIAn) derivative have been investigated by experimental and theoretical techniques. As a result of moderate biradical character and the ability of cyclopenta-fused scaffolds to stabilize both positive and negative charges, DIAn exhibits rich redox chemistry with four observable and isolable charged states. Structural and electronic properties of the DIAn system are brought to light by UV-vis-NIR and Raman spectroelectrochemical measurements. Aromatization of the diindeno-fused anthracene core upon successive single-electron injections is revealed through single-crystal X-ray diffraction of radical anion and dianion salts. We present a rare case where the pseudoaromatic/quinoidal ground state of a neutral biradical polycyclic hydrocarbon leads to a stable cascade of five redox states. Our detailed investigation of the transformation of molecular structure along all four redox events provides a clearer understanding of the nature of charge carriers in ambipolar organic field-effect transistors.

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Section: Introductionmentioning

confidence: 79%

A Biradical Balancing Act: Redox Amphoterism in a Diindenoanthracene Derivative Results from Quinoidal Acceptor and Aromatic Donor Motifs

et al. 2016

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“…Single crystals of organic semiconductors provide distinctive systems to investigate how molecular structure, including the chemical composition, atomic arrangements, and larger molecular architecture, can be tuned to precisely direct molecular packing. As such, crystal engineering, and in particular the use of solubilizing alkyl side chains to guide the molecular packing of electronically active polycyclic aromatic hydrocarbon (PAH) chromophores, is a highly active field. − …”

Section: Introductionmentioning

confidence: 99%

Theory-Driven Insight into the Crystal Packing of Trialkylsilylethynyl Pentacenes

et al. 2016

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The functionalization of oligoacenes and similar π-conjugated chromophores with trialkylsilylethynyl groups has proven to be a versatile means to enhance solubility and solution processability and engineer solid-state packing arrangements to produce organic semiconductors that demonstrate outstanding charge-carrier transport characteristics. While a general, empirical-based geometric model has been developed and implemented to direct the solid-state packing arrangements of these molecular materials, there exist numerous examples where the model falters. Here, we employ electronic structure methods to probe the noncovalent, intermolecular interactions of two closely related systems that result in two very different crystal packing configurations: triisopropylsilylethynyl (TIPS) pentacene and its triethylsilylethynyl (TES) analog. The quantum-chemical evaluation details how the slightly larger electron density contained within the volume of the TIPS moiety with respect to TES is in part responsible for the solid-state packing variations. We also make use of periodic density functional theory (DFT) methods to develop in silico polymorphs of these systems and explore the electronic characteristics of varied packing arrangements. The results suggest that TES pentacene, if processed correctly, could be developed into a material with improved charge-carrier transport characteristics when compared to its native form. Overall, the theory-driven insight developed in this work lays an important foundation to build a more robust crystal engineering paradigm for these technologically relevant organic semiconductors.

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“…The antiaromatic character resulted in unique optoelectronic properties, including a smaller highest occupied molecular orbital (HOMO)–lowest unoccupied molecular orbital (LUMO) energy gap compared to that of dihydro[1,2- b ]IF bearing an sp 3 -hybridized methylene bridge . The vulnerability of pentacene to photo and air oxidation has driven the search for a stable pentacene-like topology, offering [1,2- b ]IF as the first non-alternant analogue of linear acene, , while four additional constitutional isomers were subsequently synthesized . The π-extended [1,2- b ]IF-based derivatives have attracted attention in charge-transport and single-molecule conductance studies, in addition to the understanding of antiaromaticity, diradical, and emissive properties …”

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confidence: 99%

Syntheses and Properties of Hole-Transporting Biindenofluorenes

Sharma,

Ankita,

Mittal

et al. 2024

Org. Lett.

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Described herein is a straightforward approach to synthesizing three biindenofluorene (BIF) derivatives, composed of antiaromatic indenofluorene units, which are the first non-alternant congeners of known bipentacene. Dimerization of indeno[1,2b]fluorene and indeno[2,1-c]fluorene units by connecting carbons 3 and 3′ and carbons 2 and 2′, respectively, is shown to influence the highest occupied and lowest unoccupied molecular orbital energy levels of the resulting BIFs, affording band gaps (1.5−1.6 eV) that are smaller than that of a known indenofluorene polymer (2.3 eV). The hole mobilities of BIFs were determined to be ∼10 −2 cm 2 V −1 s −1 .

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Origins of the Indenofluorene Project: Serendipity and Other Surprises

Abstract: Origins of the Indenofluorene Project: Serendipity and Other Surprises

Cited by 10 publications

References 29 publications

A Biradical Balancing Act: Redox Amphoterism in a Diindenoanthracene Derivative Results from Quinoidal Acceptor and Aromatic Donor Motifs

A Biradical Balancing Act: Redox Amphoterism in a Diindenoanthracene Derivative Results from Quinoidal Acceptor and Aromatic Donor Motifs

Theory-Driven Insight into the Crystal Packing of Trialkylsilylethynyl Pentacenes

Syntheses and Properties of Hole-Transporting Biindenofluorenes

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