Perfluoroalkylated PAH n-Type Semiconductors

Sun, Haoran; Kramer, Jordan H.

doi:10.1016/b978-0-12-803479-8.00007-3

Cited by 5 publications

(3 citation statements)

References 102 publications

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“…If both effects are present, the M effect usually prevails over the I effect. The only notable exception is fluorine, whose −I effect due to the high EN is able to compete with its +M effect, , reflected in the low Hammett constant of σ p = 0.06. , This allows for a subtle interplay of fluorine with the parent molecular backbone. Alternant hydrocarbons (i.e., molecules with a symmetry relation of all occupied and unoccupied MOs so that E HOMO – E HOMO–1 = −( E LUMO – E LUMO+1 ) and so forth) can be treated in a qualitative way by a simple Hückel picture coupled to first/second-order perturbation, as demonstrated earlier for PF5Ac .…”

mentioning

confidence: 99%

“Though It Be but Little, It Is Fierce”: Excited State Engineering of Conjugated Organic Materials by Fluorination

Milián‐Medina

Gierschner

2016

J. Phys. Chem. Lett.

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Fluorination is frequently used to significantly change the properties of conjugated organic materials due to fluorine's exceptional properties; well-known is its impact on electronic structure, but it also impacts the geometry despite fluorine's small size. Less known, the changes in the electronic and geometrical properties may provoke drastic changes of the excited state properties like batho- and hypsochromic shifts of absorption and emission bands (inter alia leading to excited state switching), hypo- and hyperchromic effects, spectral broadening, and changes of the nonradiative deactivation pathways. The state of the art on these issues is summarized in the current Perspective to stimulate further discussions on this intriguing subject.

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confidence: 99%

“Though It Be but Little, It Is Fierce”: Excited State Engineering of Conjugated Organic Materials by Fluorination

Milián‐Medina

Gierschner

2016

J. Phys. Chem. Lett.

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“…Of particular interest are the ways that strong electron‐withdrawing groups can affect not only the electronic coupling of donors and acceptors but the degree of π–π overlap and one‐dimensional stacking . In particular, F atoms and perfluoroalkyl (R F ) groups can have desirable electronic and structural effects. For example, R F substitution can raise the electron affinities ( EA s) of polycyclic aromatic hydrocarbons (PAHs) by 0.3–0.5 eV per R F group and strengthen parallel π–π interactions while suppressing T‐shaped C−H⋅⋅⋅π interactions .…”

Section: Introductionmentioning

confidence: 99%

PAH/PAH(CF₃)_n Donor/Acceptor Charge‐Transfer Complexes in Solution and in Solid‐State Co‐Crystals

Castro

Bukovsky

Kuvychko

et al. 2019

Chemistry A European J

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A solution, solid‐state, and computational study is reported of polycyclic aromatic hydrocarbon PAH/PAH(CF3)n donor/acceptor (D/A) charge‐transfer complexes that involve six PAH(CF3)n acceptors with known gas‐phase electron affinities that range from 2.11(2) to 2.805(15) eV and four PAH donors, including seven CT co‐crystal X‐ray structures that exhibit hexagonal arrays of mixed π‐stacks with 1/1, 1/2, or 2/1 D/A stoichiometries (PAH=anthracene, azulene, coronene, perylene, pyrene, triphenylene; n=5, 6). These are the first D/A CT complexes with PAH(CF3)n acceptors to be studied in detail. The nine D/A combinations were chosen to allow several structural and electronic comparisons to be made, providing new insights about controlling D/A interactions and the structures of CT co‐crystals. The comparisons include, among others, CT complexes of the same PAH(CF3)n acceptor with four PAH donors and CT complexes of the same donor with four PAH(CF3)n acceptors. All nine CT complexes exhibit charge‐transfer bands in solution with λ max between 467 and 600 nm. A plot of E(λ max) versus [IE(donor)−EA(acceptor)] for the nine CT complexes studied is linear with a slope of 0.72±0.03 eV eV−1. This plot is the first of its kind for CT complexes with structurally related donors and acceptors for which precise experimental gas‐phase IEs and EAs are known. It demonstrates that conclusions based on the common assumption that the slope of a CT E(λ max) versus [IE−EA] plot is unity may be incorrect in at least some cases and should be reconsidered.

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“…Fluorine-containing polycyclic aromatic hydrocarbons (F-PAHs) [1] have attracted much attention in the field of material chemistry as n-type semiconductors for fabrication of electronic and optical devices [2]. In order to synthesize F-PAHs in short steps, it is inevitable to introduce fluorine or organofluorine groups into the PAH framework.…”

Section: Introductionmentioning

confidence: 99%

Fluorine-Containing Dibenzoanthracene and Benzoperylene-Type Polycyclic Aromatic Hydrocarbons: Synthesis, Structure, and Basic Chemical Properties

et al. 2018

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Intramolecular photocyclization of stilbene derivatives (Mallory reaction) is one of the efficient methods for building polycyclic aromatic hydrocarbon (PAH) frameworks, and is also expected to be applicable to synthesis of fluorine-containing PAHs (F-PAHs). In this study, dibenzoanthracene-type (4a) and benzoperylene-type (4b) F-PAHs were synthesized using the Mallory reaction of the 1,4-distyrylbenzene-type π-conjugated molecule (3a), which was prepared by addition-defluorination of available octafluorocyclopentene (OFCP) and aryllithium in three steps. The structure of 4a originating from π–π interaction was characterized by X-ray crystallographic analysis. The absorption maxima of UV-Vis spectra and emission maxima of photoluminescence spectra of the PAHs were positioned at a longer wavelength compared to those of the corresponding unsubstituted PAHs, presumably due to the electron-withdrawing nature of perfluorocyclopentene (PFCP) units. The effect of PFCP units in F-PAHs was also studied by time-dependent density functional theory (TD-DFT) calculation.

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Perfluoroalkylated PAH n-Type Semiconductors

Cited by 5 publications

References 102 publications

“Though It Be but Little, It Is Fierce”: Excited State Engineering of Conjugated Organic Materials by Fluorination

“Though It Be but Little, It Is Fierce”: Excited State Engineering of Conjugated Organic Materials by Fluorination

PAH/PAH(CF₃)_n Donor/Acceptor Charge‐Transfer Complexes in Solution and in Solid‐State Co‐Crystals

Fluorine-Containing Dibenzoanthracene and Benzoperylene-Type Polycyclic Aromatic Hydrocarbons: Synthesis, Structure, and Basic Chemical Properties

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Perfluoroalkylated PAH n-Type Semiconductors

Cited by 5 publications

References 102 publications

“Though It Be but Little, It Is Fierce”: Excited State Engineering of Conjugated Organic Materials by Fluorination

“Though It Be but Little, It Is Fierce”: Excited State Engineering of Conjugated Organic Materials by Fluorination

PAH/PAH(CF3)n Donor/Acceptor Charge‐Transfer Complexes in Solution and in Solid‐State Co‐Crystals

Fluorine-Containing Dibenzoanthracene and Benzoperylene-Type Polycyclic Aromatic Hydrocarbons: Synthesis, Structure, and Basic Chemical Properties

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PAH/PAH(CF₃)_n Donor/Acceptor Charge‐Transfer Complexes in Solution and in Solid‐State Co‐Crystals