Electron acceptors of the fluorene series. Part 6.1 Synthesis of 4,5-dinitro-9-X-fluorene-2,7-disulfonic acid derivatives, their charge transfer complexes with anthracene and sensitization of photoconductivity of poly-N-(2,3-epoxypropyl)carbazole

Mysyk, D. D.; Perepichka, Igor F.; Sokolov, Nikolai I.

doi:10.1039/a606106k

Cited by 34 publications

(31 citation statements)

References 25 publications

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“…[19] In order to design narrow-bandgap organometallic polyynes, we make use of a 9-dicyanomethylene-substituted fluorene as an electron acceptor on the grounds that they are widely used in the investigation of electron donor/acceptor interaction in charge-transfer complex formation, activation of photoconductivity of organic semiconductors and as electron transport materials. [20,21] Here, we report preliminary results on the synthesis and properties of the first examples of the soluble, low-bandgap 9-dicyanomethylenesubstituted platinum(II) acetylide complex and polymer.…”

Section: Introductionmentioning

confidence: 99%

Synthesis, Redox and Optical Properties of Low-Bandgap Platinum(II) Polyynes with 9-Dicyanomethylene-Substituted Fluorene Acceptors

Wong

Choi

et al. 2001

Macromol. Rapid Commun.

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In view of the strong electron‐withdrawing nature of the cyano substituent, a blue donor/acceptor‐type organometallic polymer (trans‐[—Pt(PBu3)2—C≡C—R—C≡C—]n (R = 9‐dicyanomethylenefluorene‐2,7‐diyl)) was prepared in good yield by CuI‐catalyzed polymerization involving the dehydrohalogenating coupling of trans‐[Pt(PBu3)2Cl2] and H—C≡C—R—C≡C—H. The thermal, redox and photoconducting properties of the polymer are reported. Electronic absorption studies indicate that it has a bandgap of 1.58 eV which is the lowest among any of the metal polyyne polymers reported in the literature. The derivatization of the polymer backbone with electron deficient dicyano‐substituted electron acceptor in the side chain is found to be effective to tune the bandgap of this class of materials while maintaining their solubility and processability.

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Section: Introductionmentioning

confidence: 99%

Synthesis, Redox and Optical Properties of Low-Bandgap Platinum(II) Polyynes with 9-Dicyanomethylene-Substituted Fluorene Acceptors

Wong

Choi

et al. 2001

Macromol. Rapid Commun.

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“…Thus, for CTC of various fluorene acceptors with low-molecular donors, e.g. anthracene, 41 N-ethylcarbazlole, 49 or N-propylcarbazole, 39 in different solvents (1,2-dichloroethane, dioxane), the molar extinction coefficients vary from 800 to 1900 M À1 cm À1 only, whereas variations in the equilibrium constants is much higher, from 1.07 to 12.1 M À1 . In line with this, in MEH-PPV:TNFon blends, the CTC molar extinctions are independent of the CTC concentration.…”

Section: Fitting the Data With The Ne Modelmentioning

confidence: 97%

“…MEH-PPV:TNFon, 6 and it is unknown for the blends of other acceptors studied in this work. Unfortunately, Benesi-Hildebrand and related linear regression methods, 41,48,49 used for determination of CTC molar extinction coefficients that are usually applied for small-molecule CTC and the method proposed in ref. 6 for threshold-like a(C a ) are inapplicable.…”

Section: Fitting the Data With The Ne Modelmentioning

confidence: 99%

Threshold-like complexation of conjugated polymers with small molecule acceptors in solution within the neighbor-effect model

Sosorev

Parashchuk

Zapunidi

et al. 2016

Phys. Chem. Chem. Phys.

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In some donor-acceptor blends based on conjugated polymers, a pronounced charge-transfer complex (CTC) forms in the electronic ground state. In contrast to small-molecule donor-acceptor blends, the CTC concentration in polymer:acceptor solution can increase with the acceptor content in a threshold-like way. This threshold-like behavior was earlier attributed to the neighbor effect (NE) in the polymer complexation, i.e., next CTCs are preferentially formed near the existing ones; however, the NE origin is unknown. To address the factors affecting the NE, we record the optical absorption data for blends of the most studied conjugated polymers, poly(2-methoxy-5-(2-ethylhexyloxy)-1,4-phenylenevinylene) (MEH-PPV) and poly(3-hexylthiophene) (P3HT), with electron acceptors of fluorene series, 1,8-dinitro-9,10-antraquinone (), and 7,7,8,8-tetracyanoquinodimethane () in different solvents, and then analyze the data within the NE model. We have found that the NE depends on the polymer and acceptor molecular skeletons and solvent, while it does not depend on the acceptor electron affinity and polymer concentration. We conclude that the NE operates within a single macromolecule and stems from planarization of the polymer chain involved in the CTC with an acceptor molecule; as a result, the probability of further complexation with the next acceptor molecules at the adjacent repeat units increases. The steric and electronic microscopic mechanisms of NE are discussed.

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“…It is known that nitrosubstituted fluorene acceptors readily form CTCs with electron donors, [26,32] including numerous TTF-family donors.…”

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confidence: 99%

Remarkable Interplay of Redox States and Conformational Changes in a Sterically Crowded, Cross‐Conjugated Tetrathiafulvalene Vinylog

Amriou¹,

Perepichka²,

Batsanov³

et al. 2006

Chemistry A European J

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Derivatives of 9-[2-(1,3-dithiol-2-ylidene)ethylidene]thioxanthene have been synthesized using Horner-Wadsworth-Emmons reactions of (1,3-dithiol-2-yl)phosphonate reagents with thioxanthen-9-ylidene-acetaldehyde (5). Further reactions lead to the sterically crowded cross-conjugated "vinylogous tetrathiafulvalene" derivative 9-[2,3-bis-(4,5-dimethyl-1,3-dithiol-2-ylidene)-propylidene]thioxanthene (10). X-ray crystallography, solution electrochemistry, optical spectroscopy, spectroelectrochemistry, and simultaneous electrochemistry and electron paramagnetic resonance spectroscopy, combined with theoretical calculations performed at the B3LYP/6-31G(d) level, elucidate the interplay of the electronic and structural properties in these molecules. For compound 10, multistage redox behavior is observed: the overall electrochemical process can be represented by 10-->10(.+)-->10(2+)-->10(4+) with good reversibility for the 10-->10(.+)-->10(2+) transformations. At the tetracation stage there is the maximum gain in aromaticity at the dithiolium and thioxanthenium rings. Theory predicts that for 10, 10(.+), and 10(2+) the trans isomers are more stable than the cis isomers (by ca. 2-18 kJ mol(-1)), whereas for 10(4+) the cis isomer becomes more stable than the trans isomer (by ca. 25 kJ mol(-1)) [trans and cis refer to the arrangement of the two dithiole moieties with respect to the central ==C(R)--C(H)== fragment]. These data explain the detection in cyclic voltammograms of both trans and cis isomers of 10 and 10(.+) during the reduction of 10(4+) at fast scan rates (>100 mV s(-1)) when the cis-trans isomerization is not completed within the timescale of the experiment. The X-ray structure of the charge-transfer complex (CTC) of 10 with 2,4,5,7-tetranitrofluorene-9-dicyanomethylenefluorene (DTeF) [stoichiometry: 10(.+)(DTeF)(2) (.-)2 PhCl] reveals a twisted conformation of 10(.+) (driven by the bulky thioxanthene moiety) and provides a very rare example of segregated stacking of a fluorene acceptor in a CTC.

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Electron acceptors of the fluorene series. Part 6.1 Synthesis of 4,5-dinitro-9-X-fluorene-2,7-disulfonic acid derivatives, their charge transfer complexes with anthracene and sensitization of photoconductivity of poly-N-(2,3-epoxypropyl)carbazole

Cited by 34 publications

References 25 publications

Synthesis, Redox and Optical Properties of Low-Bandgap Platinum(II) Polyynes with 9-Dicyanomethylene-Substituted Fluorene Acceptors

Synthesis, Redox and Optical Properties of Low-Bandgap Platinum(II) Polyynes with 9-Dicyanomethylene-Substituted Fluorene Acceptors

Threshold-like complexation of conjugated polymers with small molecule acceptors in solution within the neighbor-effect model

Remarkable Interplay of Redox States and Conformational Changes in a Sterically Crowded, Cross‐Conjugated Tetrathiafulvalene Vinylog

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