Synthetic Aspects and Electro-Optical Properties of Fluorinated Arylenevinylenes for Luminescence and Photovoltaics

Martinelli, Carmela; Farinola, Gianluca M.; Pinto, Vita; Cardone, Antonio

doi:10.3390/ma6041205

Cited by 37 publications

(22 citation statements)

References 106 publications

(118 reference statements)

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“…The polymer main‐chain was composed of the alternating sequence with fluorene and dithiophenylbenzothiadiazole (TBT). These alternating polymers are known as a class of low‐band gap polymers for fabricating organic opto‐electric devices such as photovoltaic cells and electroluminescence displays and showed the emission in the red region originated from the intramolecular charge transfer (CT) state ( λ em,max = 625 nm) . As a blue emissive unit, pyrene and DPA were introduced at the cardo carbon.…”

Section: Resultsmentioning

confidence: 99%

Energy transfer through heterogeneous dyes‐substituted fluorene‐containing alternating copolymers and their dual‐emission properties in the films

Yeo

Tanaka

Chujo

2015

J. Polym. Sci. Part A: Polym. Chem.

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We report synthesis of the modified fluorene polymers tethered to the heterogeneous types of the fluorescent dyes at the cardo carbon for obtaining the dual‐emissive solid materials. A series of the alternating fluorene copolymers modified with pyrene or 9,10‐diphenylanthracene and BODIPY at the cardo carbon based on the red‐emissive donor–acceptor structure were prepared, and their characteristics were examined. From the measurements of the optical properties, the energy transfer efficiencies were evaluated. In summary, variable energy transfer efficiencies were observed between the side chains and from the side chain to the main chain. It was indicated that the energy transfer efficiencies were strongly depended on the types of the energy donor and the detection conditions as such in the solution or film. Furthermore, it was found that the cardo fluorene units can contribute to the suppression of the energy transfer in the condensed state. Finally, the dual‐emissive polymers were obtained in the film states. This is the first example, to the best of our knowledge, not only to offer systematic information on the energy transfer between the dye molecules and the polymer main‐chains via the cardo structure but also to demonstrate the polymer‐based optical materials with the dual‐emission properties. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015, 53, 2026–2035

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Section: Resultsmentioning

confidence: 99%

Energy transfer through heterogeneous dyes‐substituted fluorene‐containing alternating copolymers and their dual‐emission properties in the films

Yeo

Tanaka

Chujo

2015

J. Polym. Sci. Part A: Polym. Chem.

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“…1,5 Fluorinated materials are employed for their hydrophobic properties, their chemical inertness and physical properties such as elasticity. [6][7][8] The introduction of long fluorinated chains or "fluorous pony-tails" can produce phase behavior that is particularly favorable for catalysis, solvent extraction and chemical synthesis. [9][10][11][12][13] Saturated hydrofluorocarbons have also found important applications as refrigerants, and propellants, but several of them will now be phased out following the Kigali agreement of 2016 for reduction of greenhouse gases, leading to disposal issues.…”

Section: Introductionmentioning

confidence: 99%

Selectivity of C–H Activation and Competition between C–H and C–F Bond Activation at Fluorocarbons

2017

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Partially fluorinated alkanes, arenes, and alkenes can be transformed by a variety of transition metal and lanthanide systems. Although the C-H bond is weaker than the C-F bond regardless of the hybridization of the carbon, the reaction of the C-F bond at the metal is usually more exothermic than the corresponding reaction of the C-H bonds. Both bonds are activated by the metal systems, but the preference for activating these bonds depends on the nature of the hydrocarbon and of the metal system, so that the reaction can be directed exclusively toward C-H or C-F bonds or yield a mixture of products. Additionally, the presence of fluorine differentiates between C-H bonds at different positions resulting in regioselective C-H bond activation; paradoxically, the strongest C-H bond reacts preferentially. The purpose of this review is to describe the field of reactions of partially fluorinated substrates with transition metal atoms, ions, and molecular complexes. The controlling physical properties (thermodynamics and kinetics) are described first, followed by a description of stoichiometric reactions, with the competition between the C-H and C-F activations as focus. A few representative catalytic systems are discussed. The review also highlights the benefit of combining experimental and theoretical studies.

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“…For compound 1b, TD-PBE0/6-311++G(d,p) calculations in vacuo 16 provided a Dm 12 value of 17.7 D, slightly lower than that computed for 1a, 19.0 D, at the same level of theory (see Table S1 † for a detailed comparison between computed properties of compounds 1a and 1b). Interestingly, unlike other D-PPV-A systems, 15 which show strong concentration quenching of NLO properties and strong solvent dependence, the mb l value of 1b in CHCl 3 19 F signals and no aggregates were observed using DLS, proving the absence of signicant intermolecular interactions in solution. This result is particularly relevant to the idea of device construction since a limiting factor is oen represented by dye loading.…”

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confidence: 98%

“…In this respect, uorination of A groups offers the possibility of modulating optical and electrical properties of push-pull organic chromophores, lowering their HOMO and LUMO energy levels and facilitating the charge transfer process, 3 thus enhancing the 2 nd order NLO response. 4 Fluorination also affects crystal packing of conjugated organic materials, 5 which is a key issue in determining their electronic and optical properties, 6 and therefore their potential use in electronic and optoelectronic devices.…”

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confidence: 99%

Fluorine-induced J-aggregation enhances emissive properties of a new NLO push–pull chromophore

et al. 2014

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A new fluorinated push-pull chromophore with good second-order NLO properties even in concentrated solution shows solid state intermolecular aryl-fluoroaryl interactions leading to J-aggregates with intense solid state luminescence.Over the last few decades, organic-based optoelectronic materials displaying good 2 nd order nonlinear optical (NLO) and emission properties have received great scientic attention. 1Among all possible substrates, linear p-conjugated organic molecules, and notably p-phenylene vinylene (PPV) derivatives, are of particular interest due to their broad absorption bands, high luminescence quantum yields, and large Stokes shis. 2Moreover, PPV structures have been used as convenient pbridges between strong electron donor (D) and acceptor (A) groups, whose electronic properties can be nely tuned by the insertion of suitable electron-withdrawing or donating substituents. In this respect, uorination of A groups offers the possibility of modulating optical and electrical properties of push-pull organic chromophores, lowering their HOMO and LUMO energy levels and facilitating the charge transfer process, 3 thus enhancing the 2 nd order NLO response. 4 Fluorination also affects crystal packing of conjugated organic materials, 5 which is a key issue in determining their electronic and optical properties, 6 and therefore their potential use in electronic and optoelectronic devices. On the other hand, linear p-conjugated materials tend to strongly aggregate in the solid state and in concentrated solutions, yielding p-stacked structures, which oen suppress luminescence and NLO properties. A good strategy to optimize both properties is to design molecules characterized by a low tendency to aggregate when dispersed or dissolved, but selfassemble into J-type aggregates in the solid state. J-aggregates are characterized by a narrow and intense absorption band, bathochromically shied with respect to the isolated molecule, and are known to enhance both the emissive 8 and the NLO properties. 9Aryl-uoroaryl interactions, 10 among others, 11 have been exploited to dictate self-assembly of large aromatic chromophores into J-aggregates. 12,13We have recently reported the synthesis, structural, and optical characterization of a new NLO chromophore consisting of a push-pull system where a PPV moiety spaces an electrondonor end, working as the halogen-bond-acceptor terminus, and a p-iodotetrauorophenyl end, working as the halogenbond-donor terminus (1a in Scheme 1).14 This chromophore, while being effective from the point of view of NLO properties, did not show any emission in the solid state and a very low one in solution (Quantum Yield, QY ¼ 0.14 in toluene), as a likely consequence of the presence of iodine. Here our attention focuses on the de-iodinated derivative 1b (Scheme 1), which being devoid of the I atom, should not only be preserved from the heavy atom effect on luminescence, but also favor the aryluoroaryl interactions with respect to self-complementary halogen bonded arrangements. This, in fac...

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Synthetic Aspects and Electro-Optical Properties of Fluorinated Arylenevinylenes for Luminescence and Photovoltaics

Cited by 37 publications

References 106 publications

Energy transfer through heterogeneous dyes‐substituted fluorene‐containing alternating copolymers and their dual‐emission properties in the films

Energy transfer through heterogeneous dyes‐substituted fluorene‐containing alternating copolymers and their dual‐emission properties in the films

Selectivity of C–H Activation and Competition between C–H and C–F Bond Activation at Fluorocarbons

Fluorine-induced J-aggregation enhances emissive properties of a new NLO push–pull chromophore

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