Cyclization of Terphenyl‐Bisfluorenols: A Mechanistic Study of the Regioselectvity

Poriel, Cyril; Barrière, Frédéric; Rault‐Berthelot, Joëlle; Thirion, Damien

doi:10.1002/chem.201901457

Cited by 8 publications

(13 citation statements)

References 59 publications

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“…Interestingly, the 1 H NMR signal of the hydrogen atom in the position 14 in 2 appears as a doublet of doublets with the coupling constants of 3 and 8 Hz. Additional 1 H spectra measured with simultaneous 19 F decoupling revealed that the additional 3 Hz coupling comes from the throughspace interaction with fluorine in the position 1. It corresponds with the close contact of these atoms in space leading to an overlap of their electron clouds.…”

Section: Synthesis Of Fluorinated Dihydroindenofluorenesmentioning

confidence: 97%

“…The cyclotrimerization of 8 c gave rise to diol 10 c, which was isolated in 50 % (Scheme 3, conditions A). It should be noted that formation of other intractable side-products was noticed by 19 F NMR analysis of the crude reaction mixture. Lowering of the reaction temperature to 150°C provided 10 c in 76 % yield (conditions B), along with reduced formation of other side-products (again confirmed by 19 F NMR analysis of the crude mixture).…”

Section: Synthesis Of Fluorinated Dihydroindenofluorenesmentioning

confidence: 99%

“…It should be noted that formation of other intractable side-products was noticed by 19 F NMR analysis of the crude reaction mixture. Lowering of the reaction temperature to 150°C provided 10 c in 76 % yield (conditions B), along with reduced formation of other side-products (again confirmed by 19 F NMR analysis of the crude mixture). In addition, the use of Ag 2 CO 3 is not strictly required, because the reaction in its absence furnished 10 c in 71 % isolated yield (conditions C).…”

Section: Synthesis Of Fluorinated Dihydroindenofluorenesmentioning

confidence: 99%

“…[3] It is probably inflicted by the presence of two cyclopentadiene rings causing a more widely opened helical shell with the less intensive steric repulsion between the terminal benzene rings. The C(1)-C (19) and C(2)-C(18) distances are 3.127 (2) [6]helicene could be also one of the factors strongly contributing to configurational instability. Finally, we attempted to synthesize octafluorinated dispirodihydroindeno[2,1-c]fluorene (1 h).…”

Section: Synthesis Of Fluorinated Dihydroindenofluorenesmentioning

confidence: 99%

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A General Synthetic Approach and Photophysical Properties of Regioselectively Fluorinated [5]‐ and [6]‐Helical Bispiroindenofluorenes

et al. 2020

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A first series of fluorinated [n]helical compounds (n = 5 and 6) with the dihydroindenofluorene scaffold was prepared in 5 or 9 (octafluorinated dihydroindenofluorene) steps and their photophysical properties were determined. Rh-catalyzed intramolecular [2 + 2 + 2] cyclotrimerization of triyndiols, which were prepared in a modular fashion from simple starting material such as fluorinated haloarylcarbaldehydes, to the intermediate [n]helical dihydroindeno[2,1-c]fluorene-5,8-diols was the crucial synthetic step and proceeded with high efficacy. Their further transformation gave the desired selectively fluorinated bispirodihydroindeno[2,1-c]fluorenes. Their absorption and emission spectra were recorded. The fluorescence quantum yields were up to 92 % and the emission maxima were red-shifted in comparison with their non-fluorinated counterparts (386-413 nm).

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Section: Synthesis Of Fluorinated Dihydroindenofluorenesmentioning

confidence: 97%

Section: Synthesis Of Fluorinated Dihydroindenofluorenesmentioning

confidence: 99%

Section: Synthesis Of Fluorinated Dihydroindenofluorenesmentioning

confidence: 99%

Section: Synthesis Of Fluorinated Dihydroindenofluorenesmentioning

confidence: 99%

See 2 more Smart Citations

A General Synthetic Approach and Photophysical Properties of Regioselectively Fluorinated [5]‐ and [6]‐Helical Bispiroindenofluorenes

et al. 2020

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“…In the field of organic semiconductors for electronics, the synthetic approach is of key importance . Indeed, for potential industrial applications, the synthesis of the host material for a PhOLED should be short, high yielding, and should use inexpensive starting materials.…”

Section: Synthesismentioning

confidence: 99%

Spirophenylacridine‐2,7‐(diphenylphosphineoxide)‐fluorene: A Bipolar Host for High‐Efficiency Single‐Layer Blue Phosphorescent Organic Light‐Emitting Diodes

Lucas

Ibraikulov

Quinton

et al. 2019

Advanced Optical Materials

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Herein, a high‐efficiency host material for single‐layer phosphorescent organic light‐emitting diodes (SL‐PhOLEDs) is reported. This host material is synthesized via an efficient approach and is constructed on the association of an electron‐rich phenylacridine unit connected by a spiro carbon atom to an electron‐deficient 2,7‐bis(diphenylphosphineoxide)‐fluorene. In addition to a high ET value and adequate highest occupied molecular orbital/lowest unoccupied molecular orbital energy levels, the key point in this molecular design is the suitable balance between hole and electron mobilities, which leads to a high‐performance blue SL‐PhOLED with an external quantum efficiency of 17.6% (current efficiency = 37.8 cd A−1 and power efficiency = 37.1 lm W−1) and a low Von of 2.5 V. This performance shows that the molecular design of the present host fulfills the criteria required for high‐efficiency SL‐PhOLEDs. The present performance is one of the highest reported to date for blue SL‐PhOLEDs and more importantly shows the potential of such a molecular design to reach very high‐performance single‐layer devices.

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Chlorinated Spiroconjugated Fused Extended Aromatics for Multifunctional Organic Electronics

et al. 2021

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various hybrid devices have been developed for real-world applications. The preparation process of hybrid devices, however, usually involves vast variety of materials, which not only increases the cost but also makes the process more cumbersome. Thus, there emerges the need to explore multifunctional organic electronic materials to simplify the preparation process and reduce the cost. Spiro-fused polycyclic aromatic compounds, with orthogonal π-subsystems linked by a sp 3-hybridized spiro-atom, have been extensively explored as organic electronic materials due to rigid 3D orthogonal configuration, good processability, excellent thermal and optical stability, and exclusive spiroconjugation effects. [4-7] Spiroconjugation, first described by Simmons and Fukunaga in 1967, refers to the delocalization and bandgap alteration that occurs upon orbital interaction between the π systems of the two spiro-fused planar pieces. [8] The unique 3D rigid spiroconjugation architecture not only reduces intermolecular electronic coupling and in turn the charge recombination but also increases charge transport capability. [9] Notably, 9,9′-spirobifluorene, the most prominent class of The synthesis of a new molecule, SFIC-Cl, is reported, which features enhanced π-electron delocalization by spiroconjugation and narrowed bandgap by chlorination. SFIC-Cl is integrated into a single-crystal transistor (OFET) and organic light-emitting diode (OLED). The material demonstrates remarkable transport abilities across various solution-processed OFETs and retains efficient radiance in a near-infrared OLED emitting light at 700 nm. Furthermore, the intermolecular multi-dimensional connection of SFIC-Cl enables the fabrication of a single-component large-area (2 × 2 cm 2) near-infrared OLED by spin-coating. The SFIC-Cl-acceptor-based solar cell shows excellent power conversion efficiency of 10.16% resulting from the broadened and strong absorption and well-matched energy levels. The study demonstrates that chlorinated spiroconjugated fused systems offer a novel direction toward the development of high-performance organic semiconductor materials for hybrid organic electronic devices.

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Cyclization of Terphenyl‐Bisfluorenols: A Mechanistic Study of the Regioselectvity

Cited by 8 publications

References 59 publications

A General Synthetic Approach and Photophysical Properties of Regioselectively Fluorinated [5]‐ and [6]‐Helical Bispiroindenofluorenes

A General Synthetic Approach and Photophysical Properties of Regioselectively Fluorinated [5]‐ and [6]‐Helical Bispiroindenofluorenes

Spirophenylacridine‐2,7‐(diphenylphosphineoxide)‐fluorene: A Bipolar Host for High‐Efficiency Single‐Layer Blue Phosphorescent Organic Light‐Emitting Diodes

Chlorinated Spiroconjugated Fused Extended Aromatics for Multifunctional Organic Electronics

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