Showing papers on "Fluorenone published in 2022"
TL;DR: Stimuli-responsive organic materials with aggregation-induced emission (AIE) characteristics have become a research hot spot in recent years due to their promising applications in information storage, organic light-emitting semiconductors (OLEDs) and... as mentioned in this paper .
Abstract: Stimuli-responsive organic materials with aggregation-induced emission (AIE) characteristics have become a research hot spot in recent years due to their promising applications in information storage, organic light-emitting semiconductors (OLEDs) and...
9 citations
TL;DR: In this article , an imide-functionalized fluorenone (FOI) and its cyanated derivative (FCNI) were constructed from a series of polymers with a high electron mobility of 0.11 cm2 V-1 s-1.
Abstract: The development of high-performance n-type polymer semiconductors is powered by the design and synthesis of electron-deficient building blocks with optimized physicochemical properties. By meticulously installing an imide group onto fluorene and its cyanated derivative, we report here two very electron-deficient building blocks, imide-functionalized fluorenone (FOI) and its cyanated derivative (FCNI), both featuring a deep-lying lowest unoccupied molecular orbital energy level down to -4.05 eV and highly coplanar framework, endowing them ideal units for constructing n-type polymers. Thus, a series of polymers are built from them, exhibiting unipolar n-type transport character with a highest electron mobility of 0.11 cm2 V-1 s-1. Hence, FOI and FCNI offer a remarkable platform for accessing high-performance n-type polymers and the imide functionalization of appropriate (hereo)arenes is a powerful strategy for developing polymers with deep-lying LUMOs for n-type organic electronics.
9 citations
TL;DR: In this article , the possibility of electrochemical hydrogen storage via conversion of proton of a proton donor into a hydrogen atom involved in covalent bonds with the liquid organic hydrogen carriers (LOHC) was explored.
7 citations
TL;DR: In this article , an imide-functionalized fluorenone (FOI) and its cyanated derivative (FCNI) were constructed from a series of polymers with high electron mobility of 0.11 cm2 V-1 s-1 .
Abstract: The development of high-performance n-type polymer semiconductors is powered by the design and synthesis of electron-deficient building blocks with optimized physicochemical properties. By meticulously installing an imide group onto fluorene and its cyanated derivative, we report here two very electron-deficient building blocks, imide-functionalized fluorenone (FOI) and its cyanated derivative (FCNI), both featuring a deep-lying lowest unoccupied molecular orbital energy level down to -4.05 eV and highly coplanar framework, endowing them ideal units for constructing n-type polymers. Thus, a series of polymers are built from them, exhibiting unipolar n-type transport character with a highest electron mobility of 0.11 cm2 V-1 s-1 . Hence, FOI and FCNI offer a remarkable platform for accessing high-performance n-type polymers and the imide functionalization of appropriate (hetero)arenes is a powerful strategy for developing polymers with deep-lying LUMOs for n-type organic electronics.
7 citations
TL;DR: In this article , the self-assemblies of a fluorenone derivative, 2-([1,1′-biphenyl]-4-yl)-7-phenyl-fluoren (2-Bp-7-PFO), with an asymmetric configuration, which exhibits efficient second-harmonic generation (SHG) response, large polarization ratio, and outstanding optical stability.
Abstract: Organic crystals demonstrating efficient nonlinear optical (NLO) effects are highly promising candidates for the next-generation photonics. However, the assembly of NLO molecules with high dipoles in a non-centrosymmetric (NCS) manner for second-order NLO effects remains a formidable challenge. Here, we develop the self-assemblies of a fluorenone derivative, 2-([1,1′-biphenyl]-4-yl)-7-phenyl-fluoren (2-Bp-7-PFO), with an asymmetric configuration, which exhibits efficient second-harmonic generation (SHG) response, large polarization ratio, and outstanding optical stability. Driven by the synergetic intermolecular interactions, 2-Bp-7-PFO molecules arrange in an NCS way with two different morphologies. The exploration of NLO properties of fluorenone derivate with asymmetrical configuration could provide a new platform for the construction of organic NLO materials and devices in the future.
6 citations
TL;DR: In this paper , an efficient approach for the enantioselective synthesis of inherently chiral calix[4]arenes via palladium-catalyzed asymmetric intramolecular C-H arylations was reported.
Abstract: We report herein an efficient approach for the enantioselective synthesis of inherently chiral calix[4]arenes via palladium-catalyzed asymmetric intramolecular C-H arylations. Using a chiral bifunctional phosphine-carboxylate ligand, the inherent chirality on macrocyclic scaffolds was induced successfully, from which a wide range of calix[4]arenes with fluorenone motifs were obtained with good yields and excellent enantioselectivities (up to >99% ee). The synthetic utility of this method was demonstrated by diverse transformations of the products, thus substantially expanding the chemical space of chiral calix[4]arenes. Further investigations of photophysical and chiroptical properties revealed that calix[4]arenes bearing two fluorenone moieties displayed remarkable glum values (up to 0.019), highlighting the great potential of inherent chirality in the development of organic optoelectronic materials.
5 citations
TL;DR: Experimental and computational studies show that the migratory insertion of CO into a Au(III)-C bond is more energetically challenging compared to other M-C bonds, but once achieved, the product is comparatively stable with respect to retro-carbonylation.
Abstract: A MeDalPhos-ligated gold(III) metallafluorene complex, generated via C–C oxidative addition of biphenylene, reacts with CO to produce 9-fluorenone. Experimental and computational studies show that this proceeds via a hitherto unknown migratory insertion of CO into a Au(III)–C bond. This process is more energetically challenging compared to other M–C bonds, but once achieved, the product is comparatively stable with respect to retro-carbonylation. Exploiting migratory insertion of CO into Au–C bonds may extend the range of products that are accessible using gold chemistry.
4 citations
TL;DR: In this paper , the synthesis, phase-transition behaviour, and mesophase structure of fluorenone-incorporated LC trimers that exhibit an emerging helical twist-bend nematic (NTB) phase were reported.
Abstract: ABSTRACT 2,7-Substituted fluorenone has a planar and slightly bent aromatic structure and is used as a building block for organic liquid crystals (LCs). Herein, we report for the first time the synthesis, phase-transition behaviour, and mesophase structure of fluorenone-incorporated LC trimers that exhibit an emerging helical twist-bend nematic (NTB) phase. The LC trimers possess a central 2,7-ether-substituted fluorenone and bilateral cyanobiphenyl groups linked via odd alkylene C n H2n spacers (n = 7 or 9) with either ether or thioether outer linkages; these are abbreviated CBOnOFlnOnOCB and CBSnOFlnOnSCB, respectively. The CBOnOFlnOnOCB trimers having only ether linkages display only the conventional nematic (N) phase, whereas the outer thioether-linked CBSnOFlnOnSCB trimers form an NTB phase below the temperature range of the N phase. Furthermore, the phase-transition behaviour of these fluorenone-based LC trimers is compared with that of the corresponding all-biphenyl-based motif trimer analogues, CBOnOBOnOCB and CBSnOBOnSCB.
2 citations
TL;DR: In this paper, an electron-deficient metal-organic framework with one-dimensional channels, Eu2(BBNDI)3(DMF)2 (MOF 1), was successfully constructed based on the naphthalene diimide derivative.
Abstract: Naphthalene diimides (NDIs), a type of electron-deficient dye molecule with high quadrupole moment and excellent redox activity, have been utilized in various fields, such as energy transfer, chemical sensing, anion transport, and photo-/electrochromic materials. In this study, an electron-deficient metal-organic framework with one-dimensional channels, Eu2(BBNDI)3(DMF)2 (MOF 1) (H2BBNDI = N,N'-bis(3-benzoic acid)naphthalene diimide), was successfully constructed based on the naphthalene diimide derivative. Because of the generation of NDI radicals by electron transfer between components, this material exhibits fast-responsive reversible photochromic properties. Moreover, it shows high efficiency and selective oxidation of 2,6-di-tert-butylphenol to its quinone derivative, aldehyde, and dimeric or trimeric phenol derivative by controlling the reaction conditions.
2 citations
TL;DR: In this article , two facile methods involving post-modification on the macrocycles and one-pot co-cyclization from different monomers were used to synthesize heterogeneous macrocycles with fluorenone and fluorenol functional groups.
2 citations
TL;DR: In this paper , the authors describe the development of a series of strong electron-deficient acceptor units, namely, fluorenone imide (FOI) and its derivatives, functionalized with various electron-withdrawing groups.
TL;DR: In this paper , a scanning tunneling microscopy (STM) study of the mixture behavior of three fluorenone derivatives at the liquid-solid interface was performed, and it was shown that the mixing ratio mainly determined the binary outcomes.
Abstract: The precise control of two-dimensional supramolecular co-assemblies presents a research topic related to advance nanotechnology. Here, we report a scanning tunneling microscopy (STM) study of the mixture behavior of three fluorenone derivatives at the liquid-solid interface. The target molecule is F-C12C13 whose structure bears asymmetrical alkyls, whereas the regulating molecules, either F-C12C12 or F-C13C13, are structurally symmetric. By STM imaging of systematic mixtures with various volumes among the sample solutions, we found that the mixing ratio mainly determined the binary outcomes. Compared with F-C12C12, F-C13C13 shows a stronger ability to dominate the patterning, explained by the larger binding and adsorption energies calculated by the force field simulations. Moreover, the odd-even effect exists in the system. Overall, we acquired knowledge about the regulating ability of bi-component supramolecular assembling, especially for structurally asymmetric molecular systems.
TL;DR: In this article , a one-pot formation of new 5- benzyl fluorenone has been found that was Pd-catalysed sp 3 C H/sp 2 C H intermolecular oxidative coupling reaction.
27 Jul 2022
TL;DR: In this paper , the Apelblat model, the Buchowski-Ksiazaczak λh model, CNIBS/R-K model, and the Jouyban-Acree model were used to predict the solubility of 2-bromo-9-fluorenone.
Abstract: This article deals with the saturated solubility and solvation behavior of 2-bromo-9-fluorenone in 10 industrial common solvents and three binary mixed solvents by means of experimental and mathematical correlations. Solubility experiments were investigated using the static equilibrium method combined with high-performance liquid chromatography (HPLC) from 278.15 to 323.15 K at atmospheric pressure. The results showed that the maximum and minimum solubility of 2-bromo-9-fluorenone was 0.0526 (mole fraction) in 1,4-dioxane at 323.15 K and 0.0002 (mole fraction) in methanol at 278.15 K, respectively, and the solubility increased with the increase in temperature in all solvents. Furthermore, the solubility data of 2-bromo-9-fluorenone was analyzed using the Apelblat model, the Buchowski–Ksiazaczak λh model in pure solvents, CNIBS/R-K model, and the Jouyban–Acree model in binary solvent mixtures. By error comparison, the Apelblat model and the CNIBS/R-K model can better predict the solubility of 2-bromo-9-fluorenone. In addition, the solvation behavior was illustrated by the KAT-LSER model in pure solvents, and the result shows that the cohesive energy density in the solution is the main factor affecting 2-bromo-9-fluorenone. Therefore, the solubility data is very important for optimizing the extraction process and recrystallizing 2-bromo-9-fluorenone to obtain a higher yield in industry production.
TL;DR: In this paper , a new series of extended linkers containing polyaromatic chromophores (biphenyl, naphthalene, anthracene, fluorene, 9,9-dimethylfluorene and fluorenone) functionalized with isonicotinoyl moieties have been synthesized by Pd-catalyzed cross-coupling reactions involving isonicamide and the appropriate aromatic dibromide.
Abstract: In this study, a new series of extended linkers containing different polyaromatic chromophores (biphenyl, naphthalene, anthracene, fluorene, 9,9-dimethylfluorene and fluorenone) functionalized with isonicotinoyl moieties have been synthesized by Pd-catalyzed cross-coupling reactions involving isonicotinamide and the appropriate aromatic dibromide. The optimized protocol led to the isolation of the target molecules in good yield and with high purity. These were characterized by 1H NMR, FTIR, MS, and elemental analysis and their solid state structures were solved by single-crystal X-ray diffraction analysis. Electronic absorption and emission spectra were collected both in solution (DMF) and in the solid state. TDDFT calculations were carried out to investigate the effect of the isonicotinoyl moieties on the spectral features of the central chromophores. Although in solution only the linker containing a fluorenone scaffold shows a weak fluorescence, all the isolated linkers turned out to be fluorescent in the solid state, thus paving the way for their use for the fabrication of fluorescent MOFs.
TL;DR: In this article , the authors investigated the photophysical pathways of benzophenone (BP), anthrone (A), and fluorenone (FL) in solvents of different polarity.
Abstract: Combined density functional theory and multireference configuration interaction methods including spin-orbit coupling and spin-vibronic interactions have been used to elucidate the photophysical pathways of benzophenone (BP), anthrone (A) and fluorenone (FL). Our results reveal that the slower S1(1nπ*) T1(3ππ*) passage of FL in the gas phase, as compared to BP and A, originates from the different electronic structures of the T1(3ππ*) states in these compounds and is not related to the planarity of the nuclear arrangement. Temperature effects on the rate constants of intersystem-crossing (ISC), reverse ISC (rISC) and fluorescence have been investigated for FL in solvents of different polarity. Experimentally observed trends for rate constants are well reproduced. A nearly temperature- and solvent-independent, slower down-hill ISC component is attributed to the El-Sayed-forbidden S1(1ππ*) T1(3ππ*) transition in these environments. The faster El-Sayed-allowed S1(1ππ*) T2(3nπ*) ISC requires thermal activation in tetrahydrofuran and acetonitrile solution so that fluorescence may compete against triplet formation. In cyclohexane solution, S1(1ππ*) and T2(3nπ*) are nearly degenerate according to our calculations. Hence S1 T2 ISC and S1 T2 rISC have similar rate constants. If T2 T1 internal conversion could be slowed down by deuteration or perfluorination, for example, FL-derivatives might show delayed fluorescence.
01 Jan 2022
TL;DR: In this article , an organic molecular crystal of the fluorenone derivative 2,7−diphenyl−9H•fluorene−9•one (DPFO) is demonstrated to feature robust high-temperature piezo and ferroelectric properties, with a relatively high local piezoelectric coefficient (d33) of ≈120 pm V−1.
Abstract: Organic polar crystalline materials, featuring the merits of lightweight, flexibility, and low fabrication costs, are emerging as promising alternatives for inorganic ferroelectrics, but so far, they are not competitive. The main reasons are the moderate polar properties of such materials and the fact that the temperature of the phase transition from polar to nonpolar states (Curie point) is typically located near room temperature. The organic molecular crystal of the fluorenone derivative 2,7‐diphenyl‐9H‐fluorene‐9‐one (DPFO) is demonstrated to feature robust high‐temperature piezo‐ and ferro‐electric properties, with a relatively high local piezoelectric coefficient (d33) of ≈120 pm V−1. The origin of the strong piezoelectricity is attributed to the presence of intrinsic domain structures in the DPFO microfiber crystals, originating from intramolecular co‐operation between the central fluorenone backbone and the external phenyl rings that are found stable up to 423 K. Moreover, this intramolecular co‐operation and the corresponding polar properties are found to depend on the thickness of the DPFO microfiber, resulting in a change from ferroelectric (<0.5 µm) to piezoelectric (≥0.5 µm) behavior. Considering the low cost and flexible production of such fluorenone‐based organic lead‐free ferroelectrics, this is a very promising strategy toward technological applications in electromechanical actuators, sensors, energy harvesters, and non‐volatile memory cells.
TL;DR: In this paper , an imide-functionalized fluorenone (FOI) and its cyanated derivative (FCNI) were constructed from a series of polymers with unipolar n-type transport character with a highest electron mobility of 0.11 cm2 V−1 s−1.
Abstract: The development of high-performance n-type polymer semiconductors is powered by the design and synthesis of electron-deficient building blocks with optimized physicochemical properties. By meticulously installing an imide group onto fluorene and its cyanated derivative, we report here two very electron-deficient building blocks, imide-functionalized fluorenone (FOI) and its cyanated derivative (FCNI), both featuring a deep-lying lowest unoccupied molecular orbital energy level down to −4.05 eV and highly coplanar framework, endowing them ideal units for constructing n-type polymers. Thus, a series of polymers are built from them, exhibiting unipolar n-type transport character with a highest electron mobility of 0.11 cm2 V−1 s−1. Hence, FOI and FCNI offer a remarkable platform for accessing high-performance n-type polymers and the imide functionalization of appropriate (hetero)arenes is a powerful strategy for developing polymers with deep-lying LUMOs for n-type organic electronics.
TL;DR: In this article , three benzofluorenone derivatives, BFA, BFB, and BFC, were studied spectroscopically in comparison with 9-fluorenone in solvents of various polarities to better understand the solvatochromism and excited-state deactivation processes in these molecules.