Showing papers on "Fluorenone published in 2013"
TL;DR: Biologically interesting fluorenone, xanthone and anthrone derivatives have been prepared via an intramolecular oxidative acylation process that uses a catalytic amount of a quaternary ammonium salt in the presence of a persulfate oxidant.
Abstract: Biologically interesting fluorenone, xanthone and anthrone derivatives have been prepared via an intramolecular oxidative acylation process. This novel direct acylation reaction proceeded without the aid of any transition metals, acids or bases, and uses a catalytic amount of a quaternary ammonium salt in the presence of a persulfate oxidant. Initial mechanistic studies have been carried out to elucidate the reaction pathway.
154 citations
TL;DR: Zhang et al. as mentioned in this paper presented a metal organic framework with zinc as the metal cation by a facile mechanochemical synthesis method, and the obtained Zn-FDC MOF features a pillared structure, in which the fluorenone chromophore units exhibit a highly ordered arrangement.
Abstract: The regular assembly of organic chromophores into ordered supramolecular solids has received much attention for developing high-performance luminescent materials. Herein, a fluorenone-containing dicarboxylate (FDC) has been organized into a metal organic framework (MOF) with zinc as the metal cation by a facile mechanochemical synthesis method. The obtained Zn–FDC MOF features a pillared structure, in which the fluorenone chromophore units exhibit a highly ordered arrangement. Compared with the pristine FDC sample, the Zn–FDC MOF presents blue-shifted emission, as well as enhanced photoluminescence quantum yield and fluorescence lifetime, demonstrating the ordered arrangement of the FDC within the MOF is beneficial for the improvement of the photo-related properties of the organic chromophore. Moreover, the Zn–FDC MOF film exhibits well-defined polarized photoemission with a polarized anisotropy of 0.10–0.15. Periodic density functional theoretical (DFT) calculations illustrate that no energy/electronic transfer occurs between the chromophore and the metal cation, and the valence electrons localized in the FDC are confined effectively due to the energy blocking action of the metal cations. Combining experimental and theoretical studies on the luminescent MOF system, this work not only gives a rapid and environmentally friendly way to prepare a highly ordered inorganic–organic hybrid system with improved fluorescence properties, but also provides a deep understanding of the electronic structure of the 2D pillared MOF. It is expected that the Zn–FDC MOF can be potentially applied as a polarized fluorescence material.
52 citations
TL;DR: Fluorenone derivatives with various lengths of peripheral alkyl chains (with carbon numbers of n = 12-18) were synthesized, and their self-assembled adlayers were investigated in solvents as mentioned in this paper.
Abstract: Fluorenone derivatives (F–OCn) with various lengths of peripheral alkyl chains (with carbon numbers of n = 12–18) were synthesized, and their self-assembled adlayers were investigated in solvents w...
51 citations
TL;DR: A fluorenone based alternating copolymer with a furan based fused aromatic moiety with a small band gap with a lower HOMO value has been designed and synthesized and tested as the active layer in organic thin-film transistors.
40 citations
TL;DR: A novel solution processable fluorenone based small molecule with an Aggregation Induced Emission Enhancement (AIEE) property and the presence of the fluore None moiety in FF triggers the AIEE property.
39 citations
TL;DR: Fluorenone derivatives were generated from aryl-substituted propiolates via a cobalt-catalyzed Diels-Alder reaction/DDQ-oxidation and Friedel-Crafts-type cyclization and several functional groups are tolerated, and good to excellent overall yields could be achieved.
35 citations
TL;DR: The absorption spectrum of fluorenone in zeolite L is calculated from first-principles simulations and the main factors affecting the spectrum of the chromophore in hydrated zeolITE L are revealed.
Abstract: The absorption spectrum of fluorenone in zeolite L is calculated from first-principles simulations. The broadening of each band is obtained from the explicit treatment of the interactions between the chromophore and its environment in the statistical ensemble. The comparison between the simulated and measured spectra reveals the main factors affecting the spectrum of the chromophore in hydrated zeolite L. Whereas each distinguishable band is found to originate from a single electronic transition, the bandwidth is determined by the statistical nature of the environment of the fluorenone molecule. The K+⋯OC motif is retained in all conformations. Although the interactions between K+ and the fluorenone carbonyl group result in an average lengthening of the CO bond and in a redshift of the lowest energy absorption band compared to gas phase or non-polar solvents, the magnitude of this shift is noticeably smaller than the total shift. An important factor affecting the shape of the band is fluorenone's orientation, which is strongly affected by the presence of water. The effect of direct interactions between fluorenone and water is, however, negligible.
34 citations
TL;DR: In this article, four new organic dyes (F1 -F4 ) comprising the triarylamine or fluorene unit as an electron-donating group, a less commonly used fluorenone spacer and a cyanoacrylic acid as the anchoring group in the molecular framework were synthesized, characterized and utilized in dye-sensitized solar cells (DSSCs).
30 citations
TL;DR: In this article, experimental and theoretical studies on the donor-dependent optical characteristics of two D-pi A-pi-D type linear fluorenone-based conjugated oligomers are presented, where fluorene and triphenylamine act as the donors, respectively.
28 citations
TL;DR: In this paper, the synthesis, chemical characterization and optical studies of three novel fluorene derivatives are reported, which comprise a D-A-D architecture with fluorenes moieties as donor groups and fluorenone or benzothiadiazole derivatives as acceptor groups.
26 citations
TL;DR: In this article, a novel chromogenic receptor, 1-(naphthalen-1yl)-3-(9-oxo-9 H -fluoren-1-yl)urea ( 1 ), utilizing fluorenone and naphthalene moieties as signaling groups was designed and synthesized.
TL;DR: In this article, a mechanism for the synthesis of catalysts for the hydrohydrazination of carbodiimides was proposed, which is closely related to that previously established for the catalysts of alkynes and allenes, and is consistent with the results of a kinetic study.
TL;DR: In this paper, the effects of fluorene-ethylene (FE) spacers on photo-physical properties of conjugated oligomers were compared. And the authors showed that the difference between donor-dependent excited state lifetimes of oligomers becomes less obvious after the introduction of FE units, but the difference in two-photon characteristics between oligomers with different donors is also decreased.
TL;DR: The negligible difference in the emission maximum between solution and solid state indicates that the vibrationally relaxed excited state, assigned as MLCT/IL, adopts a structure closely similar to the crystallographically determined one.
Abstract: Condensation of ethylenediamine with fluorenone produces a diimine with two terminal fluorophores and a flexible central backbone, N,N′-bis-fluoren-9-ylidene-ethane-1,2-diamine (flen). The diimine reacts with [Cu(MeCN)4]BF4 or CuI to produce a homoleptic compound of the stoichiometry [Cu(flen)2]BF4 or [Cu(flen)2][CuI2] respectively. Both complexes emit in the red part of the spectrum, with a maximum around 720 nm and excited state lifetime of 0.2 μs in solution. The crystal structures of the complexes reveal almost an identical Cu(I)-diimine core where the predominant forces are the intramolecular π–π interactions between the fluorenone aromatic systems resulting in considerably distorted coordination environments. The negligible difference in the emission maximum between solution and solid state indicates that the vibrationally relaxed excited state, assigned as MLCT/IL, adopts a structure closely similar to the crystallographically determined one.
TL;DR: A diketopyrrolopyrrole with fluorenone based low band gap alternating copolymer (PDPPT-alt-FN) has been synthesized via Suzuki coupling and exhibits a deep HOMO level with a lower band gap.
Abstract: A diketopyrrolopyrrole (DPP) with fluorenone (FN) based low band gap alternating copolymer (PDPPT-alt-FN) has been synthesized via Suzuki coupling. PDPPT-alt-FN exhibits a deep HOMO level with a lower band gap. Fabricated organic thin film transistors using PDPPT-alt-FN as a channel semiconductor show p-channel behaviour with the highest hole mobility of 0.083 cm2 V−1 s−1 measured in air.
TL;DR: In this article, the effect of π-spacer on the optical properties of two novel Dπ-A-π-D type fluorenone-based linear conjugated oligomers was investigated.
Abstract: Effect of π-spacer on the optical properties of two novel D-π-A-π-D type fluorenone-based linear conjugated oligomers 2,7-di((E)-2-(10-octyl-10H- phenothiazin-3-yl)vinyl)-9-fluorenone (P-FO-P) and 2,7-di((E)-2-(9,9-dioctyl-7-((E)-2-(10-octyl-10H-phenothiazin-3-yl)vinyl)-9H-fluoren-2-yl)vinyl)-9-fluorenone (P-F-FO-F-P) is investigated, where fluorenone and phenothiazine units act as the electron acceptor and donor moieties, respectively. We observe that the fluorene–ethylene (FE) spacer could modulate the steady-state spectral features. Quantum chemical calculations offer complementary information regarding the frontier orbitals and molecular structures, which confirm that the intramolecular charge transfer (ICT) transition exists in the HOMO–LUMO transitions. Nonlinear optical measurements show that the FE spacer could improve the two-photon photoluminescence yield and enhance the two-photon absorption cross-section. The results of transient absorption measurements exhibit that an ICT state exists in the relaxation process of excited state, and its generation process is obviously accelerated with the introduction of π-spacer.
TL;DR: In this article, the authors show that diarylamino-substituted fluorenones give highly persistent radical cations, some of which can be stored in the solid state for months.
TL;DR: A concise and facile synthesis of 2,8-disubstituted dithieno[3,2-b:6, 7-b]fluorenes starting from 2,7-dihydroxyfluorenone is reported.
Abstract: A concise and facile synthesis of 2,8-disubstituted dithieno[3,2-b:6,7-b]fluorenes starting from 2,7-dihydroxyfluorenone is reported. The key step involved is the tandem annulation–reduction of a 3,6-dichloro-2,7-di(alkynyl)fluorenone using Na2S·9H2O as a sulfur surrogate and reductant. The final dithiophene-fused fluorenes are obtained in reasonable yields (23–43%).
TL;DR: In this article, the hydrogen-bonding of fluorenone (FN) and FN derivatives (FODs) in hydrogen-donating methanol solvent has been investigated using time-dependent density functional theory (TDDFT) method.
Abstract: The time-dependent density functional theory (TDDFT) method has been carried out to study the hydrogen-bonding of fluorenone (FN) and FN derivatives (FODs) in hydrogen-donating methanol solvent. The ground-state geometry structure optimizations, electronic excitation energies and corresponding oscillation strengths of the low-lying electronically excited states for the isolated FN, FODs and methanol monomers and their corresponding complexes have been calculated using DFT and TDDFT methods respectively. Comparing FODs with FN, we have obtained the strength change of the hydrogen bonds and the electronic spectral shift in different excited states. At the same time, the nature of the FODs in the electronic excited states and the influence of the different substituent group have been summed up.
TL;DR: Wang et al. as mentioned in this paper, 2011CB808501] and National Natural Science Foundation of China [21073168, 21290193], National Basic Research Program of China
Abstract: National Natural Science Foundation of China [21073168, 21290193]; National Basic Research Program of China [2011CB808501]
Patent•
25 Dec 2013
TL;DR: In this article, a method for preparing 9-fluorenone through using industrial fluorene is characterized in that a raw material industrial florene (having a purity of above 95%) reacts with an oxygen-containing gas at a low temperature under stirring in a solvent comprising toluene and water under the action of an alkali as a catalyst and a quaternary ammonium salt as a phase transfer agent.
Abstract: A method for preparing 9-fluorenone through using industrial fluorene is characterized in that a raw material industrial fluorene (having a purity of above 95%) reacts with an oxygen-containing gas at a low temperature under stirring in a solvent comprising toluene and water under the action of an alkali as a catalyst and a quaternary ammonium salt as a phase transfer agent to form 9-fluorenone. The fluorene conversion rate can reach 100% under appropriate reaction conditions. The alkali and solvent recovered in the invention can be recycled without special complex treatment processes, so it is beneficial for industrialization; and in the invention, the recycle of the catalyst alkali, the phase transfer agent quaternary ammonium salt and the solvent, a recrystallization technology and the like are researched, pure fluorenone is obtained, and the complete preparation method of the 9-fluorenone is provided.
TL;DR: The rate constants for the bimolecular ET process in both normal organic solvents and RTILs have been found to be nearly equal to diffusion controlled rate calculated for the corresponding solvent.
Abstract: We report electron transfer (ET) process from the long-lived radical anions of pyrene and benzophenone to molecular acceptors, e.g., benzophenone and fluorenone, respectively, in two RTIL media, na...
Patent•
03 Apr 2013
TL;DR: In this paper, the lignans compounds are extracted from the raw materials including dried branches, leaves and/or fruits of schisandra chinensis, and the preparation method comprises the steps of extract extraction, organic solvent extraction, silica column chromatography and high pressure liquid chromatography separation.
Abstract: The invention discloses lignans compounds and a preparation method and application thereof. According to the structural formulas of the compounds, R1 is -OH, R2 is -OCH3, a molecular formula is C20H24O8, and one compound is named as marphenol E; and -OCH2O- is between R1 and R2, a molecular formula is C20H22O8, and the other compound is named as marphenol F. According to the preparation method, the lignans compounds are prepared from the raw materials including dried branches, leaves and/or fruits of schisandra chinensis. The preparation method comprises the steps of extract extraction, organic solvent extraction, silica column chromatography and high pressure liquid chromatography separation of the raw materials. The invention further discloses the application of the lignans compounds to preparation of anti-AIDS medicines. According to cytotoxicity detection on C8166 host cells and inhibition tests on an HIV-1IIIB-induced cytopathic effect (CPE) of the C8166, the two fluorenone compounds, namely the marphenol E and the marphenol F, have good anti-HIV-1 activity, the EC50 values of the two fluorenone compounds are respectively 3.47 mug/mL and 2.97 mug/mL, and the therapeutic index (IT) values of the two fluorenone compounds are respectively 21.18 and 27.64. The fluorenone compounds have novel structures and high activity, and can serve as guiding compounds of the anti-AIDS medicines.
Patent•
02 Jan 2013
TL;DR: The asymmetric spirobifluorene compounds derived from functional group conversion on different fluorene rings of the invention is low in product cost, simple in synthetic route, high in yield, and easy for industrial production; the compounds have special spiro-conjugated effect, good dissolvability and high heat stability as mentioned in this paper.
Abstract: The invention relates to asymmetric spirobifluorene compounds derived from functional group conversion on different fluorene rings. The products of the invention have a structural formula of (I), wherein R1 and R2 are various electron-withdrawing or electron-donating groups such as various alkanes, substituted aryl, substituted heterocyclic radical, substituted alkylene, substituted amino, chlorine, bromine, and iodine, and R1 is different from R2. Cheap and easily available 4,4'-dimethyl biphenyl is used as a raw material, and the compound (I) is obtained by steps of bromination, reaction with 2,7-diX fluorenone through, and respective conversion of methyls and X groups on different fluorene rings into various functional groups. The asymmetric spirobifluorene compounds derived from functional group conversion on different fluorene rings of the invention is low in product cost, simple in synthetic route, high in yield, and easy for industrial production; the compounds have special spiro-conjugated effect, good dissolvability and high heat stability, is widely applicable to fields of organic light-emitting display, organic non-linear materials, fluorescent probes, and the like.
TL;DR: In this article, the dynamics of photoinduced electron transfer (PET) reactions between the singlet (S 1 ) and the triplet (T 1 ) excited states of 9-fluorenone or simply fluorenone and a few aromatic and aliphatic amines have been investigated under both diffusive and non-diffusive conditions.
Abstract: Dynamics of photoinduced electron transfer (PET) reactions between the singlet (S 1 ) and the triplet (T 1 ) excited states of 9-fluorenone or simply fluorenone and a few aromatic and aliphatic amines have been investigated under both diffusive and non-diffusive conditions. Formation of the fluorenone anion radical confirms the electron transfer (ET) from the amines to the excited states of fluorenone. Rate constants for both the forward ET process, k CS , and the charge recombination (CR) process, k CR , have been determined in acetonitrile and benzene solutions. Sub-picosecond time-resolved transient absorption study reveals that quenching of the S 1 state in acetonitrile is biexponential. Lifetime of one of these two components is independent of quencher concentration and its values determined for aniline (7.1 ps), dimethylaniline (8.5 ps) and diethylaniline (6.8 ps) are very similar. It represents the non-diffusive component of the PET reaction. But the lifetime of the other component decreases with increasing quencher concentration and the rate of this diffusive component of the PET reaction nearly agrees with the value determined using steady state fluorescence quenching method. To determine the intrinsic values of the rates of the PET reactions involving the S 1 state of fluorenone, the PET dynamics have been studied in these three neat donor solvents. The forward ET process is biexponential and the lifetimes of these two components are very similar in these solvents and vary in the range 0.3–0.5 ps and 6–8 ps. Nonexponential dynamics of the PET reactions conducted in neat donor–solvents have been discussed using a simple solvent reorientational model.
TL;DR: The structures of 1a, 1b, 2a, 2b, 3a, 3b and 4 are determined by X-ray diffraction and bond lengths and DFT studies reveal greater π-delocalisation than in 1-3.
Abstract: Reaction of Ph2CO and py2CO with Li[N(SiMe3)2] and ArSCl (Ar = 2-O2NC6H4, 2,4-(O2N)2C6H3) yielded Ph2CNSAr (1a and 1b respectively) and py2CNSAr (2a and 2b respectively). Reaction of fluorenone, C12H8CO with Li[N(SiMe3)2] and ArSCl under similar conditions afforded C12H8CNSAr (3a and 3b respectively). Whilst reaction of fluorenone with Li[N(SiMe3)2] and SCl2 in a 2:2:1 ratio afforded the sulfur-diimide, C12H8CNSNCC12H8 (4), reaction of py2CO with Li[N(SiMe3)2] and SCl2 under similar conditions afforded the thiazyl heterocycle [py2CNS]Cl (5) via intramolecular coordination. The structures of 1a, 1b, 2a, 2b, 3a, 3b and 4 are determined by X-ray diffraction. In the case of 4, bond lengths and DFT studies reveal greater π-delocalisation than in 1–3.
Abstract: Bromination of 2,7-dinitro-9,10-phenanthrenequinone, 2,5-dinitro-9,10-phenanthrenequinone, and 2,4,7-trinitrofluorenone with bromine in concentrated sulfuric acid in the presence of acetic acid gave, respectively, 4-bromo-2,7-dinitro-9,10-phenanthrenequinone, 2-bromo-4,7-dinitro-9,10-phenanthrenequinone, and 5-bromo-2,4,7-trinitrofluorenone. No bromination occurred in the absence of nitric acid. The same brominated polynitro compounds can be obtained under analogous conditions directly from unsubstituted 9,10-phenanthrenequinone and fluorenone.
Patent•
23 Oct 2013
TL;DR: The fluorenone derivative can be used as a precursor in a synthesis and development process of a medicament, and the structural specificity of the fluoresnone derivative endows the fluornone derivative with certain use value in the field of organic synthesis as discussed by the authors.
Abstract: The invention relates to a fluorenone derivative and a preparation method thereof The fluorenone derivative is a poly-substituted fluorenone derivative, and the preparation method of the fluorenone derivative comprises the following steps: a, the synthesis of a substrate; b, the catalysis by palladium, and C, the purification of a product The fluorenone derivative can be used as a precursor in a synthesis and development process of a medicament, and the structural specificity of the fluorenone derivative endows the fluorenone derivative with certain use value in the field of organic synthesis
Patent•
05 Jun 2013
TL;DR: In this article, a method for the preparation of fluorene derivatives having a multi-photon absorption characteristic, a preparation method and applications thereof, was presented, where the materials can be used in ultrafast laser amplitude stabilizers, and the method has characteristics of mild conditions, high reaction selectivity and low cost.
Abstract: The present invention provides fluorene derivatives having a multi-photon absorption characteristic, a preparation method and applications thereof. According to the preparation method, fluorene is adopted as a raw material, potassium hydroxide is adopted as a catalyst, oxidation is performed to prepare 9-fluorenone, a bromination reaction is adopted to link bromine to the fluorene ring, the obtained compound and phenylacetylene containing an ether group (-O-R) generate a fluorenone derivative under an effect of the catalyst, and the fluorenone derivative reacts with a Lawesson reagent to generate a series of fluorene derivative materials having a multi-photon absorption characteristic, wherein the method has characteristics of mild conditions, high reaction selectivity and low cost. The materials can be used in ultrafast laser amplitude stabilizers.