- Electrocatalytic CO2 Reduction with Cis and Trans Conformers of a Rigid Dinuclear Rhenium Complex: Comparing the Monometallic and Cooperative Bimetallic Pathways
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Anthracene-bridged dinuclear rhenium complexes are reported for electrocatalytic carbon dioxide (CO2) reduction to carbon monoxide (CO). Related by hindered rotation of each rhenium active site to either side of the anthracene bridge, cis and trans conformers have been isolated and characterized. Electrochemical studies reveal distinct mechanisms, whereby the cis conformer operates via cooperative bimetallic CO2 activation and conversion and the trans conformer reduces CO2 through well-established single-site and bimolecular pathways analogous to Re(bpy)(CO)3Cl. Higher turnover frequencies are observed for the cis conformer (35.3 s-1) relative to the trans conformer (22.9 s-1), with both outperforming Re(bpy)(CO)3Cl (11.1 s-1). Notably, at low applied potentials, the cis conformer does not catalyze the reductive disproportionation of CO2 to CO and CO32- in contrast to the trans conformer and mononuclear catalyst, demonstrating that the orientation of active sites and structure of the dinuclear cis complex dictate an alternative catalytic pathway. Further, UV-vis spectroelectrochemical experiments demonstrate that the anthracene bridge prevents intramolecular formation of a deactivated Re-Re-bonded dimer. Indeed, the cis conformer also avoids intermolecular Re-Re bond formation.
- Yang, Weiwei,Sinha Roy, Sayontani,Pitts, Winston C.,Nelson, Rebekah L.,Fronczek, Frank R.,Jurss, Jonah W.
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- Synthesis of chlorinated tetracyclic compounds and testing for their potential antidepressant effect in mice
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The synthesis of the tetracyclic compounds 1-(4,5-dichloro-9,10-dihydro-9,10-ethanoanthracen- 11-yl)-N-methylmethanamine (5) and 1-(1,8-dichloro-9,10-dihydro-9,10-ethanoanthracen-11-yl)- N-methylmethanamine (6) as a homologue of the anxiolytic and antidepressant drugs benzoctamine and maprotiline were described. The key intermediate aldehydes (3) and (4) were successfully synthesized via a [4 + 2] cycloaddition between acrolein and 1,8-dichloroanthracene. The synthesized compounds were investigated for antidepressant activity using the forced swimming test. Compounds (5), (6) and (3) showed significant reduction in the mice immobility indicating significant antidepressant effects. These compounds significantly reduced the immobility times at a dose 80 mg/kg by 84.0%, 86.7% and 71.1% respectively.
- Karama, Usama,Sultan, Mujeeb A.,Almansour, Abdulrahman I.,El-Taher, Kamal Eldin
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- Dialkylaluminium-, -gallium-, and -indium-based poly-lewis acids with a 1,8-diethynylanthracene backbone
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Potential host systems based on a rigid 1,8-diethynylanthracendiyl backbone were synthesised by treatment of 1,8-diethynylanthracene with the Group 13 trialkyls AlMe3, GaMe3, InMe3, AlEt3 and GaEt3. The resulting products were characterised by IR and multinuclear NMR spectroscopy, elemental analyses and determination of their crystal structures by X-ray diffraction. The compounds are dimeric in the solid state and comprise two M2C2 heterocycles. Depending on the steric demand of the alkyl substituents at the metal atom, different types of binding modes were observed, which can be classified to lie between the ideals of side-on coordination with almost linear primary M-C≡C units and the 3c-2e coordination with symmetrically bridging alkynyl units in M-C-M bonds. As a solution in THF the dimers are broken into monomers and some are found to undergo ligand scrambling reactions. Moving four-ward: Four Lewis acidic metal atoms held together by rigid hydrocarbon frameworks can be synthesised from 1,8-diethynylanthracene with metal alkyls MR3 (M=Al, Ga, In; R=Me, Et) under alkane elimination (see figure). The arrangement of four close-lying metal functions is broken up in donor solvents like THF.
- Chmiel, Jasmin,Neumann, Beate,Stammler, Hans-Georg,Mitzel, Norbert W.
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- Mono- and Dinuclear Manganese Carbonyls Supported by 1,8-Disubstituted (L = Py, SMe, SH) Anthracene Ligand Scaffolds
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Presented herein is a synthetic scheme to generate symmetric and asymmetric ligands based on a 1,8-disubstituted anthracene scaffold. The metal-binding scaffolds were prepared by aryl chloride activation of 1,8-dichloroanthracene using Suzuki-type couplings facilitated by [Pd(dba)2] as a Pd source; the choice of cocatalyst (XPhos or SPhos) yielded symmetrically or asymmetrically substituted scaffolds (respectively): namely, Anth-SMe2 (3), Anth-N2 (4), and Anth-NSMe (6). The ligands exhibit a nonplanar geometry in the solid state (X-ray), owing to steric hindrance between the anthracene scaffold and the coupled aryl units. To determine the flexibility and binding characteristics of the anthracene-based ligands, the symmetric scaffolds were complexed with [Mn(CO)5Br] to afford the mononuclear species [(Anth-SMe2)Mn(CO)3Br] (8) and [(Anth-N2)Mn(CO)3Br] (9), in which the donor moieties chelate the Mn center in a cis fashion. The asymmetric ligand Anth-NSMe (6) binds preferentially through the py moieties, affording the bis-ligated complex [(Anth-NSMe)2Mn(CO)3Br] (10), wherein the thioether-S donors remain unbound. Alternatively, deprotection of the thioether in 6 affords the free thiol ligand Anth-NSH (7), which more readily binds the Mn center. Complexation of 7 ultimately affords the mixed-valence MnI/MnII dimer of formula [(Anth-NS)3Mn2(CO)3] (11), which exhibits a fac-{Mn(CO)3} unit supported by a triad of bridging thiolates, which are in turn ligated to a supporting Mn(II) center (EPR: |D| = 0.053 cm-1, E/|D| = 0.3, Aiso = -150 MHz). All of the metal complexes have been characterized by single-crystal X-ray diffraction, IR spectroscopy and NMR/EPR measurements - all of which demonstrate that the meta-linked, anthracene-based ligand scaffold is a viable approach for the coordination of metal carbonyls.
- Manes, Taylor A.,Rose, Michael J.
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- Transistors from a conjugated macrocycle molecule: Field and photo effects
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This study explores a conjugated macrocycle molecule and details its synthesis, molecular structure, assemblies in the solid state and application in phototransistors. The Royal Society of Chemistry.
- Zhao, Wei,Tang, Qin,Chan, Hoi Shan,Xu, Jianbin,Lo, Ka Yuen,Miao, Qian
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- Redox properties of a bis-pyridine rhenium carbonyl derived from an anthracene scaffold
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We report the synthesis of a novel bis-pyridine chelate derived from an anthracene scaffold. Complexation of the N2 ligand with rhenium carbonyl affords the Re tricarbonyl bromide complex [(Anth-N2)Re(CO)3Br]. In THF solution, the title complex exhibits two quasi-reversible reductions located near - 2.1 and - 2.5 V vs Fc/Fc+, which are similar to those observed in the free Anth-N2 ligand, suggesting the non-innocent behavior of the complexed anthracene scaffold. Under CO2 atmosphere, the title complex exhibits an electrocatalytic response consistent with CO2 → CO reduction, and the presence of electrocatalytically generated CO was confirmed by bulk electrolysis. These results suggest that alternate locations of redox activity (other than at the Re metal center, pyr donors, or bpy framework) can lead to interesting electrochemical behavior.
- Manes, Taylor A.,Rose, Michael J.
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- Polynuclear Iron(II) Complexes with 2,6-Bis(pyrazol-1-yl)pyridine-anthracene Ligands Exhibiting Highly Distorted High-Spin Centers
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Two bis-tridentate ligands L1 and L2 that contain 2,6-bis(pyrazol-1-yl) pyridine N-donor embraces introduced on a anthracene-acetylene backbone were used for the synthesis of a tetranuclear compound [Fe4(L1)4](CF3SO3)8·7CH3CN (1) and a hexanuclear compound [Fe6(L2)6](CF3SO3)12·18CH3NO2·9H2O (2). The polynuclear structures of both complexes were confirmed by X-ray diffraction studies, which revealed a [2 + 2] grid-like complex cation for 1 and a closed-ring hexagonal molecular architecture for the complex cation in 2. Although both compounds contain anthracene moieties arranged in a face-to-face manner, attempts at [4 + 4] photocyclization remain unsuccessful, which can be explained either by steric restraints or by inhibition of the photo-cycloaddition. Magnetic studies identified gradual and half-complete thermal spin crossover in the tetranuclear grid 1, where 50% of ferrous atoms exhibit thermal as well as photoinduced spin state switching and the remaining half of iron(II) centers are permanently blocked in their high-spin state. On the contrary, the hexanuclear compound 2 exhibits complete blocking in a high-spin state. Analysis of the magnetic data reveals the zero-field splitting parameter |D| ≈ 6-8 cm-1 with a large rhombicity for all high-spin iron(II) atoms in 1 or 2. The electronic structures and the magnetic anisotropies were also investigated by the multireference CASSCF/NEVPT2 method, and intramolecular exchange interactions were calculated by density functional theory methods.
- ?alitro?, Ivan,Herchel, Radovan,Fuhr, Olaf,González-Prieto, Rodrigo,Ruben, Mario
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- Organic light emitting element
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The present invention relates to an organic light emitting element having no distortion of an emission spectrum.
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Paragraph 0236-0240
(2021/01/24)
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- ANTHRACENE DERIVATIVE AND ORGANIC LIGHT EMITTING DEVICE COMPRISING THE SAME
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The present invention relates to an anthracene derivative, which improves low driving voltage and/or lifetime characteristics in an organic light emitting device, and to an organic light emitting device including the same. The anthracene derivative is rep
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Paragraph 0171-0174
(2019/06/04)
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- ANTHRACENE BASED COMPOUND AND ORGANIC LIGHT EMITTING DEVICE COMPRISING THE SAME
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The present invention provides an anthracene-based compound and an organic light emitting device comprising same. Compounds of the present invention have a substituent group containing an aryl group at 1 and 8 positions of anthracene, and have a substituent group containing an aryl group or a heterocyclic group at 10 position, so that the luminous efficiency and lifetime of an organic light emitting device can be greatly improved when the compounds are applied to the organic light emitting device.COPYRIGHT KIPO 2018
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Paragraph 0366-03688
(2018/05/24)
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- ANTHRACENE BASED COMPOUND AND ORGANIC LIGHT EMITTING DEVICE COMPRISING THE SAME
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The present specification provides a compound of chemical formula 1 and an organic light-emitting device including the same. The organic light-emitting device comprises: a first electrode; a second electrode facing the first electrode; and one or more organic material layers provided between the first electrode and the second electrode. When the compound of the present invention is applied to the organic light-emitting device, luminous efficiency and lifespans can be greatly improved.COPYRIGHT KIPO 2017
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Paragraph 0197-0200
(2017/12/17)
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- Halogenated tetracyclic compounds
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The anti-cancer compounds are represented by Formula I: wherein R1 and R2 are either both hydrogen or both halogen, and if R1 and R2 are both hydrogen, R3 and R4 are both halogen, otherwise both R3 and R4 are hydrogen; wherein R5 is CHO or NHCH3; and wherein n is 0 to 3; provided that n is 0 only when R5 is CHO, or a pharmaceutically acceptable salt or isomer thereof.
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Page/Page column 6
(2016/12/16)
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- Antidepressant compounds
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The antidepressant compounds are compounds of the formula: wherein R1 and R2 are either both hydrogen or both halogen (particularly chlorine), and if R1 and R2 are both hydrogen, R3 and R4 are both halogen (particularly chlorine), otherwise both R3 and R4 are hydrogen; or a pharmaceutically acceptable salt thereof. The compounds may be prepared by: (a) reducing 1,8-dihaloanthrquinone with zinc powder in aqueous ammonia, followed by acidic treatment to provide 1,8-dihaloanthracene; (b) Diels-Alder [4+2] cycloaddition reaction of the 1,8-dihaloanthracene and acrolein at room temperature in the presence of boron trifluoride etherate to obtain a mixture of the intermediate compounds 1,8-dihalo-9,10-dihydo-9,10-ethanoanthracene-11-carbaldehyde and 4,5-dihalo-9,10-dihydo-9,10-ethanoanthracene-11-carbaldehyde; (c) separating the mixture of carbaldehydes by column chromatography; and (d) direct reductive amination of the respective carbaldehydes to obtain the corresponding antidepressant compounds of the above formula.
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Page/Page column 5; 6
(2015/09/28)
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- Synthesis of highly emissive 1,8-diaryl anthracene derivatives and fabrication of their micro/nanostructures
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We report a new route for the synthesis of 1,8-diaryl anthracene derivatives (1-6) starting from anthraquinone. The reduction of 1,8-dichoroanthraquinone, followed by aryl-aryl coupling using modified Suzuki-Miyaura reaction conditions, furnished 1,8-diarylanthracene derivatives in a good yield. Detailed photophysical and electrochemical studies show that these anthracene derivatives emit in the blue region with a narrow FWHM and provide high quantum yields (upto 75%). The HOMO and LUMO energy levels of these compounds are in the ranges of -5.62 to 5.71 and 2.68-2.79 eV, respectively. Furthermore, anthracene derivative 5 was used for a surfactant assisted self assembling process to obtain micro/nanostructures. Compound 5 formed microplates in polyvinylpyrrolidone (PVP) and nanowires with an average diameter of ～290 nm in cetyltrimethylammonium bromide (CTAB). The absorption and emission properties of the micro/nanoassemblies of compound 5 showed a red shift of about 12 nm. It was also noticed that the emission intensity of 5 was retained even in the nanoassemblies, and was found to be comparable with that of the solution of 5 in organic solvents. DFT calculations suggest that multiple hydrogen bonding interactions are possible between two interacting monomers of 5. We believe that the possibility of H-bonding interactions in 5 is one of the factors that may aid the formation of micro/nanoassemblies. The blue emitting properties, compatible HOMO and LUMO energy levels, and highly blue emitting micro/nanoassemblies of these compounds make them suitable materials for organic light emitting devices (OLEDs).
- Agarwal, Neeraj,Patil, Manish,Patil, Mahendra
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p. 98447 - 98455
(2015/12/04)
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- Synthesis of novel macrocyclic tetraamides
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A simple and facile route has been described for the synthesis of macrocyclic tetraamides. This method is applicable for the preparation of a variety of macrocyclic tetraamides of various heteroatom substitutions.
- Mehta, Barun Kumar,Rambabu, Dandela,Raja, Guttikonda,Prasad,Fang, Jim-Min,Rao, Mandava Venkata Basaveswara
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p. 756 - 761
(2014/07/07)
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- Phospor, arsenic and antimony compounds based upon diaryl-anellated diaryl-anellated bicyclo'2.2.n! parent substances and catalysts containing same
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Novel compounds of phosphorus, of arsenic and of antimony can be used as ligands to form complexes of metals of transition group VIII which can be used in catalysts for hydroformylation, hydrocyanation, carbonylation, hydrogenations, oligomerization and polymerization of olefins and for metathesis.
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- Tweezers hosts for intercalation of Lewis base guests: Tuning physico-chemical properties of cofacial porphyrin dimers
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The synthesis and both spectroscopic and electrochemical studies of a bis-porphyrinic tweezer are reported, as well as the insertion of Lewis base guests into the host bis-porphyrinic cavity, monitored through physico-chemical characteristics.
- Brettar,Gisselbrecht,Gross,Solladie
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p. 733 - 734
(2007/10/03)
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- Synthesis and characterization of novel cobalt aluminum cofacial porphyrins. First crystal and molecular structure of a heterobimetallic biphenylene pillared cofacial diporphyrin
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The synthesis of the novel family of heterodinuclear complexes (DP)CoAl(OR) (where DP4- is the tetraanion of the diporphyrin biphenylene DPB or the diporphyrin anthracene DPA, and R = CH3, CH2CH3, or CH2C6H5) is reported. These complexes were obtained by selective metalation of the cofacial diporphyrins with cobalt and aluminum. Each (DP)CoAl(OR) complex was characterized by mass spectrometry and UV-vis, IR, ESR, and 1H NMR spectroscopies. Unusually large paramagnetic shifts were observed for the protons on axial ligands bound to aluminum and for the porphyrinic N-H protons of the monocobalt DPB and DPA complexes. Analysis of the paramagnetic shifts indicates that the main contribution to isotropic shifts arises from a through space (or dipolar) interaction of an unpaired electron on cobalt(II). Structural data were deduced from the 1H NMR study. In addition, the molecular structure of the cobalt(II) aluminum(III) ethoxide diporphyrin biphenylene (DPB)CoAl(OCH2CH3) was determined by X-ray diffraction. This is the first crystal structure of a heterobimetallic cofacial diporphyrin. (DPB)CoAl(OCH2CH3) (C78H81N8OCoAl·C7H 8) crystallizes in the triclinic system, space group P1?. Its lattice constants are as follows: a = 13.095 (4) A?, b = 16.836 (3) A?, c = 16.986 (3) A?, α = 87.47 (1)°, β= 70.40 (3)°, γ = 85.90 (2)°, V = 3516 A?3, Z = 2, R(F) = 5.30%, Rw(F) = 5.27%, GOF = 2.5 for 6800 reflections with I ≥ 3σ(I). No metal-metal interaction occurs (Co-Al = 4.370 (1) A?), and both porphyrin moieties are slipped by α = 29.8°. Finally, the tedious synthesis of the (DPA)H4 free-base porphyrin has been extensively modified, and several new reaction steps are presented leading to significant increases in both scale and yield.
- Guilard, Roger,Lopez, Michel Angel,Tabard, Alain,Richard, Philippe,Lecomte, Claude,Brandes, Stéphane,Hutchison, James E.,Collman, James P.
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p. 9877 - 9889
(2007/10/02)
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- Unsymmetrically Substituted 1,8-Diarylanthracenes
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Unsymmetrically substituted 1,8-diarylanthracenes where the aryl rings are m-tolyl (5), o-tolyl (6), and 2,3-dimethylphenyl (7) have been synthesized; the barriers to aryl ring rotation in these hydrocarbons were found to be 5.3, 10.4, and 16.3 kcal/mol, respectively.Addition of either an acetoxyl (14) or a methyl (15) substituent at C-9 of the dixylylanthracene gave mixtures of cis and trans isomers that also exhibited rotation of an aryl ring within the temperature range 25-120 deg C.X-ray crystal structures for the cis- (14b) and trans- (14a) 9-acetoxydixylylanthracenes demonstrated significant distortion in the geometry of the anthracene ring, permitting rotation of the aryl rings with unexpected ease in solutions at temperatures above 100 deg C.
- House, Herbert O.,Hrabie, Joseph A.,VanDerveer, Don
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p. 921 - 929
(2007/10/02)
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