- High molecular weight CuII coordination polymers and their characterisation by electrospray mass spectrometry (ESMS)
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The ligands L and ligand L* self-assemble with CuII in different solvents to give a mixture of coordination polymers. These artificial nanostructures have been characterised with the help of ESMS, the only analytical tool that allows their unambiguous characterisation. Kinetic and thermodynamic ESMS studies have excluded the possibility that these compounds form aggregates during the ES process.
- Nierengarten, Helene,Rojo, Javier,Leize, Emmanuelle,Lehn, Jean-Marie,Van Dorsselaer, Alain
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Read Online
- Unprecedented One-Pot Reaction towards Chiral, Non-Racemic Copper(I) Complexes of [2.2]Paracyclophane-Based P,N-Ligands
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Herein, we report a simple one-pot route to enantiopure copper(I) complexes featuring a unique [2.2]paracyclophane-based P,N-ligand system. Phosphine and pyridine moieties can be varied allowing the modular synthesis of these rigid and stable [2.2]paracyclophane-based P,N-ligands. These P,N-ligands are a new ligand class for different transition-metal complexes, which is shown exemplarily for palladium(II).
- Braun, Carolin,Nieger, Martin,Br?se, Stefan
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Read Online
- Synthesis, photophysics, and reverse saturable absorption of 7-(benzothiazol-2-yl)-9,9-di(2-ethylhexyl)-9: H -fluoren-2-yl tethered [Ir(bpy)(ppy)2]PF6 and Ir(ppy)3 complexes (bpy = 2,2′-bipyridine, ppy = 2-phenylpyridine)
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We report the synthesis, photophysics, and reverse saturable absorption of five iridium(iii) complexes 1-5 with 7-(benzothiazol-2-yl)-9,9-di(2-ethylhexyl)-9H-fluoren-2-yl (BTF) pendant attached to the 2-phenylpyridine ligand (1: [Ir(bpy)(BTF-ppy)2]PF6; 2: [Ir(bpy)(BTF - ppy)2]PF6; 3: Ir(ppy)2(BTF-ppy); 4: Ir(ppy)(BTF-ppy)2; 5: (BTF-ppy)3, where bpy = 2,2′-bipyridine and ppy = 2-phenylpyridine). The effects of the extended π-conjugation of the ppy ligand and the increased number of BTF-ppy ligand, as well as the effects of neutral complex vs. cationic complex were evaluated. All complexes exhibit predominantly ligand-localized 1π,π? transitions below 430 nm and charge-transfer transitions between 430 and 550 nm. They all emit at room temperature and at 77 K, mainly from the metal-to-ligand charge transfer (3MLCT)/ligand-to-ligand charge transfer (3LLCT) states for 1 and 2, and from the BTF-ppy ligand-centered 3π,π? excited states with significant contributions from the 3MLCT states for 3-5. The triplet excited states of 1-5 also manifest broad transient absorption (TA) in the visible to the near-IR spectral region. The electronic absorption, emission, and ns transient absorption are all red-shifted by extending the π-conjugation of the ppy ligand or increasing the number of BTF-ppy ligand. The energies of the lowest singlet and triplet excited states of the neutral complex 4 are lowered compared to those of its cationic counterpart 1; while the transient absorbing triplet excited state of 4 is much longer lived than that of 1. These complexes all exhibit strong reverse saturable absorption (RSA) for ns laser pulses at 532 nm, with a trend of 5 ex/σ0) at 532 nm with the triplet quantum yield also playing a role for complexes 3-5. It appears that the increased number of BTF-ppy ligand reduces the RSA of the neutral complexes while the increased π-conjugation of the ppy ligand in the cationic complexes improves the RSA. However, the neutral complex 4 exhibits a weaker RSA at 532 nm than its cationic counterpart 1.
- Li, Zhongjing,Li, Hui,Gifford, Brendan J.,Peiris, Wadumesthrige D. N.,Kilina, Svetlana,Sun, Wenfang
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Read Online
- A Near-Infrared-II Emissive Chromium(III) Complex
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The combination of π-donating amido with π-accepting pyridine coordination units in a tridentate chelate ligand causes a strong nephelauxetic effect in a homoleptic CrIII complex, which shifts its luminescence to the NIR-II spectral range. Previously explored CrIII polypyridine complexes typically emit between 727 and 778 nm (in the red to NIR-I spectral region), and ligand design strategies have so far concentrated on optimizing the ligand field strength. The present work takes a fundamentally different approach and focusses on increasing metal–ligand bond covalence to shift the ruby-like 2E emission of CrIII to 1067 nm at 77 K.
- Jiménez, Juan-Ramón,Pfund, Bj?rn,Piguet, Claude,Prescimone, Alessandro,Sinha, Narayan,Wenger, Oliver S.
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Read Online
- Illuminating Stannylation
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We have developed photoboosted stannylation reactions of terminal alkynes (linear-selective hydrostannylation) and fluoroarenes (defluorostannylation), in which the stannyl anion is photoexcited to an excited triplet (T1) stannyl diradical species. This u
- Sakamoto, Kyoka,Nagashima, Yuki,Wang, Chao,Miyamoto, Kazunori,Tanaka, Ken,Uchiyama, Masanobu
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supporting information
p. 5629 - 5635
(2021/05/04)
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- The kinetics and mechanism of interconversion within a system of [Fe2L 3]4+helicates and [Fe4L 6]8+cages
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Nature builds simple molecules into highly complex assemblies, which are involved in all fundamental processes of life. Some of the most intriguing biological assemblies are those that can be precisely reconfigured to achieve different functions using the same building blocks. Understanding the reconfiguration of synthetic self-assembled systems will allow us to better understand the complexity of proteins and design useful artificial chemical systems. Here we have prepared a relatively simple system in which two distinct self-assembled structures, a [Fe2L3]4+ helicate and a [Fe4L6]8+ cage that are formed from the same precursors, coexist at equilibrium. We have measured the rates of interconversion of these two species and propose a mechanism for the transformation.
- Al-Fayaad, Hydar A.,Arachchige, Kasun S. A.,Brock, Aidan J.,Clegg, Jack K.,Luis, Ena T.,McMurtrie, John C.,Micallef, Aaron S.,Siddique, Rashid G.,Thoburn, John D.
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supporting information
p. 4918 - 4921
(2021/05/26)
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- Dynamer and Metallodynamer Interconversion: An Alternative View to Metal Ion Complexation
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A bifunctional molecule containing both a bidentate binding site for metal ions and an aminopyrimidine H-bond donor-acceptor site has been synthesized, and its properties, in its free and coordinated forms, have been established in solution and in the solid state by analytical and spectroscopic methods as well as by X-ray structure determinations. Structural characterization has shown that it forms a one-dimensional H-bonded polymeric assembly in the solid state, while spectroscopic measurements indicate that it also aggregates in solution. The reaction of a simple Fe(II) salt with this assembly results in the emergence of two geometrical isomers of the complex: [FeL3](BF4)2·9H2O - C1 (meridional, mer) and [FeL3]2(SiF6)(BF4)2·12H2O - C2 (facial, fac). While, complex C1 in the solid state generates a one-dimensional H-bonded polymer involving just two ligands on each Fe center, with the chirality of the complex units alternating along the polymer chain, the structure of complex C2 shows NH···N interactions seen in both the ligand and mer complex (C1) structures to be completely absent. Physicochemical properties of the free and complexed ligand differ substantially.
- Brzechwa-Chodzyńska, Anna,Gilski, Miros?aw,Harrowfield, Jack M.,Stefankiewicz, Artur R.,Zieliński, Micha?
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supporting information
p. 8552 - 8561
(2020/07/04)
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- Observation of an inversion in photophysical tuning in a systematic study of luminescent triazole-based osmium(II) complexes
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In a systematic survey of luminescent bis(terdentate) osmium(II) complexes, a tipping point involving a reversal in photophysical tuning is observed whereby increasing stabilization of the ligand-based lowest unoccupied molecular orbital (LUMO) results in a blue shift in the optical absorption and emission bands. The complexes [Os(N^N′^N″)2]2+ [N^N′^N″ = 2,6-bis(1-phenyl-1,2,3-triazol-4-yl)pyridine (Os1), 2,6-bis(1-benzyl-1,2,3-triazol-4-yl)pyrazine (Os2), 6-(1-benzyl-1,2,3-triazol-4-yl)-2,2′-bipyridyl (Os3), 2-(pyrid-2-yl)-6-(1-benzyl-1,2,3-triazol-4-yl)pyrazine (Os4), 2-(pyrazin-2-yl)-6-(1-benzyl-1,2,3-triazol-4-yl)pyridine (Os5), and 6-(1-benzyl-1,2,3-triazol-4-yl)-2,2′-bipyrazinyl (Os6)] have been prepared and characterized, and all complexes display phosphorescence ranging from the orange to near-IR regions of the spectrum. Replacement of the central pyridine in the ligands of Os1 by the more π-accepting pyrazine in Os2 results in a 55 nm red shift in the triplet metal-to-ligand charge-transfer-based emission band, while a larger red shift of 107 nm is observed for the replacement of one of the triazole donors in the ligands of Os1 by a second pyridine ring in Os3 (λemmax = 702 nm). Interestingly, replacement of the central pyridine ring in the ligands of Os3 by pyrazine (Os4, λemmax = 702 nm) fails to result in a further red shift in the emission band. Reversal of the relative positions of the pyridine and pyrazine donors in Os5 (λemmax = 733 nm) compared to Os4 does indeed result in the expected red shift in the emission with respect to that for Os3 based on the increased π-acceptor character of the ligands present. However, an inversion in emission tuning is observed for Os6, in which the incorporation of a second pyrazine donor in the ligand architecture results in a blue shift in the optical absorption and emission maxima (λemmax = 710 nm). Electrochemical studies reveal that while incorporating pyrazine in the ligands indeed results in an expected anodic shift in the first reduction potential through stabilization of the ligand-based LUMO, there is also a concomitant anodic shift in the OsII/OsIII-based oxidation potential. This stabilization of the metal-based highest occupied molecular orbital (HOMO) thus nullifies the effect of stabilization of the LUMO in Os4 compared to Os3, resulting in these complexes having coincident emission maxima. For Os6, stabilization of the HOMO through the incorporation of two pyrazine donors in the ligand structure now exceeds stabilization of the LUMO, resulting in a larger HOMO?LUMO gap and a counterintuitive blue shift in the optical properties in comparison with those of Os5. While it is known that the replacement of ligands (e.g., replacing bipyridyl with bipyrazinyl) can result in a larger HOMO?LUMO energy gap through greater stabilization of the HOMO, these results importantly allow us to capture the tipping point at which this inversion in photophysical tuning occurs. This therefore enables us to explore the limits available in emission tuning with a relatively simple and minimalist ligand structure.
- Scattergood, Paul A.,Roberts, James,Omar, Salem A.E.,Elliott, Paul I.P.
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p. 8607 - 8621
(2019/08/21)
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- Synthesis and Characterization of 2-(2-Pyridinyl)pyrazine and 2,2′-Bipyrazine Derivatives
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A convenient and high yield preparation of derivatives of 2-(2-pyridinyl)pyrazine and derivatives of 2,2′-bipyrazine compounds from their derivatives of bromopyrazine using Stille coupling is reported. X-ray structures, elemental analyses, 1H, 13C-NMR, and mass spectral data of the compounds are given.
- KomReddy, Venugopal,Rillema, D. Paul,Nguyen, Huy,Kadel, Lava
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p. 972 - 979
(2019/02/05)
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- Aromatic compound and organoelectroluminescent device comprising the compound
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The present invention relates to a novel aromatic compound and an organic electroluminescent device comprising the same. The present invention relates to an organic electroluminescent device including an aromatic compound. (by machine translation)
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Paragraph 0224-0230
(2019/12/10)
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- ATF6 INHIBITORS AND USES THEREOF
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Compounds as inhibitors of Activating Transcription Factor 6 (ATF6) are provided. The compounds may find use as therapeutic agents for the treatment of diseases or disorders mediated by ATF6 and may find particular use in the treatment of viral infections, neurodegenerative diseases, vascular diseases, or cancer.
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Paragraph 0378; 0377
(2019/10/29)
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- Design, synthesis and biological evaluation of deuterated Vismodegib for improving pharmacokinetic properties
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Vismodegib is an oral and high selective hedgehog (Hh) inhibitor used for the treatment of basal cell carcinoma (BCC). In this work, analogs of Vismodegib with deuterium-for-hydrogen replacement at certain metabolically active sites were prepared and found to have a better pharmacokinetic properties in mice. In particular, deuterated compound SKLB-C2211 obviously altered the blood circulation behavior compared to its prototype, which was demonstrated by significantly prolonged blood circulation half-life time (t1/2) and increased AUC0→∞. These results suggested SKLB-C2211 had the potential to be a long-acting inhibitor against Hh signaling pathway, and laid the foundation for the further research of its druggability.
- Wang, Fangying,Jiang, Hongxia,Deng, Yufang,Yu, Jiang,Zhan, Miao,Zhao, Lifeng,Chen, Yuanwei
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p. 2399 - 2402
(2018/06/25)
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- Stannylation of Aryl Halides, Stille Cross-Coupling, and One-Pot, Two-Step Stannylation/Stille Cross-Coupling Reactions under Solvent-Free Conditions
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Solvent-free protocols for palladium-catalyzed stannylation of aryl halides, Stille cross-coupling, and one-pot, two-step stannylation/Stille cross-coupling (SSC) are reported for the first time. (Het)aryl halides bearing acceptor, donor, as well as sterically demanding substituents are stannylated and/or coupled in high yields. The reactions are catalyzed by conventional palladium(II) acetate/PCy3 [Pd(OAc)2/PCy3] under air, using available base CsF, and without the use of high purity reagents. The developed synthetic procedures are versatile, robust, and easily scalable. The absence of solvent, and the elimination of isolation procedures of aryl stannanes makes the SSC protocol simple, step economical, and highly efficient for the synthesis of biaryls in a one-pot two-step procedure.
- Gribanov, Pavel S.,Golenko, Yulia D.,Topchiy, Maxim A.,Minaeva, Lidiya I.,Asachenko, Andrey F.,Nechaev, Mikhail S.
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supporting information
p. 120 - 125
(2018/01/17)
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- Organic compound with tetrahedral-like geometry
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An organic compound with a tetrahedral-like geometry is disclosed. The organic compound has a structure represented by formula (I): wherein A1 to A4 each independently represent a 5-membered or 6-membered unsaturated ring; B1 represents direct bonding, —C—, —O—, —N—, —S— or —C═C—; m is 0 or 1; each of Ra's is independently hydrogen, fluorine, oxygen, substituted or unsubstituted C1-C12 alkyl or substituted or unsubstituted C6-C12 aryl; and n is an integer of 0 to 2.
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Page/Page column 65-67
(2018/03/25)
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- Platinum coordination compound, organic light emitting diode, and apparatus capable of emitting visible light or near infrared light
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The present invention provides a platinum coordination compound, an organic light emitting diode, and an apparatus capable of emitting visible light or near infrared light. The platinum coordination compound has a structure represented by the following general formula (I), wherein A1-A4 are respectively and independently an unsaturated 5-membered ring or an unsaturated 6-membered ring, X is carbonor nitrogen, the formal charge number of the first chelating ligand having A1 and A4 is negative univalence, and the formal charge number of the second chelating ligand having A2 and A3 is negative univalence. According to the present invention, the platinum coordination compound has advantages of stable structure, excellent luminous efficiency and simple synthesis steps. The general formula (I)is defined in the specification.
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Paragraph 0073; 0074
(2018/07/07)
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- Organic compound having tetrahedron-like configuration
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The present invention relates to an organic compound having a tetrahedron-like configuration, wherein the organic compound has a structure represented by the following general formula (I) defined in the specification, A1-A4 are respectively and independently an unsaturated five-membered ring or an unsaturated six-membered ring, B is a direct bond , -C, -O-, -N-, -S-, or -C=C-, m is 0 or 1, Ris hydrogen, fluorine, substituted or unsubstituted C1-C12 alkyl, or substituted or unsubstituted C6-C12 aryl, and n is an integer of 0-2. The organic compound of the present invention has excellentphotoelectric property.
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Paragraph 0264; 0266; 0269
(2018/07/07)
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- Novel 4-(2-pyrimidinylamino)benzamide derivatives as potent hedgehog signaling pathway inhibitors
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A series of novel hedgehog signaling pathway inhibitors have been designed and synthesized based on our previously reported scaffold of 4-(2-pyrimidinylamino)benzamide. The Hh signaling pathway inhibitory activities were evaluated by Gli-luciferase reporter method and most compounds showed more potent inhibitory activities than vismodegib. Three compounds were picked out to evaluated in vivo for their PK properties, and compound 23b bearing a 2-pyridyl A-ring and (morpholin-4-yl)methylene at 3-position of D-ring demonstrated satisfactory PK properties. This study suggested the 4-(2-pyrimidinylamino)benzamides were a series of potent Hh signaling pathway inhibitors, deserving to further structural optimization.
- Xin, Minhang,Zhang, Liandi,Tu, Chongxing,Tang, Feng,Wen, Jun
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p. 5029 - 5036
(2018/09/27)
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- CYCLIC SULFAMIDE COMPOUNDS AND METHODS OF USING SAME
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The present disclosure provides, in part, cyclic sulfamide compounds, and pharmaceutical compositions thereof, useful as modulators of Hepatitis B (HBV) core protein, and methods of treating Hepatitis B (HBV) infection.
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Page/Page column 230-231
(2018/09/21)
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- Stille and Suzuki Cross-Coupling Reactions as Versatile Tools for Modifications at C-17 of Steroidal Skeletons – A Comprehensive Study
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Herein, we report on a comparative Stille and Suzuki cross-coupling study of steroidal vinyl (pseudo)halides with different boronic acids and tributyltin organyls. Furthermore, we have investigated the “inverse” case of those cross-coupling reactions, i.e., the reaction of a steroidal vinylpinacolatoborane or a tributyltin steroid with various bromides. The development of both methods allows the introduction of different residues at C-17 of steroid skeletons providing access to a broad variety of steroid analogues which are of high interest for biological screenings or natural product synthesis. (Figure presented.).
- Koch, Vanessa,Nieger, Martin,Br?se, Stefan
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supporting information
p. 832 - 840
(2017/03/11)
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- [2.2]Paracyclophanes with N-Heterocycles as Ligands for Mono- and Dinuclear Ruthenium(II) Complexes
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[2.2]Paracyclophane, with its unique structure, allows the design of unusual 3D structures by functionalization of this rigid and stable hydrocarbon scaffold. Therefore different mono- and homodisubstituted [2.2]paracyclophanes with pyridyl, pyrimidyl and oxazolinyl substituents were developed in order to evaluate their ability as bridging ligands for two ruthenium centres. With the successfully synthesized [2.2]paracyclophane-based N-donor functions, the cycloruthenation reaction using [RuCl2(p-cymene)]2 as precursor was explored. Compared to 2-phenylpyridine, the [2.2]paracyclophane derivative is clearly inferior in the cycloruthenation reaction, resulting in poor yields for the neutral complexes. By addition of KPF6, the cationic complexes can be obtained in good yields and are formed diastereoselectively in case of a pyridyl substituent, resulting in only one diastereomer for dinuclear ruthenium complexes of bispyridyl-substituted [2.2]paracyclophanes as bridging ligands.
- Braun, Carolin,Nieger, Martin,Thiel, Werner R.,Br?se, Stefan
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supporting information
p. 15474 - 15483
(2017/11/09)
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- Noncovalent Interactions in Ir-Catalyzed C-H Activation: L-Shaped Ligand for Para-Selective Borylation of Aromatic Esters
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An efficient strategy for the para-selective borylation of aromatic esters is described. For achieving high para-selectivity, a new catalytic system has been developed modifying the core structure of the bipyridine. It has been proposed that the L-shaped ligand is essential to recognize the functionality of the oxygen atom of the ester carbonyl group via noncovalent interaction, which provides an unprecedented controlling factor for para-selective C-H activation/borylation.
- Hoque, Md Emdadul,Bisht, Ranjana,Haldar, Chabush,Chattopadhyay, Buddhadeb
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supporting information
p. 7745 - 7748
(2017/06/21)
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- Substituted aminopyrimidine compounds and their method and use thereof
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The invention relates to a new aminopyrimidine compound and an application thereof as a drug for treating disorder or diseases related to PI3-kinase abnormity in a free form or a pharmaceutically acceptable salt and preparation form. The invention also relates to a pharmaceutical composition which contains the new aminopyrimidine compound and an application of the pharmaceutical composition in treating mammal disorder or diseases and especially treating human disorder or diseases related to the PI3-kinase abnormity, such as treatment of immunity and inflammatory diseases of PI3-kinase regulation which plays a leading role in a leucocyte function and treatment of proliferative diseases which are related to PI3-kinase activity and include but not limited to leukaemia and solid tumor.
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Paragraph 0767; 0768; 0769
(2017/12/28)
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- 3-(1H-BENZO[D]IMIDAZOL-2-YL)-1H-PYRAZOLO[4,3-B]PYRIDINES AND THERAPEUTIC USES THEREOF
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4-Azaindazole compounds for treating various diseases and pathologies are disclosed. More particularly, the present invention concerns the use of a 4-azaindazole compound or analogs thereof, in the treatment of disorders characterized by the activation of Wnt pathway signaling (e.g., cancer, abnormal cellular proliferation, angiogenesis, fibrotic disorders, bone or cartilage diseases, and osteoarthritis), the modulation of cellular events mediated by Wnt pathway signaling, as well as genetic diseases and neurological conditions/disorders/diseases due to mutations or dysregulation of the Wnt pathway and/or of one or more of Wnt signaling components. Also provided are methods for treating Wnt-related disease states.
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Paragraph 0691; 0692
(2017/02/28)
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- A Novel Iron(II) Preferring Dopamine Agonist Chelator as Potential Symptomatic and Neuroprotective Therapeutic Agent for Parkinson's Disease
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Parkinson's disease (PD) is a progressive neurodegenerative disorder, and development of disease-modifying treatment is still an unmet medical need. Considering the implication of free iron(II) in PD, we report here the design and characterization of a novel hybrid iron chelator, (-)-12 (D-607) as a multitarget-directed ligand against PD. Binding and functional assays at dopamine D2/D3 receptors indicate potent agonist activity of (-)-12. The molecule displayed an efficient preferential iron(II) chelation properties along with potent in vivo activity in a reserpinized PD animal model. The compound also rescued PC12 cells from toxicity induced by iron delivered intracellularly in a dose-dependent manner. However, Fe3+ selective dopamine agonist 1 and a well-known antiparkinsonian drug pramipexole produced little to no neuroprotection effect under the same experimental condition. These observations strongly suggest that (-)-12 should be a promising multifunctional lead molecule for a viable symptomatic and disease modifying therapy of PD.
- Das, Banibrata,Kandegedara, Ashoka,Xu, Liping,Antonio, Tamara,Stemmler, Timothy,Reith, Maarten E. A.,Dutta, Aloke K.
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p. 723 - 730
(2017/04/26)
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- Synthesis and Characterization of a Ruthenium(II) Complex for the Development of Supramolecular Photocatalysts Containing Multidentate Coordination Spheres
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The synthesis of the new bis-heteroleptic RuII complex [(tbbpy)2Ru(dptpphz)](PF6)2 (7), that exhibits a tetradentate coordination sphere for a second metal centre, and its characterization are presented. The complex shows similar photostability and redox properties regarding the first ligand-centred reductions compared to its tpphz analogue. Concentration-dependent NMR investigations were performed and a dimerization constant (KD = 83 ± 5) could be calculated, which was significantly lower than that of other tpphz systems. Photophysical investigations reveal a stabilizing effect of the two electron-withdrawing 2-pyridyl substituents on π–π* transition of the phenazine sphere. The typical H2O-induced light-switch effects have also been observed. To further highlight the potential of the tetradentate coordination site, the ZnII adduct of 7 was prepared and preliminary studied.
- Huber, Fabian L.,Nauroozi, Djawed,Mengele, Alexander K.,Rau, Sven
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supporting information
p. 4020 - 4027
(2017/09/20)
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- PLATINUM COMPLEX, OLED AND APPARATUS FOR PROVIDING VISIBLE EMISSION OR NEAR-INFRARED EMISSION
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A platinum complex, an OLED and an apparatus for providing visible emission or near-infrared (NIR) emission using the same are described.? The platinum complex has a structure represented by formula (I): (I) wherein A1 to A4 each independently represent a 5-membered or 6-membered unsaturated ring, a first chelating ligand including A1 and A4 fragments has a minus one formal charge, and a second chelating ligand including A2 and A3 fragments has a minus one formal charge.
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Paragraph 0036
(2018/03/28)
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- METHOD FOR PRODUCING 14 GROUP METAL LITHIUM COMPOUND
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PROBLEM TO BE SOLVED: To provide a method for quantitatively producing a group 14 metal lithium compound under a mild condition. SOLUTION: The method for producing a group 14 metal lithium compound represented by formula (4): R4-nMLin comprises reacting a compound represented by formula (1): R4-nMXn and lithium in the presence of a polycyclic aromatic compound represented by formula (2) or formula (3). [In formula (1) and formula (2), R is a hydrocarbon group; M is a metal atom selected from Si, Ge and Sn; X is a halogen atom or R3M- (R and M are the same as mentioned above); and n is 1 or 2] and [R1 is H or a hydrocarbon group; and m is an integer of 0 to 5.] SELECTED DRAWING: None COPYRIGHT: (C)2016,JPOandINPIT
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Paragraph 0085; 0087- 0088
(2016/10/31)
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- Visible light-harvesting tricarbonyl Re(I) complex: Synthesis and application in intracellular photodynamic effect and luminescence imaging
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Re(I) tricarbonyl rhenium(I) complexes attracted much attention owing to the good cellular uptake ability and rich photophysical properties. However, normally Re(I) complexes show short triplet state lifetime and weak absorption in the visible spectra region, and the absorption wavelength usually is shorter than 450 nm. These features are detrimental to the applications of Re(I) complexes in the areas such as photodynamic therapy (PDT) and luminescence bioimaging. Herein, a novel tricarbonyl rhenium(I) complex Re-1 with strong visible light-absorbing ability (624 nm, ε=5.69×104 L/(mol cm)), long-lived triplet excited state (τ T=448.9 μs) and moderate fluorescence quantum yield (Φ F=41.6%) was prepared. The photophysical properties of Re-1 were studied with steady state UV-Vis absorption and luminescence spectroscopies, nanosecond transient absorption spectroscopy, as well as DFT/TDDFT calculations. Re-1 was used for intracellular PDT and luminescence imaging studies. The results indicate that Re-1 shows low dark toxicity, but it is able to kill cancer cells on illumination with 635 nm LED.
- Zhong, Fangfang,Yuan, Xiaolin,Zhao, Jianzhang,Wang, Quan
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- 3-(1H-BENZO[D]IMIDAZOL-2-YL)-1H-PYRAZOLO[3,4-C]PYRIDINE AND THERAPEUTIC USES THEREOF
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Azaindazole compounds for treating various diseases and pathologies are disclosed. More particularly, the present invention concerns the use of an azaindazole compound or analogs thereof, in the treatment of disorders characterized by the activation of Wnt pathway signaling (e.g., cancer, abnormal cellular proliferation, angiogenesis, fibrotic disorders, bone or cartilage diseases, and osteoarthritis), the modulation of cellular events mediated by Wnt pathway signaling, as well as genetic diseases and neurological conditions/disorders/diseases due to mutations or dysregulation of the Wnt pathway and/or of one or more of Wnt signaling components. Also provided are methods for treating Wnt-related disease states.
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Page/Page column 0875
(2016/04/20)
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- Heteroleptic Ir(III) phosphors with bis-tridentate chelating architecture for high efficiency OLEDs
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A bis-tridentate iridium complex represented by a formula (I): where R3 to R8, R21 to R23, R9, R10, X1, X2, and X3 are as defined in the specification.
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Page/Page column 11
(2016/01/09)
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- Antiaromatic compounds and organic light-emitting device comprising the same
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The present invention relates to an anti-aromatic compound and an organic light emitting device comprising the same. According to one embodiment of the present invention, provided is an anti-aromatic compound represented by chemical formula 1. The organic light emitting device comprising the anti-aromatic compound can obtain high efficiency and long lifespan properties.COPYRIGHT KIPO 2016
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Paragraph 0470-0472
(2016/10/10)
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- An alcohol soluble amino-functionalized organoplatinum(ii) complex as the cathode interlayer for highly efficient polymer solar cells
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A small-molecule amino-functionalized organoplatinum(ii) complex Pt-N has been developed. The unique properties of Pt-N, including a well-defined chemical structure, an excellent solubility in environmentally friendly polar solvents and good electron extraction to high work-function metals, make it a promising candidate for cathode interfacial modification of solution processed multilayer polymer solar cells (PSCs). The resultant PSCs with an ITO/PEDOT:PSS/PTB7:PC71BM/interlayer/Al device configuration exhibited significantly improved efficiencies from 3.62% for an unmodified device to 8.89% by using a Pt-N cathode interlayer, benefiting from the dramatic enhancement in the open circuit voltage (0.53 V for bare Al PSCs to 0.75 V for Pt-N/Al PSCs), the fill factor (43.58% for bare Al PSC to 72.49% for Pt-N/Al PSC), and a slight increase in short-circuit current density. These results indicate that Pt-N is a new promising candidate as the cathode interlayer for highly efficient PSCs. This journal is
- Liu, Shengjian,Zhang, Guichuan,Lu, Junming,Jia, Jianchao,Li, Wei,Huang, Fei,Cao, Yong
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p. 4372 - 4379
(2015/05/13)
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- Stannyl-Lithium: A Facile and Efficient Synthesis Facilitating Further Applications
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We have developed a highly efficient, practical, polycyclic aromatic hydrocarbon (PAH)-catalyzed synthesis of stannyl lithium (Sn-Li), in which the tin resource (stannyl chloride or distannyl) is rapidly and quantitatively transformed into Sn-Li reagent at room temperature without formation of any (toxic) byproducts. The resulting Sn-Li reagent can be stored at ambient temperature for months and shows high reactivity toward various substrates, with quantitative atom efficiency.
- Wang, Dong-Yu,Wang, Chao,Uchiyama, Masanobu
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supporting information
p. 10488 - 10491
(2015/09/28)
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- 3-(BENZOIMIDAZOL-2-YL)-INDAZOLE INHIBITORS OF THE WNT SIGNALING PATHWAY AND THERAPEUTIC USES THEREOF
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Indazole compounds for treating various diseases and pathologies are disclosed. More particularly, the present disclosure concerns the use of an indazole compound or analogs thereof, in the treatment of disorders characterized by the activation of Wnt pathway signaling (e.g., cancer, abnormal cellular proliferation, angiogenesis, Alzheimer's disease, lung disease and osteoarthritis), the modulation of cellular events mediated by Wnt pathway signaling, as well as genetic diseases and neurological conditions/disorders/diseases due to mutations or dysregulation of the Wnt pathway and/or of one or more of Wnt signaling components. Also provided are methods for treating Wnt-related disease states.
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Paragraph 0455
(2014/07/22)
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- A miniaturized voltammetric pH sensor based on optimized redox polymers
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A miniaturized pH sensor based on the voltammetric determination of the potential difference between a pH dependent toluidine blue O modified redox polymer and a pH independent osmium complex modified redox polymer was developed. Gold micro electrodes of various dimensions were modified with the two redox polymers by non-manual deposition procedures. Square wave voltammetry was used to determine the oxidation potentials of the polymer bound redox species allowing the precise determination of the pH value of the electrolyte solution without the need of a stable reference electrode.
- P?ller, Sascha,Schuhmann, Wolfgang
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p. 101 - 107
(2014/12/11)
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- Sonochemical synthesis of bis(tri-n-butylstannyl) aromatic compounds via Barbier-like reactions
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This paper reports a study of the synthesis of aryltri-n-butylstannanes via a sonochemical Barbier reaction of aryl- and heteroaryl bromides with bis(tri-n-butyltin) oxide (2) in THF. Our results demonstrate that, despite previous reports on contrary, the aryltributylstannanes can also be obtained under the same reaction conditions via sonicated reactions between aryl monobromides and tri-nbutyltin chloride (2). A comparative study of the reactions of electrophiles 2 and 3 with bromobenzene, 2-bromopyridin, o- and m-bromoanisole, m-bromotoluene, 9-bromophenthrene, and 9-bromoanthracene, indicates that the corresponding aryl- and heteroaryl-tri-n-butylstannyl derivatives are obtained in about the sameyields. Best reaction conditions and the results obtained in the investigation of the sonicated reactions between several aromatic and heteroaromatic dibromides are also reported. It was found that the reactions using 1,2-, 1,3-, and 1,4-dibromobenzenes, 4,40-dibromobiphenyl, 1,4-dibromonaphthalene, 2,5-and 3,5-dibromopyridines, and 2,5-dibromothiophene lead to the corresponding bis(tri-n-butylstannylated) derivatives in many cases in very high yields. Also the excellent results obtained in the sonicated reactions of 1,3,5-tribromobenzene with 2 and 3 are reported.
- Gerbino, Darío C.,Fidelibus, Pablo M.,Mandolesi, Sandra D.,Ocampo, Romina A.,Scoccia, Jimena,Podestá, Julio C.
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- 1H-PYRAZOLO[3,4-B]PYRIDINES AND THERAPEUTIC USES THEREOF
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Provided herein are compounds according to Formulas (I) or (II) and pharmaceutically acceptable salts thereof, and compositions comprising the same, for use in various methods, including treating cancer, abnormal cellular proliferation, angiogenesis, Alzheimer's disease, lung disease, osteoarthritis, idiopathic pulmonary fibrosis and neurological conditions/disorders/diseases.
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Paragraph 0592
(2013/11/19)
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- A polyaromatic terdentate binding unit with fused 5,6-membered chelates for complexing s-, p-, d-, and f-block cations
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The polyaromatic terdentate ligand 6-(azaindol-1-yl)-2,2′-bipyridine (L7) combines one 5-membered chelate ring with a fused 6-membered chelate ring. It is designed to provide complexation properties intermediate between 2,2′;6′,2″-terpyridine (L1) (two fused 5-membered chelate rings) and 2,6-bis(azaindol-1-yl)pyridine (L6) (two fused 6-membered chelate rings). In polar organic solvents, L7 displays remarkable affinities for the successive fixation of two small univalent cations M = H+ or Li +, leading to stable [Mm(L7)]m+ (m = 1-2) complexes. Upon reaction with M = Mg2+ or Zn2+ cations, the large positive charge densities borne by the metals result in the successive cooperative complexation of two ligands to give [M(L7)n] n+ (n = 1-2). For small Sc3+, unavoidable traces of water favor the formation of the protonated ligand at millimolar concentrations in acetonitrile, but the use of larger Y3+ cations leads to [Y(L7) n]n+ (n = 1, 2), for which stability constants of log(β1,1Y,L7) = 2.9(5) and log(β1,2Y,L7) = 5.3(4) are estimated. The complexation behaviors are supported by speciations in solution, thermodynamic analyses, and solution and solid-state structures.
- Hoang, Thi Nhu Y.,Humbert-Droz, Marie,Dutronc, Thibault,Guenee, Laure,Besnard, Celine,Piguet, Claude
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p. 5570 - 5580
(2013/06/26)
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- MATERIALS FOR ORGANIC ELECTROLUMINESCENCE DEVICES
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The invention relates to pyrimidine derivatives according to formula (I), and to organic electroluminescent devices comprising said pyrimidine derivatives as electron transport material.
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Paragraph 0098; 0099
(2013/03/26)
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- Visible light-absorbing rhenium(i) tricarbonyl complexes as triplet photosensitizers in photooxidation and triplet-triplet annihilation upconversion
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We prepared N^N Re(i) tricarbonyl chloride complexes (Re-1 and Re-2) that give very strong absorption of visible light. To this end, it is for the first time that boron dipyrimethane (Bodipy) was used to prepare Re(i) tricarbonyl chloride complexes. The π-conjugation linker between the π-conjugation framework of the antenna Bodipy and the Re(i) coordination centre ensures efficient intersystem crossing (ISC). Re-0 without visible light-harvesting ligand was prepared as a model complex in the photophysical studies. Re-1 (with Bodipy) and Re-2 (with carbazole-ethynyl Bodipy) show unprecedented strong absorption of visible light at 536 nm (ε = 91700 M-1 cm -1) and 574 nm (ε = 64600 M-1 cm-1), respectively. Interestingly, different from Re-0, Re-1 and Re-2 show fluorescence of the ligand, not the phosphorescence of the Re(i) coordination centre. However, long-lived triplet excited states were observed upon visible light excitation (τT = 104.0 μs for Re-1; τT = 127.2 μs for Re-2) vs. the short lifetime of Re-0 (τT = 26 ns). With nanosecond time-resolved transient absorption spectroscopy and DFT calculations, we proved that the triplet excited states of Re-1 and Re-2 are localized on the Bodipy ligands. The complexes were used as triplet photosensitizers for two triplet-triplet-energy-transfer (TTET) processes, i.e.1O2 mediated photooxidation and triplet-triplet annihilation (TTA) upconversion. With the strong visible light-harvesting ability, Re-1 proved to be a better 1O2 photosensitizer than the conventional triplet photosensitizer tetraphenylporphyrin (TPP). Significant upconversion was observed with Re-1 as the triplet photosensitizer. Our result is useful for preparation of Re(i) tricarbonyl chloride complexes that show strong absorption of visible light and long-lived triplet excited states and for the application of these complexes as triplet photosensitizers in photocatalysis, photodynamic therapy and TTA upconversion. The Royal Society of Chemistry 2013.
- Yi, Xiuyu,Zhao, Jianzhang,Sun, Jifu,Guo, Song,Zhang, Hongli
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supporting information
p. 2062 - 2074
(2013/02/26)
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- Facile synthesis of 3-arylpyridine derivatives by palladacycle-catalyzed Stille cross-coupling reaction
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The Stille cross-coupling reaction of a variety of aryl halides (X=Cl, Br, I) with 3-alkylstannylpyridines highly catalyzed by cyclopalladated ferrocenylimine has been developed. This reaction allows formation of arylpyridine derivatives in moderate to excellent yields. Functional groups on aryl halides, such as amino, hydroxyl, keto, and aldehyde are tolerated and the reactions with arylbenzoxale substrates also proceed well.
- Ma, Gaizhi,Leng, Yuting,Wu, Yusheng,Wu, Yangjie
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p. 902 - 909
(2013/07/25)
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- Green light-excitable naphthalenediimide acetylide-containing cyclometalated Ir(iii) complex with long-lived triplet excited states as triplet photosensitizers for triplet-triplet annihilation upconversion
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Naphthalenediimide (NDI) was connected to the ligand of a cyclometalated Ir(iii) complex (Ir-1) via a CC triple bond to enhance the absorption in the visible region and to access long-lived triplet excited states. Ir(ppy) 2(bpy)[PF6] (Ir-2, ppy = 2-phenylpyridine and bpy = 2,2′-bipyridine) was used as a model complex. The photophysical properties of the complexes were studied with steady state and time-resolved spectroscopy. Ir-1 shows strong absorption in the visible region (ε = 11 000 M -1 cm-1 at 542 nm) and in comparison Ir-2 shows typically weak absorption in the visible region (ε -1 cm -1 above 400 nm). Room temperature near IR emission at 732 nm (ΦP = 0.1%) was observed for Ir-1, which is attributed to the NDI localized emissive triplet excited state, by transient absorption spectra and DFT calculations on the spin density surface. The lifetime of the NDI-localized triplet excited state is up to 130.0 μs, which is rarely reported for Ir(iii) complexes. In comparison, Ir-2 shows phosphorescence at 578 nm and the triplet state lifetime is a typical value of 0.3 μs. The complexes were used as triplet photosensitizers for triplet-triplet annihilation (TTA) upconversion and an upconversion quantum yield of 6.7% was observed with Ir-1. No upconversion was observed with Ir-2 as the triplet photosensitizer at the same experimental conditions.
- Ma, Lihua,Guo, Song,Sun, Jifu,Zhang, Caishun,Zhao, Jianzhang,Guo, Huimin
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p. 6478 - 6488
(2013/07/26)
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- A sensitive sensor for Cu(II) based on a novel diarylethene with a bipyridyl moiety
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A novel diarylethene with a bipyridyl unit has been designed and synthesized for the first time. Its photochromic behaviors could be modulated by protonation and coordination with Cu(II). The absorption maximum of the closed-ring isomer shifted from 569 to 666 nm when trifluoroacetic acid was added. Furthermore, the closed-ring isomer behaved as a sensitive colorimetric sensor, exhibiting an open-ring reaction upon exposure to Cu(II). Its high selectivity toward Cu(II) over other competitive species makes the 'naked-eye' detection of Cu(II) possible.
- Zheng, Chunhong,Liu, Gang,Pu, Shouzhi
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supporting information
p. 5791 - 5794
(2013/10/01)
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- PYRIDINE- 2- DERIVATIVES AS SMOOTHENED RECEPTOR MODULATORS
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The present application relates to compounds of Formula (I), and Formula (II), or pharmaceutically acceptable salt thereof, wherein A, X, Y, Z, e, f, R1, R2, R3, R4, R5, R5b, R6, R7, R8, R9, R10, R11,R20, R21, R22 and R23 are defined herein. These novel pyridine derivatives that are useful in therapy, in particular for treating diseases or conditions mediated by Smo, including the treatment of abnormal cell growth, such as cancer, in mammals. Additional embodiments relate to methods of using such compounds in the treatment of abnormal cell growth in mammals, especially humans, and to pharmaceutical compositions containing such compounds.
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Page/Page column 59
(2012/05/05)
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- IRAK INHIBITORS AND USES THEREOF
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The present invention relates to compounds and methods useful for inhibiting one or more interleukin-l receptor-associated kinases ("IRAK"). In some embodiments, a provided compound inhibits IRAK-1 and IRAK-4. The invention also provides pharmaceutically acceptable compositions comprising compounds of the present invention and methods of using said compositions in the treatment of various disorders.
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Page/Page column 202-204
(2012/07/28)
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- Unusual nitro-coordination of europium(iii) and terbium(iii) with pyridinyl ligands
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A new ligand family based on picoline, bipyridine and terpyridine containing a nitro moiety has been synthesized and its coordination and sensitization ability for lanthanide ions has been studied. Three new complexes were characterized by X-ray single crystal diffraction and all three show uncommon coordination of the nitro moiety to the lanthanide ion. 5cTb, a terpyridine-nitro derivative with Tb(NO3)3, crystallizes in the orthorhombic space group Pbca with a = 15.125(3), b = 13.776(3), c = 18.716(4) A, and V = 3899.8(13) A3 and is isostructural with its Eu(iii) analog (5cEu) with cell parameters a = 15.1341(4), b = 13.7070(4), c = 18.8277(5) A. 6Eu, a tripodal amine with a nitro-derivatized pyridine with Eu(CF3SO3)3, crystallizes in the triclinic space group P1 with a = 11.067(2), b = 11.633(2), c = 12.772(3) A, α = 110.94(3), β = 97.49(3), γ = 91.42(3)° and V = 1518.1(5) A3. Finally, ligand 5a, a bipyridine-nitro derivative, crystallizes in the orthorhombic space group P21/n with a = 3.7128(3), b = 11.7806(8), c = 19.9856(14) A, β = 92.925(2)° and V = 873.01(11) A3. All four ligands show sensitization of Eu(iii) and Tb(iii) luminescence.
- De Bettencourt-Dias, Ana,Bauer, Sebastian,Viswanathan, Subha,Maull, Brandi C.,Ako, Ayuk M.
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p. 11212 - 11218
(2012/10/29)
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- LINEAR PYRIDAZINE AND PYRROLE COMPOUNDS, METHOD FOR OBTAINING THEM AND APPLICATIONS
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The present invention relates to linear pyridazine compounds, and more particularly to those of these compounds which are oligopyridazine compounds, to processes for obtaining them, to their uses, and also to their reduction to pyrroles and to the uses of the pyrrole, pyridazinylpyrrole and oligopyrrole compounds obtained. The invention relates in particular to the uses as medicaments, in particular for treating pathologies such as cancer, bacterial infections or parasitic infections, and also the applications in the materials, environmental, electronics and optics field.
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Page/Page column 33
(2010/02/16)
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- BENZOXAZOLE CARBOXAMIDE INHIBITORS OF POLY(ADP-RIBOSE)POLYMERASE (PARP)
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A compound having the structure set forth in Formula (I) or Formula (II): wherein the variables Y, R1, R2, R3, and R4 are as defined herein. Provided herein are inhibitors of poly(ADP-ribose)polymerase activity. Also described herein are pharmaceutical compositions that include at least one compound described herein and the use of a compound or pharmaceutical composition described herein to treat diseases, disorders and conditions that are ameliorated by the inhibition of PARP activity.
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Page/Page column 53
(2009/08/16)
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- MACROCYCLIC INHIBITORS OF HEPATITIS C VIRUS
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Inhibitors of HCV replication of formula (I) and the N-oxides, salts, or stereoisomers thereof, wherein each dashed line (represented by ------) represents an optional double bond; X is N, CH and where X bears a double bond it is C; R1 is -OR6, -NH-SO2R7; R2 is hydrogen, and where X is C or CH, R2 may also be C1-6alkyl; R3 is hydrogen, C1-6alkyl, C1-6alkoxyC1-6alkyl, or C3-7cycloalkyl; n is 3, 4, 5, or 6; R4 and R5 independently from one another are hydrogen, halo, hydroxy, nitro, cyano, carboxyl, C1-6alkyl, C1-6alkoxy, C1-6alkoxyC1-6alkyl, C1-6alkylcarbonyl, C1-6alkoxy- carbonyl, amino, azido, mercapto, C1-6alkylthio, polyhaloC1-6alkyl, aryl or Het; W is aryl or Het; R6 is hydrogen; aryl; Het; C3-7cycloalkyl optionally substituted with C1-6alkyl; or C1-6alkyl optionally substituted with C3-7cycloalkyl, aryl or with Het; R7 is aryl; Het; C3-7cycloalkyl optionally substituted with C1-6alkyl; or C1-6alkyl optionally substituted with C3-7cycloalkyl, aryl or with Het; aryl is phenyl or naphthyl, each optionally substituted with 1-3 substituents; Het is a 5 or 6 membered saturated, partially unsaturated or completely unsaturated heterocyclic ring containing 1 - 4 heteroatoms each independently selected from N, O or S, and optionally substituted with 1 -3 substituents; pharmaceutical compositions containing compounds (I) and processes for preparing compounds (I). Bioavailable combinations of the inhibitors of HCV of formula (I) with ritonavir are also provided.
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Page/Page column 104
(2008/06/13)
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- Electronic influence of the thienyl sulfur atom on the oligomerization of ethylene by cobalt(II) 6-(thienyl)-2-(imino)pyridine catalysis
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The position of the sulfur atom in the thienyl group of 6-(thienyl)-2-(imino)pyridine ligands strongly affects the catalytic activity of the corresponding tetrahedral high-spin dihalide CoII complexes in the oligomerization of ethylene to α-olefins upon activation with methylaluminoxane (MAO). Complexes with the sulfur atom in the 3-position of the thienyl ring catalyze the selective conversion of ethylene to 1-butene, while catalysts containing thien-2-yl groups give C4-C14 a-olefins. In situ EPR experiments showed the occurrence of a spin state changeover with the formation of low-spin CoII species upon activation of the catalyst precursors by MAO. DFT calculations suggest that only thien-2-yl rings allow for the coordination of the sulfur atom to the cobalt center in the MAO-activated systems.
- Bianchini, Claudio,Gatteschi, Dante,Giambastiani, Giuliano,Rios, Itzel Guerrero,Ienco, Andrea,Laschi, Franco,Mealli, Carlo,Meli, Andrea,Sorace, Lorenzo,Toti, Alessandro,Vizza, Francesco
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p. 726 - 739
(2008/10/09)
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- Nitrogenous tetrahydropyridyl-alkyl-heterocycles with tnf activity
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This invention relates to nitrogenous (tetrahydropyridyl)(alkyl)heterocycles, to pharmaceutical compositions comprising them, to processes for preparing them and to the method of use thereof in the treatment of pain and diseases related to immune and inflammatory disorders.
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