- The dependence of oxygen sensitivity on the molecular structures of Ir(iii) complexes and their application for photostable and reversible luminescent oxygen sensing
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Three Ir(iii) complexes IrC1, IrC2, and IrC3 substituted with 4-(diphenylamino)phenyl (TPA), 4-(9H-carbazol-9-yl)phenyl (Cz1), and 9-phenyl-9H-carbazol-3-yl (Cz2) moieties were prepared and fully characterized as phosphorescent emitters. In comparison with Ir(ppy)3, introduction of TPA, Cz1, and Cz2 moieties strongly improved the oxygen sensitivities of IrC1-IrC3. Short-decayed IrC1 with I0/I100 of 168.6 and KappSV of 202.2 bar-1 in THF exhibited the highest sensitivity for oxygen. TPA and Cz moieties caused remarkable collision radius variations of the Ir(iii) complexes with 2.13 ± 0.08 for σIrC1/σIr(ppy)3, 1.24 ± 0.06 for σIrC2σIr(ppy)3, and 1.54 ± 0.08 for σIrC3σIr(ppy)3. For demonstrating the dependence of oxygen sensitivity on the molecular structure of the oxygen-sensitive probes (OSPs), the delocalization of spin populations (DSPs) has been applied for the first time to confirm the collision radius variations of Ir(iii) complexes. Remarkable DSPs were found on the TPA, Cz1, and Cz2 moieties with the spin population (percentage of the spin population) of 0.23210 (11.61%), 0.08862 (4.43%), and 0.13201 (6.60%), respectively. And strong linear correlations (R2 = 0.997) between the collision radius variations and spin population on TPA and Cz moieties were apparent. The DSPs could be used to describe the dependence of oxygen sensitivity on the molecular structure of the OSPs. For achieving real-time oxygen sensing, the photostability, oxygen sensing performance, and operational stability of IrC1-IrC3 and Ir(ppy)3 immobilized in ethyl cellulose (EC) were investigated. The IrC1-EC film demonstrated outstanding photostability after 60 min of irradiation and excellent operational stability for continuous oxygen monitoring with no attenuation of the original emission intensity in 4000 s. This study quantified and analyzed the dependence of oxygen sensitivity on the molecular structure of Ir(iii) complexes for the first time and illustrated a feasible approach to achieve high-efficiency sensors for real-time monitoring of oxygen.
- Xing, Yang,Qiao, Chengfang,Li, Xinmin,Li, Chun,Wang, Honghao,Li, Fayun,Di, Ling,Yang, Zhanxu
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Read Online
- The influence of molecular structure on collision radius for optical sensing of molecular oxygen based on cyclometalated Ir(iii) complexes
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Three triphenylamine (TPA) substituted cyclometalated Ir(iii) complexes IrA1, IrA2, and IrA3 based on Ir(ppy)3 were synthesized and applied as phosphorescent probes for the monitoring of molecular oxygen. The phosphorescence intensity of all the Ir(iii) complexes in tetrahydrofuran (THF) was gradually quenched with an increase of oxygen concentration. The increase of TPA substituents on the meta-position of 2-phenylpyridine (IrA1-IrA3) gradually improved the oxygen sensitivity of cyclometalated Ir(iii) complexes. IrA3 showed the highest oxygen sensitivity in THF with a KappSV of 204.8 bar?1 and a limit of detection (LOD) of 0.27 mbar. The relationship between molecular structure and the collision radiuses (σ) of all the Ir(iii) complexes has been investigated on the basis of the Demas model and the fundamental expression of luminescence quenching systems by oxygen. The ratio of collision radiuses are σIrA1/σIr(ppy)3 = 1.27 ± 0.05, σIrA2/σIr(ppy)3 = 1.72 ± 0.10, and σIrA3/σIr(ppy)3 = 2.13 ± 0.07, respectively. The introduction and increase of TPA substituents can obviously increase the collision radiuses of cyclometalated Ir(iii) complexes which leading to potential oxygen sensitivity. And the incremental effect of collision radiuses caused by the introduction of TPA substituents resulted in outstanding oxygen sensitivity of IrA3. The results demonstrate for the first time evidence between molecular structure and oxygen sensitivity of the emitters for optical sensing.
- Di, Ling,Xing, Yang,Wang, Xiaoning,Zheng, Daoyuan,Yang, Yang,Li, Fayun
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Read Online
- Recyclable Ruthenium Catalyst for Distal meta-C?H Activation
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We disclose the unprecedented hybrid-ruthenium catalysis for distal meta-C?H activation. The hybrid-ruthenium catalyst was recyclable, as was proven by various heterogeneity tests, and fully characterized with various microscopic and spectroscopic techniques, highlighting the physical and chemical stability. Thereby, the hybrid-ruthenium catalysis proved broadly applicable for meta-C?H alkylations of among others purine-based nucleosides and natural product conjugates. Additionally, its versatility was further reflected by meta-C?H activations through visible-light irradiation, as well as para-selective C?H activations.
- Choi, Isaac,Müller, Valentin,Wang, Yanhui,Xue, Kai,Kuniyil, Rositha,Andreas, Loren B.,Karius, Volker,Alauzun, Johan G.,Ackermann, Lutz
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Read Online
- Photostable Fluorophenyl-Substituted Cyclometalated Platinum(II) Emitters for Monitoring of Molecular Oxygen in Real Time
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The effects of fluorophenyl substituents on the photoluminescence, redox properties, and oxygen sensing behaviors of the cyclometalated Pt(II) complexes are reported. The Pt(II) complexes with fluorophenyl substituents at the para position on the phenyl r
- Xing, Yang,Liu, Chun,Xiu, Jing-Hai,Li, Jiu-Yan
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Read Online
- Manipulating MLCT transition character with ppy-type four-coordinate organoboron skeleton for highly efficient long-wavelength Ir-based phosphors in organic light-emitting diodes
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Inspired by the intriguing optoelectronic characteristics of the 2-phenylpyridine-type (ppy-type) four-coordinate organoboron skeleton, we envisage a molecular design strategy by manipulating the MLCT transition character to develop high-performance long-wavelength Ir-based phosphors with a ppy-type four-coordinate organoboron skeleton for organic light-emitting diodes (OLEDs). Three ppy-type cyclometalated Ir(iii) complexes are successfully prepared.IrOBNandIrPBNexhibit the expected long-wavelength phosphorescent emission at 620 and 604 nm, respectively, due to the electron-accepting ability of the pyridine coordinated with the boron atom (pyd(B)) in extending the π-conjugated length for the LUMO, thus leading to stabilization of the LUMO. Interestingly,IrMBNshows a green phosphorescence at 514 nm. The more electron-deficient pyd(B) inIrMBNleads to a reorganized and localized LUMO distribution pattern mainly on pyd(B) rather than the pyridine coordinated with the Ir atom (pyd(Ir)), shortening the π-conjugation length for the LUMO, hence resulting in an elevated LUMO. Benefiting from the high rigidity of the ppy-type four-coordinate organoboron skeleton, these three ppy-type cyclometalated Ir(iii) complexes show high PLQY (ca.0.6-1). Beneficially, we can achieve impressive electroluminescence (EL) performance based onIrPBNwith the highest efficiencies of a maximum external quantum efficiency (ηext) of 26.0%, a maximum current efficiency (ηL) of 42.0 cd A?1, and a maximum power efficiency (ηP) of 38.5 lm W?1, respectively. All these excellent results convincingly demonstrate the effectiveness of our molecular design strategy and the great potential of the ppy-type four-coordinate organoboron skeleton in developing high-performance Ir-based phosphors.
- Deng, Xuming,Feng, Zhao,Sun, Yuanhui,Wu, Zhaoxin,Yang, Xiaolong,Yu, Yue,Zhong, Daokun,Zhou, Guijiang
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supporting information
p. 12650 - 12660
(2021/10/06)
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- Chromium-Catalyzed Reductive Cleavage of Unactivated Aromatic and Benzylic C-O Bonds
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Reductive cleavage of aromatic and benzylic C-O bonds by chromium catalysis is reported. This deoxygenative reaction was promoted by low-cost CrCl 2precatalyst combined with poly(methyl hydrogen siloxane) as the mild reducing agent, providing a strategy in forming reduced motifs by cleavage of unactivated C-O bonds. A range of functional groups such as bromide, chloride, fluoride, hydroxyl, amino, and alkoxycarbonyl can be retained in the reduction.
- Yuan, Shuqing,Ling, Liang,Tang, Jinghua,Luo, Meiming,Zeng, Xiaoming
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p. 3343 - 3350
(2021/07/02)
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- Preparation method and application of tetradentate platinum (II) complex
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The invention relates to a preparation method and application of a novel tetradentate platinum (II) complex, and belongs to the field of OLED (organic light-emitting diode) materials. The complex has a structural formula shown in the specification, and is
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Paragraph 0051-0053
(2021/06/12)
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- Electron transport material, preparation method thereof and organic light-emitting device
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The invention discloses an electron transport material, a preparation method thereof and an organic light-emitting device, and belongs to the technical field of chemical and organic light-emitting materials, in the structural general formula of the electron transport material, m and n are independently 0 or 1, and m and n are not 0 at the same time; W, Q and Z are independently C or N, and at least one of W, Q and Z is N; X and Y are independently O or S. By introducing a benzoheterocycle rigid structure, the electron transport material provided by the invention has good film-forming property and thermal stability. The electron transport material provided by the invention has high electron injection and movement rates. The electron transport material can improve the electron transport efficiency from an electron transport layer to a light-emitting layer, thereby improving the light-emitting efficiency of a device, reducing the driving voltage of the device, and enhancing the durability of the obtained organic light-emitting device.
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Paragraph 0106-0110
(2021/04/14)
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- Preparation method and application of a class of cyclometalated platinum coordination compounds
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The invention discloses a preparation method and application of a class of cyclometalated platinum coordination compounds, and belongs to the field of phosphorescent materials. According to the invention, seven platinum coordination compounds are synthesi
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Paragraph 0028-0030
(2020/10/30)
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- BLUE AND NARROW BAND GREEN AND RED EMITTING METAL COMPLEXES
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The present invention includes tetradentate platinum (II) complexes for narrow band green and red phosphorescent emitters. The present invention also includes blue emitting metal complexes with six-membered chelate rings based on fused carbazole. The pres
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Paragraph 0082; 0083
(2019/09/20)
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- Transition-Metal-Free Decarboxylative Arylation of 2-Picolinic Acids with Arenes under Air Conditions
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A facile, transition-metal-free, and direct decarboxylative arylation of 2-picolinic acids with simple arenes is described. The oxidative decarboxylative arylation of 2-picolinic acids with arenes proceeds readily via N-chloro carbene intermediates to afford 2-arylpyridines in satisfactory to good yields under transition-metal-free conditions. This new type of decarboxylative arylation is operationally simple and scalable and exhibits high functional-group tolerance. Various synthetically useful functional groups, such as halogen atoms, methoxycarbonyl, and nitro, remain intact during the decarboxylative arylation of 2-picolinic acids.
- Zhang, Xitao,Feng, Xiujuan,Zhou, Chuancheng,Yu, Xiaoqiang,Yamamoto, Yoshinori,Bao, Ming
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supporting information
p. 7095 - 7099
(2018/11/23)
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- Organic metal compounds and organic light emitting diodes comprising the same
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PURPOSE: An organic metal compound is provided to have excellent thermal properties and light emitting efficiency, thereby being useful for a display and lighting device. CONSTITUTION: An organic metal compound is represented by chemical formula 1. In chemical formula 1, each of R and Z is hydrogen, deuterium, cyano, halogen hydroxy, nitro, C1-40 alkyl, C1-40 alkoxy, C1-40 alkylamino, C6-40 arylamino, C3-40 heteroarylamino, C1-40 alkoxy group, C1-40 alkylamino, C6-40 aryl group, C3-40 aryloxy group, germanium, phosphorous, and boron; each of A, B, C, D, and E is a substituted or unsubstituted aromatic cycle, or substituted or unsubstituted hydrocycle, X is carbon or nitrogen, G is chemical bond or C1-4 alkylene which can be substituted by (R-Zi)n.
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Paragraph 0154; 0155; 0157-0160
(2018/12/01)
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- Direct Alkenylation of Allylbenzenes via Chelation-Assisted C-C Bond Cleavage
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A novel method for direct transformation of allyl groups in allylbenzene derivatives to alkenyl groups via rhodium-catalyzed C-C bond cleavage is reported. The alkenylation with styrenes of allylbenzenes containing pyridyl and pyrazolyl groups as a directing group proceeded efficiently to give alkenylation products. We also developed a new protocol for transformation of an ortho-prenylated phenol to an aniline derivative.
- Onodera, Shunsuke,Ishikawa, Soya,Kochi, Takuya,Kakiuchi, Fumitoshi
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supporting information
p. 9788 - 9792
(2018/05/31)
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- Synthesis of Bi(hetero)aryls via Sequential Oxidation and Decarboxylation of Benzylamines in a Batch/Fully Automated Continuous Flow Process
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Catalytic dehydrogenative cross-coupling of two C–H bonds represents a green strategy in view of the atom- and step-economy. However, the challenge is to discover a new innovative bond strategy, especially for the direct coupling between Csp2–H
- Mahajan, Bhushan,Aand, Dnyaneshwar,Singh, Ajay K.
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supporting information
p. 2831 - 2835
(2018/06/21)
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- ONE STEP DIRECT ARYLATION OF COMMODITY CHEMICALS TO SPECIALTY CHEMICALS BY TANDEM CATALYTIC PLATFORM
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The present invention relates to a continuous direct arylation process based on a tandem catalyst for synthesizing specialty chemicals. A method for synthesizing an aryl-aryl structure from a substrate selected from the group consisting of benzyl alcohol, benzyl amine and toluene which are low value added compounds is developed using a silver ion-containing tandem catalyst. The method is applied for synthesizing hexaphenyl arylene and can be applied for synthesizing high value added compounds (not only natural substances and chemical compounds but pharmaceutical and agricultural pesticide relative fields) directly from primary raw materials through the reaction.COPYRIGHT KIPO 2017
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Paragraph 0044-0048; 0106
(2018/02/28)
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- 2 - (3 - halogen-phenyl) pyridine derivatives for preparing method
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The invention discloses a preparation method of a 2-(3-halogen phenyl) pyridine derivative. The preparation method comprises the following steps: dissolving 2-phenylpyridine or substitutive 2-phenylpyridine (I) and N-halogenated butyl diimide (II) into a
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Paragraph 0031; 0032; 0034
(2017/08/25)
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- meta-C?H Bromination on Purine Bases by Heterogeneous Ruthenium Catalysis
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Methods for positionally selective remote C?H functionalizations are in high demand. Herein, we disclose the first heterogeneous ruthenium catalyst for meta-selective C?H functionalizations, which enabled remote halogenations with excellent site selectivity and ample scope. The versatile heterogeneous Ru@SiO2catalyst was broadly applicable and could be easily recovered and reused, which set the stage for the direct fluorescent labeling of purines. In contrast to palladium, rhodium, iridium, or cobalt complexes, solely the ruthenium catalysis manifold provided access to meta-halogenated purine derivatives, illustrating the unique power of ruthenium C?H activation catalysis.
- Warratz, Svenja,Burns, David J.,Zhu, Cuiju,Korvorapun, Korkit,Rogge, Torben,Scholz, Julius,Jooss, Christian,Gelman, Dmitri,Ackermann, Lutz
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supporting information
p. 1557 - 1560
(2017/02/05)
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- Directed Aromatic C-H Activation/Acetoxylation Catalyzed by Pd Nanoparticles Supported on Graphene Oxide
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The first solid-supported directed aromatic C-H activation/acetoxylation has been successfully developed by using palladium nanoparticles supported on graphene oxide (PdNPs/GO) as a catalyst. The practicability of this method is demonstrated by simple preparation of catalyst, high catalytic efficiency, wide functional group tolerance, and easy scale up of the reaction. A hot filtration test and Hg(0) poisoning test indicate the heterogeneous nature of the catalytic active species.
- Zhang, Yi,Zhao, Yu,Luo, Yu,Xiao, Liuqing,Huang, Yuxing,Li, Xingrong,Peng, Qitao,Liu, Yizhen,Yang, Bo,Zhu, Caizhen,Zhou, Xuechang,Zhang, Junmin
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supporting information
p. 6470 - 6473
(2017/12/26)
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- ORGANOMETALLIC COMPOUND AND ORGANIC LIGHT-EMITTING DEVICE INCLUDING THE SAME
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An organometallic compound represented by Formula 1: wherein in Formula 1, groups and variables are the same as described in the specification.
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Paragraph 0205; 0209; 0210
(2017/09/21)
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- Green light iridium (III) complex and a method of preparing the same
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The present invention provides a green light iridium (III) complex and a method of preparing the same, which has a formula as follows: wherein m is 2 or 3; at least one of Ar1, Ar2, Ar3, Ar4, and Ar5
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Page/Page column 9; 10
(2016/05/09)
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- A pyridine phongl as the nuclear in the three compounds and methods for their preparation and use
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The invention belongs to the technical field of organic electroluminescence materials, and discloses a compound using tripyridylbenzene as a core as well as a preparation method and application thereof. The compound can be prepared by synthesizing a halog
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Paragraph 0057; 0058; 0075
(2016/11/02)
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- 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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p. 41214 - 41218
(2016/05/19)
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- Organometallic compound and organic light-emitting device including the same
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Organic metal compound and said organometallic compounds is disclosure is an organic light emitting device. (by machine translation)
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Paragraph 0308; 0313; 0314; 0315
(2016/10/07)
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- Directed meta-Selective Bromination of Arenes with Ruthenium Catalysts
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A Ru-catalyzed direct C?H activation/meta-bromination of arenes bearing pyridyl, pyrimidyl, and pyrazolyl directing groups has been developed. A series of bromo aryl pyridines and pyrimidines have been synthesized, and further coupling reactions have also been demonstrated for a number of representative functionalized arenes. Preliminary mechanistic studies have revealed that this reaction may proceed through radical-mediated bromination when NBS is utilized as the bromine source. This type of transformation has opened up a new direction for the radical non-ipso functionalization of metal with regard to future C?H activation development that would allow the remote functionalization of aromatic systems.
- Yu, Qingzhen,Hu, Le'An,Wang, Yue,Zheng, Shasha,Huang, Jianhui
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p. 15284 - 15288
(2016/01/25)
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- Ruthenium-Catalyzed meta-Selective C-H Bromination
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The first example of a transition-metal-catalyzed, meta-selective C-H bromination procedure is reported. In the presence of catalytic [{Ru(p-cymene)Cl2}2], tetrabutylammonium tribromide can be used to functionalize the meta C-H bond of 2-phenylpyridine derivatives, thus affording difficult to access products which are highly predisposed to further derivatization. We demonstrate this utility with one-pot bromination/arylation and bromination/alkenylation procedures to deliver meta-arylated and meta-alkenylated products, respectively, in a single step. Taking position: 2-Phenylpyridines undergo meta-selective bromination using tetrabutylammonium tribromide under ruthenium catalysis, thus affording products that are highly predisposed to further derivatization. The bromination can be combined with arylation and alkenylation chemistry to access meta-arylated and meta-alkenylated products, respectively, in a one-pot operation.
- Teskey, Christopher J.,Lui, Andrew Y. W.,Greaney, Michael F.
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p. 11677 - 11680
(2015/10/05)
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- Silver-catalyzed arylation of (hetero)arenes by oxidative decarboxylation of aromatic carboxylic acids
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A long-standing challenge in Minisci reactions is achieving the arylation of heteroarenes by oxidative decarboxylation of aromatic carboxylic acids. To address this challenge, the silver-catalyzed intermolecular Minisci reaction of aromatic carboxylic acids was developed. With an inexpensive silver salt as a catalyst, this new reaction enables a variety of aromatic carboxylic acids to undergo decarboxylative coupling with electron-deficient arenes or heteroarenes regardless of the position of the substituents on the aromatic carboxylic acid, thus eliminating the need for ortho-substituted aromatic carboxylic acids, which were a limitation of previously reported methods.
- Kan, Jian,Huang, Shijun,Lin, Jin,Zhang, Min,Su, Weiping
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supporting information
p. 2199 - 2203
(2015/02/19)
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- METAL COMPOUNDS, METHODS, AND USES THEREOF
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Disclosed herein are metal compounds useful in devices, such as, for example, OLEDs.
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- PHOSPHORESCENT MATERIALS
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Novel organic compounds containing a twisted aryl group are provided. In particular, the compounds provided contain a 2-phenylpyridine ligand having a twisted aryl group on the pyridine portion of the ligand. The compounds may be used in organic light emitting devices, particularly as emitting dopants. Devices comprising the compounds containing twisted aryl may demonstrate improved color, efficiency, stability and manufacturing. Additionally, methods are provided for making homoleptic Ir (III) compounds which may contain a twisted aryl.
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Paragraph 0184; 0185
(2015/11/16)
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- Copper-catalyzed aerobic synthesis of 2-arylpyridines from acetophenones and 1,3-diaminopropane
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A copper-catalyzed reaction providing direct access to 2-arylpyridines from acetophenones and 1,3-diaminopropane is described. A range of electronically diverse acetophenones undergo this transformation, affording 2-arylpyridines in good yields. (Chemical Equation Presented).
- Xi, Long-Yi,Zhang, Ruo-Yi,Liang, Shuai,Chen, Shan-Yong,Yu, Xiao-Qi
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supporting information
p. 5269 - 5271
(2015/01/09)
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- NOVEL SILYLATED METAL COMPLEXES
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Novel metal complexes containing silyl substitution are provided. Depending on the location of the substitution, compounds that emit in the yellow or green portions of the spectrum can be produced. These compounds are useful as components of OLED devices.
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Paragraph 0159; 0160
(2014/02/15)
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- Palladium-catalyzed trifluoromethylthiolation of aryl C-H bonds
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A method for monotrifluoromethylthiolation of arenes via palladium-catalyzed directed C-H bond activation was described. The reaction was compatible with a variety of functional groups. Initial mechanistic studies disclosed that the turnover limiting step of the catalytic cycle did not involve C-H activation.
- Xu, Chunfa,Shen, Qilong
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supporting information
p. 2046 - 2049
(2014/05/06)
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- Synthesis and self-assembly of NCN-pincer Pd-complex-bound norvalines
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The NCN-pincer Pd-complex-bound norvalines Boc-D/L-[PdCl(dpb)]Nva-OMe (1) were synthesized in multigram quantities. The molecular structure and absolute configuration of 1 were unequivocally determined by single-crystal X-ray structure analysis. The robustness of 1 under acidic/basic conditions provides a wide range of N-/C-terminus convertibility based on the related synthetic transformations. Installation of a variety of functional groups into the N-/C-terminus of 1 was readily carried out through N-Boc- or C-methyl ester deprotection and subsequent condensations with carboxylic acids, R 1COOH, or amines, R2NH2, to give the corresponding N-/C-functionalized norvalines R1-D/L-[PdCl(dpb)]Nva- R2 2-9. The dipeptide bearing two Pd units 10 was successfully synthesized through the condensation of C-free 1 with N-free 1. The robustness of these Pd-bound norvalines was adequately demonstrated by the preservation of the optical purity and Pd unit during the synthetic transformations. The lipophilic Pd-bound norvalines L-2, Boc-L-[PdCl(dpb)]Nva-NH-n-C 11H23, and L-4, n-C4H9CO-L- [PdCl(dpb)]Nva-NH-n-C11H23, self-assembled in aromatic solvents to afford supramolecular gels. The assembled structures in a thermodynamically stable single crystal of L-2 and kinetically stable supramolecular aggregates of L-2 were precisely elucidated by cryo-TEM, WAX, SAXS, UV/Vis, IR analyses, and single-crystal X-ray crystallography. An antiparallel β-sheet-type aggregate consisting of an infinite one-dimensional hydrogen-bonding network of amide groups and π-stacking of PdCl(dpb) moieties was observed in the supramolecular gel fiber of L-2, even though discrete dimers are assembled through hydrogen bonding in the thermodynamically stable single crystal of L-2. The disparate DSC profiles of the single crystal and xerogel of L-2 indicate different thermodynamics of the molecular assembly process. Metalated amino acids: A series of NCN-pincer Pd-complex-bound norvaline derivatives was successfully synthesized without loss of the optical purity and Pd unit. Efficient self-assembly properties of these Pd-norvalines were found to afford well-regulated Pd arrays both in the single crystal and in the supramolecular gel. A solvent-dependent configuration control of the Pd array was corroborated by means of single-crystal X-ray crystallography and cryo-TEM analysis. Copyright
- Ogata, Kazuki,Sasano, Daisuke,Yokoi, Tomoya,Isozaki, Katsuhiro,Yoshida, Ryota,Takenaka, Toshio,Seike, Hirofumi,Ogawa, Tetsuya,Kurata, Hiroki,Yasuda, Nobuhiro,Takaya, Hikaru,Nakamura, Masaharu
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p. 12356 - 12375
(2013/09/23)
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- METAPHENYLENE POLYMER COMPOUND AND LIGHT EMITTING DEVICE USING THE SAME
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A polymer compound comprising a constitutional unit represented by the following formula (2) and a constitutional unit represented by the following formula (1), wherein R1 represents an alkyl group or the like, and R2 and R3 /s
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- Synthesis and characterization of solution-processable highly branched iridium (III) complex cored dendrimer based on tetraphenylsilane dendron for host-free green phosphorescent organic light emitting diodes
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Solution processable highly branched iridium(III) complex fac-tris(2-phenylpyridyl)iridium-cored dendrimer based on tetraphenylsilane dendron and 2-ethylhexyloxy surface groups was prepared. The structure of dendrimer was confirmed by nuclear magnetic resonance, mass and infrared studies. Thermogravimetric analysis and differential scanning calorimetry studies show the thermal stability (T5%) of 625 K with high glass transition temperature of 423 K. Photoluminescence studies of dendrimer showed the core emission at 516 nm in solution and at 521 nm in film, indicating the highly branched non-conjugated tetrahedral tetraphenylsilane dendrons around the core highly inhibit the intermolecular interactions between the cores in the film. The solution processed green emitting phosphorescent organic light emitting diodes based on dendrimer were fabricated and characterized. The device using host free dendrimer as emitter showed the external quantum efficiency of 0.4%. The results show the potential of this new type of dendritic emitting structure in highly efficient solution processed host-free green phosphorescent organic light emitting diodes.
- Kim, Seul-Ong,Zhao, Qinghua,Thangaraju,Kim, Jang Joo,Kim, Yun-Hi,Kwon, Soon-Ki
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experimental part
p. 139 - 145
(2011/12/04)
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- Synthesis of a novel ligand containing phenyl pyridine
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In this article, we provide a new, efficient route to synthesize 2-[3-(3,4-bis(2-ethylhexyloxy)phenyl]phenyl pyridine ligand from readily available starting materials. The target compound was obtained by a condensation reaction and Suzuki coupling reaction. Structures of compounds were demonstrated by 1H NMR, 13C NMR, and high-resolution mass spectrometry. The advantages of this synthetic route are simple operation, mild reaction conditions, and good yields.
- Yu, Mingxin,Fang, Haiyan,Yue, Youfeng,Chen, Yenchun,Chen, Showan
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experimental part
p. 58 - 63
(2010/03/04)
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- Metal-containing dendrimers
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This invention relates to a light emitting device which comprises at least one layer that contains an organometallic dendrimer having a core comprising a metal cation. The invention also relates to organometallic dendrimers and methods for producing the s
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- Silicon-containing dendritic tris-cyclometalated Ir(iii) complex and its electrophosphorescence in a polymer host
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In this paper, we present the synthesis and characterization of a new highly phosphorescent cyclometalated Ir(iii) complex with a silane-based dendritic substituent. The Ir(iii) complex showed 74 ± 3% of absolute phosphorescence quantum efficiency in the film state. In addition, efficient electrophosphorescence (32.8 cd A-1) employing an Ir(iii) complex-poly(N-vinylcarbazole) system device is observed. Study of a series of electroluminescent, spectroscopic, and electrochemical data of the Ir(iii) complex and the reference Ir(ppy)3 reveals superior performance of the new Ir(iii) complex. The Royal Society of Chemistry.
- You, Youngmin,An, Cheng-Guo,Lee, Deug-Sang,Kim, Jang-Joo,Park, Soo Young
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p. 4706 - 4713
(2007/10/03)
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- NOVEL AZALIDE AND AZALACTAM DERIVATIVES AND PROCESS FOR THE PRODUCTION OF THE SAME
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A compound represented by the following general formula (1) or a pharmaceutically acceptable salt thereof, which is useful for a prophylactic and/or therapeutic treatment of a microbial infectious disease. [R1 is hydrogen atom, or a linear C1-6 alkylcarbonyl group; R2 is hydrogen atom, or a C1-6 alkylcarbonyl group; R3 is hydrogen atom, a C1-6 alkyl group, a C1-6 alkylcarbonyl group, a C1-6 alkenyl group, a C2-6 alkenylcarbonyl group, a C2-6 alkynyl group, or an Ar-B- group (Ar represents an aryl group, or a heterocyclic group, and B is a C1-6 alkyl group, a C1-6 alkylcarbonyl group, a C2-6 alkenyl group, a C2-6 alkenylcarbonyl group, or a C2-6 alkynyl group); R5, R6, R7, and R8 represent hydrogen atom, a C1-6 alkyl group, a C2-6 alkenyl group, a C2-6 alkynyl group, or an Ar-B'- group (B' is a C1-6 alkyl group, a C2-6 alkenyl group, or a C2-6 alkynyl group); X is oxygen atom, or an -NR4- group (R4 is hydrogen atom, a C1-6 alkyl group, or a C1-6 alkyl group which may be substituted with an Ar group); and R4' is hydrogen atom, or a group represented by the aforementioned formula (a) (R3" and R4" represent hydrogen atom, or a linear or branched C1-6 alkylcarbonyl group)]
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Page/Page column 45
(2010/11/08)
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- Regioselectivity in palladium-catalyzed C-H activation/oxygenation reactions
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(Chemical Equation Presented) Palladium-catalyzed directed C-H activation/oxygenation reactions have been explored in a series of meta-substituted aryl pyridine and aryl amide derivatives. These transformations tolerate a diverse array of electron-donatin
- Kalyani, Dipannita,Sanford, Melanie S.
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p. 4149 - 4152
(2007/10/03)
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- Synthesis and deprotonation of 2-(halophenyl)pyridines and 1-(halophenyl)isoquinolines
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The ability of the 2-pyridyl and 1-isoquinolyl groups to direct metalation was studied in the benzene series. For this purpose, 2-(halophenyl)pyridines and 1-(halophenyl)isoquinolines were prepared. Interestingly, nucleophilic addition reactions on the azine ring were not observed under kinetic control using butyllithium, and the substrates were cleanly deprotonated on the benzene ring: the azine ring acidifies the adjacent hydrogen H2 (N-H2 interaction through space and/or inductive electron-withdrawing effect) and probably favors the approach of butyllithium (chelation). Under thermodynamic conditions using lithium dialkylamides, the presence of the azine group makes the lithio derivative at C2′ more stable (chelation and/or inductive electron-withdrawing effect). This was evidenced in two ways: (1) syntheses of 2-halophenyllithiums (F, Cl, Br) substituted at C6 by a 2-pyridyl or 1-isoquinolyl group without elimination of lithium halide and (2) iodine migration from C2′ to C4′ when treating 2-(3-halo-2-iodophenyl) pyridines or 1-(3-fluoro-2-iodophenyl)isoquinoline with LTMP. Comparisons between the 2-pyridyl and fluoro units showed the latter was the stronger directing group for deprotonation.
- Mongin, Florence,Rebstock, Anne-Sophie,Trecourt, Francois,Queguiner, Guy,Marsais, Francis
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p. 6766 - 6771
(2007/10/03)
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