- Functional Pyrimidinyl Pyrazolate Pt(II) Complexes: Role of Nitrogen Atom in Tuning the Solid-State Stacking and Photophysics
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Pt(II) metal complexes are known to exhibit strong solid-state aggregation and are promising for realization of efficient emission in fabrication of organic light emitting diodes (OLED) with nondoped emitter layer. Four pyrimidine–pyrazolate based chelates, together with four isomeric Pt(II) metal complexes, namely: [Pt(pm2z)2], [Pt(tpm2z)2], [Pt(pm4z)2], and [Pt(tpm4z)2], are isolated and systematically investigated for their structure–property relationships for practical OLED applications. Detailed single molecular and aggregated structures are revealed by photophysical and mechanochromic measurements, grazing-incidence X-ray diffraction, and theoretical approaches. These results suggest that these Pt(II) emitters pack like a deck of playing cards under vacuum deposition, and their emission energy is not only affected by the single molecular designs, but notably influenced by their intermolecular packing interaction, i.e., Pt···Pt separations that are arranged in the order: [Pt(tpm4z)2] > [Pt(pm4z)2] > [Pt(tpm2z)2] > [Pt(pm2z)2]. Nondoped OLED with emission ranging from green to red are prepared, to which the best performances are recorded for [Pt(tpm2z)2], giving maximum external quantum efficiency (EQE) of 27.5% at 103 cd m?2, maximum luminance of 2.5 × 105 cd m?2 at 17 V, and with stable CIEx,y of (0.56, 0.44).
- Ganesan, Paramaguru,Hung, Wen-Yi,Tso, Jen-Yung,Ko, Chang-Lun,Wang, Tsai-Hui,Chen, Po-Ting,Hsu, Hsiu-Fu,Liu, Shih-Hung,Lee, Gene-Hsiang,Chou, Pi-Tai,Jen, Alex K.-Y.,Chi, Yun
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- Structure-dependent regioselectivity of a roll-over cyclopalladation occuring at 2,2′-bipyridine-type ligands
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In this work, different bipyridine-analogue ligands bearing a dimethylamino group in the meta-position of one of the heterocyclic rings were synthesized and reacted with palladium(II) acetate under identical conditions. Cyclometallated palladium(II) complexes with C,N- or C,N,N’-coordinating chelate ligands are formed which were characterized by elemental analysis, 1H and 13C NMR spectroscopy, and single crystal X-ray diffraction analysis. In the case of the mononuclear, C,N,N’-coordinated complex, which is formed by an attack of the palladium(II) site at of the N-methyl groups, the primarily coordinating acetato ligand is exchanged against a chlorido ligand, which is liberated from the solvent dichloromethane by a nucleophilic substitution reaction. In contrast, cyclometallation occurring at one of the six-membered heterocycles leads to dinuclear acetato-bridged palladium(II) complexes.
- Becker, Yanik,Sch?n, Florian,Becker, Sabine,Sun, Yu,Thiel, Werner R.
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- A direct access to heterobimetallic complexes by roll-over cyclometallation
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Complexes of the type [Cp?Ir(N,N′)Cl]+ (N,N′ = 2-(2-dialkylaminopyrimidin-4-yl)pyrimidine) can undergo roll-over cyclometallation leading to a novel N,N′-donor site. Following this strategy heterobimetallic complexes including iridium(iii) and a Group X metal centre in the oxidation state +II were achieved.
- Sch?n,Leist,Neuba,Lang,Braun,Sun,Niedner-Schatteburg,Br?se,Thiel
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supporting information
p. 12016 - 12019
(2017/11/10)
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- 1,2,4-TRIAZINE-4-AMINE DERIVATIVES
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According to the invention there is provided a compound of formula A1 which may be useful in the treatment of a condition or disorder ameliorated by the inhibition of the A1- A2b or, particularly, the A2a receptor wherein the compound of formula A1 has the structure, wherein, A represents Cy1 or HetA; Cy1 represents a 5- to 14-membered aromatic, fully saturated or partially unsaturated carbocyclic ring system comprising one, two or three rings, which Cy1 group is optionally substituted by one or more R4a substituents; HetA represents a 5- to 14-membered heterocyclic group that may be aromatic, fully saturated or partially unsaturated, and which contains one or more heteroatoms selected from O, S and N, which heterocyclic group may comprise one, two or three rings and which HetA group is optionally substituted by one or more R4b substituents; B represents a Cy2 or HetB; Cy2 represents a 3- to 10-membered aromatic, fully saturated or partially unsaturated carbocyclic ring system comprising one or two rings, which Cy2 group is optionally substituted by one or more R4c substituents; HetB represents a 3- to 10-membered heterocyclic group that may be aromatic, fully saturated or partially unsaturated, and which contains one or more heteroatoms selected from O, S and N, which heterocyclic group may comprise one or two rings and which HetB group is optionally substituted by one or more R4d substituents.
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Page/Page column 95
(2011/09/14)
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- S-6-METH0XY-2- (2- (3- (PYRIMID-2-YL) IS0XAZ0L-5-YL) PYRROLIDIN-1-YL) -4- (5-METHYL-IH-PYRAZOL-S-YLAMINO) PYRIMIDINE AND POLYMORPHIC FORMS THEREOF AS MODULATORS OF THE INSULIN-LIKE GROWTH
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There is provided novel pyrimidine derivatives of formula (I) or pharmaceutically acceptable salsts thereof, processes for their preparation, pharmaceutical compositions containing them and their use in therapy.
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Page/Page column 37
(2008/12/04)
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- Metal ion chelates of lipophilic alkyl diazinyl ketoximes as hydrolytic catalysts
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A series of lipophilic dodecyl hetaryl ketoximes (hetaryl = pyridin-2-yl, pyridazin-3-yl, pyrimidin-2-yl, pyrimidin-4-yl, pyrazin-2-yl as well as their methyl hetaryl homologues was synthesized and hydrolytic activity of their chelates with Co2+, Ni2+, Cu2+ and Zn2+ in a micellar matrix of hexadecyltrimethylammonium bromide or in homogeneous aqueous solutions was investigated using 4-nitrophenyl acetate, 4-nitrophenyl hexanoate and 4-nitrophenyl diphenyl phosphate as model substrates. While Co2+ and Cu2+ chelates are almost inactive, those of Ni2+ and Zn2+ exhibit considerable activity. None of the studied chelates promotes hydrolysis of the used phosphate. The effective species are chelates of the metal : ligand stoichiometry 1 : 3 and 1 : 1 with Ni2+ and Zn2+, respectively, when the ester cleavage proceeds in the micellar matrix. The 1 : 2 stoichiometry was found in aqueous solutions of Ni2+ and Zn2+ chelates of methyl ketoximes.
- Cibulka, Radek,Hampl, Frantisek,Martinu, Tomas,Mazac, Jiri,Totevova, Sonja,Liska, Frantisek
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p. 1159 - 1179
(2007/10/03)
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- Synthesis of New ν-Triazolopyrimidinium Salts
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New ν-triazolo- and ν-triazolopyrimidinium salts 12a-e, 13a-c have been synthesized via oxidation (i.e. cyclohydrogenation) of the appropriate pyrimidyl ketone arylhydrazones 3a-e, 6a-c using TBB (2,4,4,6-tetrabromocyclohexa-2,5-dien-1-one)
- Batori, S.,Messmer, A.
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p. 1041 - 1046
(2007/10/02)
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- ACIDIFYING EFFECTS OF AZA GROUPS IN THE NH ACIDITY OF AMINOAZINES AND THE CH ACIDITY OF ACETYLAZINES
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The pK values for a series of aminoazines and acetylazines containing one, two, or three aza groups in the ring were determined in dimethyl sulfoxide.There is a good linear correlation between pK values of the investigated NH and CH acids.The acidifying effects (ΔpK) of the aza groups at positions 2, 3, or 4 in relation to the side chain were determined and had values of 3.1, 2.4, and 4.5 logarithmic units in the aminoazines and 3.5, 2.9 and 4.8 logarithmic units respectively in the acetylazines.Except in the case of two ortho-located aza groups the effects are additive.Compared with dimethyl sulfoxide water has a differentiating effect on the acidity of the aminoazines, and this is explained by the formation of hydrogen bonds between the molecules of the proton-donating solvent and the aza groups of the anions of the aminoazines.
- Terekhova, M. I.,Petrov, E. S.,Mikhaleva, M. A.,Shkurko, O. P.,Mamaev, V. P.,Shatenshtein, A. I.
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- PYRIMIDINES. 73. SYNTHESIS OF ACETYLPYRIMIDINES
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It is shown that the use of benzene as the solvent in the preparation of 2- and 4-acetylpyrimidines from cyanopyrimidines via the Grignard reaction makes this reaction a practical method for the preparation of pyrimidinyl ketones.Preparatively convenient methods for the preparation of 4-acetylpyrimidine from 4-ethylpyrimidine through the α-oximino derivative and 5-acetylpyrimidine from 4,6-dichloro derivatives of pyrimidine are proposed.
- Naumenko, I. I.,Mikhaleva, M. A.,Mamaev, V. P.
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p. 710 - 714
(2007/10/02)
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