- Reprint of structural diversity of cobalt(II) coordination compounds involving bent imidazole ligand: A route from 0D dimer to 3D coordination polymer
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Mixed ligand approach could be successfully applied to design porous three-dimensional coordination polymers, involving 1,3-bis(imidazol-1-yl)benzene (1,3-bib) as ligand. Five novel Co(II) compounds with different dimensionality have been synthesized. Utilizing only 1,3-bib in the solvothermal reaction with Co(II) salts, only molecular dimer Co2(bib)2Cl4 or 1D polymer Co2(1,3-bib)2(NO3)2 could be synthesized. Copolymerization technique using additional linear dicarboxylates 1,4-benzenedicarboxylate (1,4-bdc) or 2,6- naphthalenedicarboxylate (2,6-ndc) facilitates the formation of 2D layered coordination polymers Co(1,3-bib)(1,4-bdc) and Co(1,3-bib)(2,6-ndc). Utilizing 4,4′-biphenyldicarboxylate (4,4′-bpdc) as a co-linker, a 3D metal-organic framework Co3(1,3-bib)(4,4′-bpdc)3 (DUT-58, DUT-Dresden University of Technology), possessing two interpenetrated uninodal 8-connected frameworks, has been obtained. DUT-58 exhibits a specific surface area of 1208 m2/g and adsorbs 27 mg/g hydrogen (maximum excess value at 30 bar and 77 K), 0.18 g/g n-butane (at 293 K) and 72 mg/g methane (maximum excess value at 60 bar and 298 K).
- Schlechte, Laura,Bon, Volodymyr,Grünker, Ronny,Klein, Nicole,Senkovska, Irena,Kaskel, Stefan
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- Silver(I) and copper(I) complexes with bis-NHC ligands: Dinuclear complexes, cubanes and coordination polymers
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Silver(I) and copper(I) complexes containing neutral bis(N-heterocyclic carbene) (NHC) ligands and coordinated or non-coordinated chloride, bromide, iodide, or tetrafluoroborate anions, were synthesised. The nature of the anions impacts deeply the structu
- Charra, Valentine,De Frémont, Pierre,Breuil, Pierre-Alain R.,Olivier-Bourbigou, Hélène,Braunstein, Pierre
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- Synthesis of AuI- and AuIII-Bis(NHC) Complexes: Ligand Influence on Oxidative Addition to AuISpecies
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The oxidation chemistry of a range of AuI-bis(NHC) (NHC = N-heterocyclic carbene) complexes with hypervalent iodine(III) oxidants has been explored. AuI-bis(NHC) precursors have been synthesised by treatment of the corresponding [Au(NHC)Cl] derivatives with imidazol(idin)ium salts in the presence of K2CO3. The reactivity of the AuIcomplexes towards PhICl2has revealed an influence of the nature of the NHC ligands present in the complex on the outcome of the oxidation reaction: small and more strongly electron-donating NHC ligands favoured the formation of a AuIIIspecies. On the basis of these results, a AuIcomplex bearing two 1-butyl-3-methylimidazol-2-ylidene (BMIM) ligands has been synthesised. This complex reacted with PhICl2and also – for the first time in Au-NHC systems – with PhI(OAc)2and PhI(OAcF)2(OAcF= trifluoroacetate), affording stable AuIII-(NHC)2complexes bearing acetate ligands.
- Collado, Alba,Bohnenberger, Jan,Oliva-Madrid, María-José,Nun, Pierrick,Cordes, David B.,Slawin, Alexandra M. Z.,Nolan, Steven P.
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- Efficient Route to 1,3-Di-N-imidazolylbenzene. A Comparison of Monodentate vs Bidentate Carbenes in Pd-Catalyzed Cross Coupling
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(Equation Presented) A new bis(carbene) ligand architecture has been developed and was evaluated in the Suzuki-Miyaura cross-coupling reaction of various aryl halides with phenylboronic acid. Several new bis(carbene) ligands were tested in different carbe
- Vargas, Victor C.,Rubio, Ramel J.,Hollis, T. Keith,Salcido, Martha E.
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- Synthesis, air stability, photobleaching, and DFT modeling of blue light emitting platinum CCC-N-heterocyclic carbene pincer complexes
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The recently reported metalation/transmetalation route for the synthesis of CCC-bis(NHC) pincer ligand supported transition-metal complexes was extended to Pt. 2-(1,3-Bis(N-butylimidazol-2-ylidene)phenylene)(chloro)platinum(II) (1) and its bromo analogue 2 were synthesized and characterized. X-ray crystal structure determinations revealed complexes 1 and 2 to have distorted-square- planar configurations around the metal. Photophysical and thermal properties of these complexes are reported, and their extended photostability in air is discussed and contrasted. Density functional theory (DFT) and time-dependent density functional theory (TD-DFT) computations of the ground state and various low-lying excited states have revealed admixing of Pt 5d orbitals and the ligand π* orbitals for both the ground state and the low-lying excited states of complex 1, indicating the low-lying states to be a mixture of metal-to-ligand charge-transfer and ligand-centered transition (MLCT-LC). Somewhat surprisingly, the computed gas-phase geometry of the excited state of complex 1 had a significant distortion, mostly about the Caryl-Pt-Cl angle. These complexes were congeners of materials for organic light emitting diodes (OLEDs).
- Zhang, Xiaofei,Wright, Ashley M.,Deyonker, Nathan J.,Hollis, T. Keith,Hammer, Nathan I.,Webster, Charles Edwin,Valente, Edward J.
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- Nanoscale metallogel via self-assembly of self-assembled trinuclear coordination rings: Multi-stimuli-responsive soft materials
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A rare variety of coordination rings having the M3L6 composition are prepared by the combination of Pd(NO3)2 with an imidazolyl or benzimidazolyl appended bidentate non-chelating ligand (i.e.L1 or L2). The varia
- Ganta, Sudhakar,Chand, Dillip Kumar
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- Spin-Canted Antiferromagnetic Ordering in Transition Metal-Organic Frameworks Based on Tetranuclear Clusters with Mixed V- and Y-Shaped Ligands
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Four transition metal-organic frameworks were solvothermally synthesized with V-shaped 1,3-bis(1-imidazolyl)benzene (bib) and two Y-shaped carboxylate ligands (1,3,5-benzenetricarboxylic acid (H3btc) and 3,5-pyridinedicarboxylic acid (H2pydc)), namely, {[M2(μ3-OH)(bib)(btc)]·H2O}n (M = Co (1) and Fe (2)) and {[M′2(μ3-OH)(μ2-NO3)(bib)(pydc)]·solvents}n (M′ = Co (3) and Ni (4)). All of them are characterized by single-crystal X-ray diffraction, infrared spectrosopy, and powder X-ray diffraction. Both complexes 1 and 2 present two-dimensional (3,8)-connected layer structures, and the point symbol is (3.42)2(34.46.56.68.73.8), but Fe2 in 2 is weakly coordinated to O5 as a trigonal bipyramidal geometry compared with the tetrahedral Co2 in 1, while complexes 3 and 4 exhibit three-dimensional pillar-layer structures with (3,8)-connected tfz-d net. Interestingly, nitrate anions with a rare μ2-η2 coordination mode take part in coordination, and rectangular channels along the c axis exist in 3 and 4. Magnetic studies indicate that 1 and 2 present antiferromagnetic behaviors, while 3 and 4 show the coexistence of spin-canting and long-range magnetic ordering.
- Cao, Chen,Liu, Sui-Jun,Yao, Shu-Li,Zheng, Teng-Fei,Chen, Yong-Qiang,Chen, Jing-Lin,Wen, He-Rui
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- Directed Ortho Calciation of 1,3-Bis(3-isopropylimidazol-2-ylidene)benzene
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The deprotonation of 1,3-bis(3-isopropylimidazol-2-ylidene)benzene with Me3SiCH2CaX (X = Br, I) in tetrahydrofuran (THF) yields the ether adducts of the corresponding 2,6-bis(3-isopropylimidazol-2-ylidene)phenylcalcium halides (X = B
- Koch, Alexander,Krieck, Sven,G?rls, Helmar,Westerhausen, Matthias
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- Crystal engineering with palladium(II)-based self-assembled binuclear complexes as tectons
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A series of binuclear palladium(II)-based self-assembled metallomacrocycles of Pd2L′2L2 type compositions were synthesized by complexation of an imidazole appended non-chelating bidentate ligand L with different cis-protec
- Ganta, Sudhakar,Jagan, Rajamony,Chand, Dillip K.
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- ORGANOMETALLIC COMPOUND, ORGANIC LIGHT-EMITTING DEVICE INCLUDING THE SAME
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The invention relates to an organometallic compound, an organic light-emitting device including the same. The organometallic compound is represented by Formula 1. The organic light-emitting device includes a first electrode, a second electrode, and an org
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Paragraph 0686; 0689; 0694-0695
(2021/05/29)
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- [3+2+1]coordination configuration iridium metal complex, preparation method thereof and organic electroluminescent device
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The invention belongs to the technical field of organic photoelectric materials, and discloses an iridium metal complex with [3+2+1] coordination configuration as well as a preparation method and an application thereof. The iridium metal complex has a structure as shown in a formula (I). According to the iridium metal complex, emission wavelength from deep ultraviolet to infrared, relatively highquantum efficiency and adjustable phosphorescence lifetime are realized by synergistically adjusting bidentate ligands and utilizing the strong field ligand effect of tridentate ligands and monodentate ligands. The iridium metal complex is applied to preparation of an object material of a light-emitting layer in an organic light-emitting device. The invention further discloses an organic light-emitting device, at least one functional layer contains the iridium metal complex, the complex is used as an object material of a light-emitting layer, and the OLED device with high blue light emitting efficiency is prepared.
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Paragraph 0095-0097
(2020/06/24)
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- PLATINUM COMPLEXES FOR BLUE OLED APPLICATION
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Described herein are compounds that are platinum emitters and, more particularly compounds that are platinum emitters of blue light and their applications in blue emitting organic light-emitting diodes (OLED). Also disclosed herein are devices that compri
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Page/Page column 22
(2017/08/07)
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- Probing Conformational Variation in Luminescent Dinuclear Gold(I) N-Heterocyclic Carbene Complexes
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A series of six dinuclear AuI complexes bearing arene-bridged bidentate imidazolylidene (N-heterocyclic carbene, NHC) ligands have been synthesized and characterized. The ligand arene linkers (benzene, pyridine, pyrazine) and NHC-wingtip R-groups (methyl, benzyl) were modified to investigate the influence of these groups on the preference for two distinct conformational isomeric forms. These two conformations differ in their Au···Au distances; an open form with an Au···Au separation of ca. 7 ? and a twisted conformation with a short Au···Au distance of ca. 3 ?. Five of the complexes were structurally characterized using X-ray crystallography. Photophysical studies on the complex with a pyridyl linker group and benzyl wingtip groups showed that the twisted conformation resulted in a low-energy (LE) photoluminescence emission that is associated with the intermolecular aurophilic interaction. In contrast, no room temperature (r.t.) photoluminescence was observed for the open conformation in the solid state, while a high-energy (HE) emission was observed at 77 K. The pyridyl linked complexes were non-emissive in solution at room temp., but upon freezing to form a glassy matrix at 77 K, dual HE and LE emissions were observed that closely match the solid-state spectra for open and twisted complexes, respectively. These observations, in combination with a thorough theoretical investigation, provide important insights into the conformational behavior of complexes of this type. The use of low temperature frozen glasses to trap individual components of conformationally diverse samples for photoluminescence investigations represents a novel approach to study the dynamic and conformational behavior of dinuclear AuI complexes in solution.
- Pell, Thomas P.,Stringer, Bradley D.,Tubaro, Cristina,Hogan, Conor F.,Wilson, David J. D.,Barnard, Peter J.
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p. 3661 - 3674
(2017/08/23)
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- Effect of positive-charges in diphosphino-imidazolium salts on the structures of Ir-complexes and catalysis for hydroformylation
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The effect of positive charges in the diphosphino-imidazolium salts of L2 was investigated in terms of coordinating character, structures of corresponding Ir-complexes and catalysis for hydroformylation. It was found that the involved positive charges exhibited strong electron-withdrawing effect on the neighbored phosphine fragment, rendering L2 more π-acceptor ability than the corresponding neutral counterpart of L1. Consequently, the changed coordinating ability of L1 and L2 led to the variety in the structures and components for the Ir-complexes (Ir-L1a, Ir-L1b, Ir-L2a, and Ir-L2b). The complexation of L2 with Ir(acac)(CO)2 led to a novel five-coordinate Ir(II)-complex of Ir-L2a chelated by a PCC (phosphine-carboanion-carbene) pincer in tripodal mode, whereas the complexation of L1 with Ir(acac)(CO)2 led to a four-coordinate square-planar Ir(I)-complex of Ir-L1a chelated by a PCP (phosphine-carboanion-phosphine) pincer. In addition, the different catalytic performances of these Ir-complexes ligated by L1 and L2 for hydroformylation of olefins were investigated.
- Zhang, Heng,Li, Yong-Qi,Wang, Peng,Lu, Yong,Zhao, Xiao-Li,Liu, Ye
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p. 337 - 343
(2015/12/01)
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- Metal complexes with di(N-heterocyclic carbene) ligands bearing a rigid: Ortho -, meta or para -phenylene bridge
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Three novel dinuclear bis-dicarbene silver(i) complexes of general formula [Ag2(MeIm-phenylene-MeIm)2](PF6)2 (Im = imidazol-2-ylidene) were synthesized. The corresponding copper(i) and gold(i) complexes were obt
- Monticelli, Marco,Tubaro, Cristina,Baron, Marco,Basato, Marino,Sgarbossa, Paolo,Graiff, Claudia,Accorsi, Gianluca,Pell, Thomas P.,Wilson, David J. D.,Barnard, Peter J.
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p. 9540 - 9552
(2016/07/06)
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- Bimetallic N-Heterocyclic Carbene Rh(I) Complexes: Probing the Cooperative Effect for the Catalyzed Hydroelementation of Alkynes
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A series of bimetallic N-heterocyclic carbene Rh(I) complexes (13, 14, 16, 18, 19, and 21) were prepared, in which two metal fragments are linked to a central organic scaffold. These complexes were investigated as catalysts for the hydroelementation of al
- Diachenko, Vera,Page, Michael J.,Gatus, Mark R. D.,Bhadbhade, Mohan,Messerle, Barbara A.
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p. 4543 - 4552
(2015/10/06)
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- DINUCLEAR METAL COMPLEXES COMPRISING CARBENE LIGANDS AND THE USE THEREOF IN OLEDS
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The present invention relates to dinuclear metal-carbene complexes comprising a central atom selected from platinum and palladium, where both metal atoms are cyclometalated to the same aromatic group, to OLEDs (Organic Light-Emitting Diodes) which compris
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Page/Page column 48
(2014/02/15)
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- Metal and halogen dependence of the rate effect in hydroamination/ cyclization of unactivated aminoalkenes: Synthesis, characterization, and catalytic rates of CCC-NHC hafnium and zirconium pincer complexes
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1,3-Bis(3′-butylimidazol-1′-yl)benzene dibromide (2b) or 1,3-bis(3′-butylimidazol-1′-yl)benzene dichloride (2c) was reacted with a stoichiometric amount of Zr(NMe2)4 or Hf(NMe 2)4 yielding four new early transit
- Clark, Wesley D.,Cho, Joon,Valle, Henry U.,Hollis, T. Keith,Valente, Edward J.
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p. 534 - 540
(2014/03/21)
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- Phosphane-ligated ionic palladium complexes: Synthesis, characterization and application as efficient and reusable precatalysts for the homogeneous carbonylative sonogashira reaction under CuI-free conditions
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The stable ionic PdII complexes 1A-4A were synthesized through the complexation of PdCl2(MeCN)2 with the phosphane-functionalized ionic liquids (FILs) 1-4 with π-acceptor character. Single-crystal X-ray diffraction analyses showed that 1A-4A were all composed of PdII-centred square-planar cations and triflate (OTf-, CF3SO3-) counteranions. The complex cations in 1A-3A possessed structural similarity to trans-PdCl2(PPh 3)2. The cation in 4A was a new PdII-centered planar complex ligated by the phosphane-carbon anion-carbene (PCC) pincer in a tripodal manner. The stabilities of 1A-4A were improved due to the intensive π-backbonding interaction between the Pd and P atoms. When complexes 1A-4A were used as precatalysts for homogeneous carbonylative Sonogashira coupling of PhI with phenylacetylene free of CuI, 1A-3A exhibited excellent catalytic behaviour with a TON of up to 1700 at a CO pressure of 0.5 MPa and moderate temperature of 100 °C, whereas 4A exhibited poor activity towards the transformation of PhI due to the high stability of 4A. The recycling experiments of 3A in [Bpy]BF4 (as a solvent) indicated that 3A could be recycled for 5 runs with neither activity loss nor metal leaching into the organic phase. Complex 3A also proved to be a general precatalyst for the carbonylative Sonogashira couplings of a wide range of aryl iodides with phenylacetylene. The selectivity of the desired carbonylation product depended more on electronic effects than the steric effects of the substituents of the aryl iodides. The ionic palladium complexes 1A-4A ligated by imidazolium-based-phosphanes were prepared and shown, by single-crystal X-ray diffraction analyses, to be composed of PdII-centered square-planar cations and OTf- counteranions. The complexes were tested as precatalysts for the homogeneous carbonylative Sonogashira coupling of aryl iodides with phenylacetylene. Copyright
- Zhang, Jing,Wang, Yongyong,Zhao, Xiaoli,Liu, Ye
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p. 975 - 985
(2014/03/21)
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- Phosphane-ligated ionic palladium complexes: Synthesis, characterization and application as efficient and reusable precatalysts for the homogeneous carbonylative sonogashira reaction under CuI-free conditions
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The stable ionic PdII complexes 1A-4A were synthesized through the complexation of PdCl2(MeCN)2 with the phosphane-functionalized ionic liquids (FILs) 1-4 with π-acceptor character. Single-crystal X-ray diffraction analyses showed that 1A-4A were all composed of PdII-centred square-planar cations and triflate (OTf-, CF3SO3-) counteranions. The complex cations in 1A-3A possessed structural similarity to trans-PdCl2(PPh3)2. The cation in 4A was a new PdII-centered planar complex ligated by the phosphane-carbon anion-carbene (PCC) pincer in a tripodal manner. The stabilities of 1A-4A were improved due to the intensive π-backbonding interaction between the Pd and P atoms. When complexes 1A-4A were used as precatalysts for homogeneous carbonylative Sonogashira coupling of PhI with phenylacetylene free of CuI, 1A-3A exhibited excellent catalytic behaviour with a TON of up to 1700 at a CO pressure of 0.5 MPa and moderate temperature of 100 °C, whereas 4A exhibited poor activity towards the transformation of PhI due to the high stability of 4A. The recycling experiments of 3A in [Bpy]BF4 (as a solvent) indicated that 3A could be recycled for 5 runs with neither activity loss nor metal leaching into the organic phase. Complex 3A also proved to be a general precatalyst for the carbonylative Sonogashira couplings of a wide range of aryl iodides with phenylacetylene. The selectivity of the desired carbonylation product depended more on electronic effects than the steric effects of the substituents of the aryl iodides.
- Zhang, Jing,Wang, Yongyong,Zhao, Xiaoli,Liu, Ye
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p. 975 - 985
(2015/04/27)
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- (CC*) Cyclometalated binuclear N-heterocyclic biscarbene platinum(ii) complexes-highly emissive phosphorescent emitters
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A series of bimetallic N-heterocyclic carbene (NHC) platinum(ii) complexes with the general formula [Pt(NHC)(L)]2Ph were synthesized, which are composed of two [Pt(NHC)(L)] (L = acetylacetone, dipivaloylmethane or dimesitoylmethane; NHC = 3-met
- Tronnier, Alexander,Strassner, Thomas
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supporting information
p. 9847 - 9851
(2013/08/23)
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- Toward molecular rotors: Tetra-N-heterocyclic carbene Ag(i)-halide cubane-type clusters
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1,3-Bis(3′-butylimidazol-1′-yl)benzene diiodide (2a), 1,3-bis(3′-but-3′′-enyl-imidazolium-3′-yl)benzene diiodide (2b), 1,3-bis(3′-pent-4′′-enyl-imidazolium-3′- yl)benzene diiodide (2c), 1,3-bis(4′-butyl-1′,2′,4′- triazolium-1′-yl)benzene diiodide (2d), or
- Clark, Wesley D.,Tyson, Ginger E.,Keith Hollis,Valle, Henry U.,Valente, Edward J.,Oliver, Allen G.,Dukes, Matthew P.
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p. 7338 - 7344
(2013/07/25)
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- Platinum (II) Di (2-Pyrazolyl) Benzene Chloride Analogs and Uses
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Synthesis of platinum(II) di(2-pyrazolyl)benzene chloride and analogs includes forming a 1,3-di-substituted benzene including two aromatic five-membered heterocycles, and reacting the 1,3-di-substituted benzene with an acidic platinum-containing solution
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Page/Page column 3
(2011/12/14)
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- Halogen-bond-induced activation of a carbon-heteroatom bond
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Benzhydryl bromide can be activated by novel halogen-bond donors and subsequently undergoes a Ritter-like reaction with acetonitrile (see scheme). Comparative experiments with non-iodinated reference compounds and tests with added acids indicate that halo
- Walter, Sebastian M.,Kniep, Florian,Herdtweck, Eberhardt,Huber, Stefan M.
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supporting information; experimental part
p. 7187 - 7191
(2011/09/16)
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- CCC-N-heterocyclic carbene pincer complexes: Synthesis, characterization and hydroamination activity of a hafnium complex
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Our methodology for the stoichiometric preparation of CCC-NHC pincer complexes of Zr has been extended to Hf. The CCCBu-NHC pincer Hf complex has been characterized by X-ray crystal structure analysis. Catalytic activity in the intramolecular h
- Cho, Joon,Hollis, T. Keith,Valente, Edward J.,Trate, Jaclyn M.
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experimental part
p. 373 - 377
(2011/02/16)
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- Helical nonracemic tubular coordination polymer gelators from simple achiral molecules
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A novel class of helical nonracemic tubular coordination polymers, which can immobilize a wide range of solvents at very low concentrations, have been synthesized for the first time in the absence of chiral influences and appended groups. The Royal Societ
- Zhang, Shiyong,Yang, Shengyong,Lan, Jingbo,Yang, Shuaijun,You, Jingsong
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supporting information; experimental part
p. 6170 - 6172
(2009/05/06)
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- Synthetic approaches to sterically hindered N-arylimidazoles through copper-catalyzed coupling reactions
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Optimization studies allowed the efficient synthesis of a simple structural motif based on meta-bis(1-imidazolyl)benzenes 1 through copper-catalyzed coupling of 1,3-diiodobenzene and imidazole under mild reaction conditions. This protocol was then used to prepare a representative sterically hindered N-arylimidazole 2a, the most common structural motif among N-heterocyclic carbenes (NHC). Having optimized the main variables governing CuI-catalyzed imidazole N-arylation, the first Ullmann-type synthesis of N-mesitylimidazole (2a) is reported. Moreover, the coupling between boronic acids as the aryl donor partners and either imidazole or benzimidazole was examined; in all cases the reactions proceeded in very low yield. Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005.
- Alcalde, Ermitas,Dinares, Immaculada,Rodriguez, Sandra,De Miguel, Cristina Garcia
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p. 1637 - 1643
(2007/10/03)
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- Aminoarenethiolate-copper(I)-catalyzed amination of aryl bromides
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(Chemical Equation Presented) Aminoarenethiolate-copper(I) complexes are known to be efficient catalysts for carbon-carbon bond formation. Here, we show the first examples that these thiolate-copper(I) complexes are efficient for carbon-nitrogen bond formation reactions as well. N-Arylation of benzylamine and imidazole with bromobenzene was achieved either in NMP as solvent or under solvent-free conditions in the presence of 2.5 mol % of aminoarenethiolate- copper(I) complex only.
- Jerphagnon, Thomas,Van Klink, Gerard P. M.,De Vries, Johannes G.,Van Koten, Gerard
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p. 5241 - 5244
(2007/10/03)
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