618092-28-7Relevant academic research and scientific papers
Syntheses of highly unsaturated isocyanides via organometallic pathways
Mujkic, Monika,Lentz, Dieter
, p. 839 - 849 (2012)
The carbon carbon coupling reaction by nucleophilic attack of (CO) 5Cr(CN-CFCF2) 1 by lithium or Grignard compounds 2a-i yields the isocyanide complexes (CO)5Cr(CN-CFCF-R) 3a-i (a R = CHCH2, b R = CHCF2, c R = CCH, d R = CC-SiMe3, e R = CC-Ph, f R = CC-C6F4OMe, g R = CC-C 6H3(CF3)2, h R = C6F 5, i R = C6H3(CF3)2) as mixtures of E and Z isomers. The dinuclear complexes 5a-c are obtained from the reaction of 1 with the dilithio or dimagnesium compound 4a-c as the Z,Z-, E,Z- and E,E-isomers, respectively. (CO)5Cr(CN-CFCF-CC-CC-CFCF-NC)Cr(CO) 57 is obtained as a mixture of Z,Z-, Z,E- and E,E-isomers from (CO)5Cr(CN-CFCF-CC-H 3d by Eglington-Glaser coupling. (CO) 5Cr(CN-CFCF-CC-CFCF-NC)Cr(CO)56 and (CO) 5Cr(CN-CFCF-CC-CC-CFCF-NC)Cr(CO)57 react with octacarbonyldicobalt forming the cluster compounds Z,Z-[{η2- μ2-(CO)5Cr(CN-CFCF-CC-CFCF-NC)Cr(CO) 5}Co2(CO)6] Z,Z-8, E,Z-[{η2- μ2-(CO)5Cr(CN-CFCF-CC-CFCF-NC)Cr(CO) 5}Co2(CO)6] E,Z-8 and E,E-[{η2- μ2-(CO)5Cr(CN-CFCF-CC-CFCF-NC)Cr(CO) 5}Co2(CO)6] E,E-8 and Z,Z-[{η2- μ2-(CO)5Cr(CN-CFCF-CC-CC-CFCF-NC)Cr(CO) 5}{Co2(CO)6}2] Z,Z-9, E,Z-[{η2-μ2-(CO)5Cr(CN-CFCF-CC-CC-CFCF- NC)Cr(CO)5}{Co2(CO)6}2] E,Z-9 and E,E-[{η2-μ2-(CO)5Cr(CN-CFCF-CC-CC-CFCF- NC)Cr(CO)5}{Co2(CO)6}2] Z,Z-9, respectively. The crystal and molecular structures of E-3d, Z-3h, Z,Z-8, E,Z-8 and Z,Z-9 were elucidated by single-crystal X-ray crystallography.
Aggregation induced emission-emissive stannoles in the solid state
Lork, Enno,Ramirez Y Medina, Isabel-Maria,Rohdenburg, Markus,Staubitz, Anne
supporting information, p. 9775 - 9778 (2020/09/07)
The optoelectronic and structural properties of six stannoles are reported. All revealed extremely weak emission in solution at 295 K, but intensive fluorescence in the solid state with quantum yields (ΦF) of up to 11.1% in the crystal, and of up to 24.4% (ΦF) in the thin film.
Pluripotent Features of Doubly Thiophene-Fused Benzodiphospholes as Organic Functional Materials
Higashino, Tomohiro,Ishida, Keiichi,Sakurai, Tsuneaki,Seki, Shu,Konishi, Tatsuki,Kamada, Kenji,Imahori, Hiroshi,Imahori, Hiroshi
supporting information, p. 6425 - 6438 (2019/04/26)
Linear ladder-type π-conjugated molecules have attracted much interest because of their intriguing physicochemical properties. To modulate their electronic structures, an effective strategy is to incorporate main-group elements into ladder-type π-conjugated molecules. In line with this strategy, a variety of ladder-type π-conjugated molecules with main-group elements have been synthesized to explore their potential utility as organic functional materials. In this context, phosphole-based π-conjugated molecules are highly attractive, owing to their unique optical and electrochemical properties, which arise from the phosphorus atom. Herein, the synthesis and physicochemical properties of doubly thiophene-fused benzodiphospholes, as a new class of phosphole-based ladder-type π-conjugated molecule, are reported. Systematic investigations into the physicochemical properties of doubly thiophene-fused benzodiphospholes revealed their pluripotent features: intense near-infrared fluorescence, excellent two-photon absorption property, and remarkably high electron-transporting ability. This study demonstrates the potential utility of doubly thiophene-fused benzodiphospholes as organic functional materials for biological imaging, nonlinear optics, organic transistors, and organic photovoltaics.
Systematic Experimental and Computational Studies of Substitution and Hybridization Effects in Solid-State Halogen Bonded Assemblies
Nguyen, Suong T.,Ellington, Thomas L.,Allen, Katelyn E.,Gorden, John D.,Rheingold, Arnold L.,Tschumper, Gregory S.,Hammer, Nathan I.,Watkins, Davita L.
, p. 3244 - 3254 (2018/05/09)
A quantitative assessment of the substituent, hybridization, and crystal-packing effects on the electronic, structural, and vibrational properties of halogen bonded systems is presented. Through a combined experimental and theoretical approach employing R
Catalytic Activation of Trimethylsilylacetylenes: A One-Pot Route to Unsymmetrical Acetylenes and Heterocycles
Lasányi, Dániel,Mészáros, ádám,Novák, Zoltán,Tolnai, Gergely L.
, p. 8281 - 8291 (2018/06/11)
For the synthesis of unsymmetrical acetylenes, a Sonogashira coupling-deprotection-Sonogashira coupling reaction sequence is often used. Removal of protecting groups requires harsh conditions or an excess of difficult to handle and expensive reagents. Herein, we disclose a novel catalytic method for the selective deprotection of trimethylsilylacetylenes in Sonogashira reaction. The reagent hexafluorosilicic acid, an inexpensive nontoxic compound, was used to promote the selective desilylation. This method enables the efficient synthesis of unsymmetric acetylenes with other silylated functional groups present. Further possibilities of the method were explored by synthesis of heterocycles.
1,2,3-TRIAZOLE DERIVATIVE AND INSECTICIDE AND ACARICIDE CONTAINING SAID DERIVATIVE AS ACTIVE INGREDIENT
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Paragraph 0228; 0229, (2018/10/30)
The present invention provides a 1,2,3-triazole derivative and an insecticide or acaricide containing the 1,2,3-triazole derivative as an active ingredient.
Electron-density distribution tuning for enhanced thermal stability of luminescent gold complexes
Yamada, Shigeyuki,Yamaguchi, Shun,Tsutsumi, Osamu
, p. 7977 - 7984 (2017/08/17)
Structure-property relationships of newly synthesized luminescent gold complexes were examined from the viewpoint of material applications. In particular, we investigated the effect of controlling the molecular electron-density distribution by introducing trifluoromethyl substituents into the complexes. The structures of the molecular aggregates were not affected by the trifluoromethyl substituents, as all the complexes formed antiparallel dimers in the crystal state. Moreover, we found that the trifluoromethyl substituents enhanced the thermal stability of the complexes without significantly changing the luminescence behaviour. Thus, while the thermal stability of these materials depends on the molecular structure, i.e. the molecular electron-density distribution, the luminescence behaviour mainly depends on the molecular aggregate structure. These results suggest that various material properties, e.g. luminescence colour and thermal stability, can be controlled independently by tuning the structures of molecules and molecular aggregates using trifluoromethyl substituents.
Synthesis of 3-substituted isoindolin-1-ones via a tandem desilylation, cross-coupling, hydroamidation sequence under aqueous phase-transfer conditions
Munoz, Socrates B.,Aloia, Alexandra N.,Moore, Alexander K.,Papp, Attila,Mathew, Thomas,Fustero, Santos,Olah, George A.,Surya Prakash
supporting information, p. 85 - 92 (2015/12/30)
A simple and expedient method for the synthesis of 3-methylene-isoindolin-1-ones 4 under aqueous phase-transfer conditions has been developed. Starting from 2-iodobenzamides 1 and (silyl)alkynes, the products are obtained in high yields and short reaction times (30 min) with the use of inexpensive CuCl/PPh3 catalyst system in the presence of n-Bu4NBr (TBAB) as a phase-transfer agent. Terminal alkynes are conveniently "unmasked" upon in situ desilylation under the reaction conditions. Alkynes possessing heterocyclic moieties were also found as amenable substrates. Furthermore, a one-pot process starting from 2-iodobenzamides 1, aryl halides (bromides or iodides) and trimethylsilylacetylene (TMSA) as a convenient acetylene surrogate was also shown to be feasible under Pd/Cu catalysis.
From bis(silylene) and bis(germylene) pincer-type nickel(II) complexes to isolable intermediates of the nickel-catalyzed sonogashira cross-coupling reaction
Gallego, Daniel,Brueck, Andreas,Irran, Elisabeth,Meier, Florian,Kaupp, Martin,Driess, Matthias,Hartwig, John F.
supporting information, p. 15617 - 15626 (2013/11/06)
The first [ECE]Ni(II) pincer complexes with E = SiII and E = GeII metallylene donor arms were synthesized via C-X (X = H, Br) oxidative addition, starting from the corresponding [EC(X)E] ligands. These novel complexes were fully characterized (NMR, MS, and XRD) and used as catalyst for Ni-catalyzed Sonogashira reactions. These catalysts allowed detailed information on the elementary steps of this catalytic reaction (transmetalation → oxidative addition → reductive elimination), resulting in the isolation and characterization of an unexpected intermediate in the transmetalation step. This complex, {[ECE]Ni acetylide → CuBr} contains both nickel and copper, with the copper bound to the alkyne π-system. Consistent with these unusual structural features, DFT calculations of the {[ECE]Ni acetylide → CuBr} intermediates revealed an unusual E-Cu-Ni three-center-two-electron bonding scheme. The results reveal a general reaction mechanism for the Ni-based Sonogashira coupling and broaden the application of metallylenes as strong σ-donor ligands for catalytic transformations.
Cruciform π-systems: Hybrid phenylene-ethynylene/phenylene-vinylene oligomers
Wilson, James N.,Josowicz, Mira,Wang, Yiqing,Bunz, Uwe H. F.
, p. 2962 - 2963 (2007/10/03)
The cruciform pentamers 3a-g were synthesized by a combined Horner-Sonogashira approach; their band gaps vary significantly with emission varying from blue to red depending upon their substituent pattern.
