New Cu(I) Coordination Complexes Based on Tetrathiafulvalene Substituted Triazol‐pyridine Ligand: Synthesis,Properties and Theoretical Studies

Two Cu(I) complexes based on the thioethyl‐bridged triazol‐pyridine ligand with tetrathiafulvalene unit (TTF‐TzPy, L ), [Cu(I)(Binap)(L)]BF₄ ( 5 , Binap=2,2’‐bis(diphenylphosphino)‐1,1’‐binaphthyl) and [Cu(I)(Xantphos)(L)]BF₄ ( 6 , Xantphos=9,9‐dimethyl‐4,5‐bis(diphenylphosphino)‐xanthene), have been synthesized. All new compounds are characterized by elemental analyses, ¹H NMR and mass spectroscopies. The complex 5 has been determined by X‐ray structure analyses which shows that the central copper (I) ion assumes distorted tetrahedral geometry. The photophysical, computational and electrochemical properties of L and 5 ‐ 6 have been investigated. The most representative molecular orbital energy‐level diagrams and the spin‐allowed singlet? singlet electronic transitions of the three compounds have been calculated with density functional theory (DFT) and time‐dependent DFT (TD‐DFT). The luminescence bands of Cu(I) complexes 5 ‐ 6 have been assigned as mixed intraligand and metal‐to‐ligand charge transfer ³(MLCT+π→π^*) transitions through analysis of the photophysical properties and DFT calculations. The electrochemical studies reveal that 5 ‐ 6 undergo reversible TTF/TTF^+?/TTF²⁺ redox processes and one irreversible Cu⁺→Cu²⁺ oxidation process.     

Copper(I)-1,1,1-tris(diphenylphosphinomethyl)ethane complexes with different coordination modes tuned by auxiliary ligands and their spectroscopic properties

Three mono-, bi- and tetranuclear copper(I) complexes, [Cu(phen)(triphos-O)]BF₄ (1) (phen = 1,10-phenanthroline, triphos = 1,1,1-tris(diphenylphosphinomethyl)ethane), [Cu₂(bipy)(triphos)₂](BF₄)₂ (2) (bipy = 4,4′-bipyridine), and [Cu₄(MeOC^N^N)₄(triphos)₂(bipy)](BF₄)₄ (3) (MeOC^N^N = 6-(4-methoxyphenyl)-2,2′-bipyridine), have been synthesized and characterized by NMR spectroscopy, electrospray ionization, and matrix-assisted laser desorption ionization time-of-flight mass spectrometries, elemental analysis, and X-ray crystal analysis. The crystal structure investigation revealed the copper ions of the complexes have pseudo-tetrahedral coordination geometry. The electronic absorption spectra of 1, 2, and 3 contain low-energy bands at 350–500 and 400–650 nm, which are assigned to d(Cu) → π*(phen or bipy) and a mixture of d(Cu) → π*(MeOC^N^N) and d(Cu) → π*(bipy) transitions, respectively. Complex 2 displays a strong, long-lived solid-state emission with a maximum at 555 nm and lifetime of 13.6 μs at room temperature. Photoinduced electron-transfer properties of 2 and 3 involving nanosecond time-resolved absorption spectroscopy and electron spin resonance techniques were studied.     

A Novel One‐Dimensional Copper Mellitate Complex Featured by {Cu(H2O)2(urea)[C6(COO)4(COOH)2]}n2n– Polyanions

Blue monoclinic single crystals of the novel one‐dimensional [H₃N‐(CH₂)₆‐NH₃][Cu(H₂O)₂(urea)(μ₂‐C₆(COO)₄(COOH)₂)] · H₂O coordination polymer were prepared in aqueous solution at room temperature in the presence of 1,6‐diaminohexane and urea [space group P2₁/n (no. 14) with a = 958.48(9), b = 1465.74(11), c = 1821.14(12) pm, β = 97.655(8)°]. The Cu²⁺ cation is coordinated in a square pyramidal manner by two oxygen atoms stemming from the dihydrogen mellitate tetraanion, one oxygen atom from the urea molecule, and two water molecules. The Cu–O distances are in the range of 193.3(2) and 229.4(2) pm. The connection between Cu²⁺ and [C₆(COO)₄(COOH)₂]^4– yields infinite chain‐like polyanions parallel to [1$\bar{}$ 01] with a composition of {Cu(H₂O)₂(urea)[C₆(COO)₄(COOH)₂]}_n^2n–. The dihydrogen mellitate tetraanion adopts a μ₂ coordination mode. The [(H₃N–(CH₂)₆–NH₃)]²⁺ cations are accommodated between the chains as counter cations. The hexane‐1,6‐diammonium cations adopt a partial synclinal conformation. The chains are connected by strong and weak hydrogen bonds. Magnetic measurements reveal a paramagnetic Curie‐Weiss behavior and a magnetic moment of 1.93 μ_B per Cu²⁺. Thermoanalytical investigations in air show that the complex is stable up to 135 °C, and the following decomposition processes yield CuO.     

Copper(I) Clusters with Trifunctional Silyl Amide Ligands. Synthesis and Crystal Structures of [Li(THF)4]2[Cu10{RSi(NPh)3}4] (R = Me,Ph, Vin)

Treatment of CuCl with the lithiated silyl amides RSi(NLiPh)₃ (R = Me, Ph, Vin) in THF as solvent led to the formation of the novel Cu^I cluster compounds [Li(THF)₄]₂[Cu₁₀{RSi(NPh)₃}₄]. For each of the three compounds the X‐ray crystal structure analysis revealed similar Si₄N₁₂Cu₁₀ cores which are based on cubane like Cu₈ cores bearing two additional peripheral copper atoms. The copper atoms are coordinated nearly linearly by the μ₅‐bridging silyl amide ligands with Cu–N distances in the range of 187.1(3) to 194.5(4) pm and N–Cu–N angles of 171.6(1) to 178.7(1)°. For each of the compounds the structural parameters are very similar which indicates that the structures are barely influenced by the different steric requirements of the organic groups bound to silicon.     

Crystal Structure and Magnetic Properties of a Hexanuclear Copper(II) Carboxylate

The synthesis and characterisation of the hexanuclear copper(II) carboxylate complex [Cu(O₂CCHPhOC₂H₄OC₂H₄OCH₃)₂]₆ ( 1 ) is described. Single‐crystal X‐ray structure analysis reveals that the copper(II) ions are arranged in a six‐membered ring which adopts a chair‐like conformation. The copper(II) ions are bridged by μ₂‐ and μ₃‐coordinating carboxylates. The magnetic behavior of 1 was measured between 2 and 300 K, revealing at low temperature a weak antiferromagnetic interaction. The χ_M(T) dependency was fitted mathematically with one coupling constant J₁ and a paramagnetic impurity α.     

介孔Fe-Cu复合金属氧化物纳米粉催化剂催化低温CO氧化

以环氧丙烷为凝胶剂,采用简便低廉的无表面活性剂的溶胶-凝胶法制备了一系列不同Cu/Fe摩尔比的高比表面积介孔Fe-Cu复合氧化物纳米粉末。运用微反应器-色谱体系考察了它们在低温CO氧化反应中的催化性能。采用X射线衍射、N2吸附-脱附、热重-差热分析、程序升温还原、傅里叶变换红外光谱和透射电镜对所制样品进行了表征。结果表明,这些介孔Fe-Cu复合氧化物催化剂具有纳米晶结构、窄的孔径分布和高的比表面积,在低温CO氧化反应中表现出高的活性和稳定性。 CuO的添加影响了Fe2O3的结构和催化性能。当CuO含量为15 mol%时,催化剂具有最高的比表面积和催化活性,在低温CO氧化反应中表现出较高的催化稳定性。     

Cu催化吲哚啉的炔丙基烷基化/脱氢对映选择性合成手性N-炔丙基吲哚化合物(英文)

基于吲哚啉的Cu催化不对称炔丙基烷基化及DDQ脱氢策略,成功合成了手性N-炔丙基吲哚化合物.通过使用一个结构刚性的酮亚胺三齿P,N,N-配体,反应获得了很好的对映选择性.该方法反应条件温和、底物适用范围广、产物收率高、立体选择性好,为手性N-炔丙基吲哚化合物的合成提供了一条简捷、高效的新途径.     

高效液相色谱法检测木材产品中8-羟基喹啉铜

采用高效液相色谱法测定木材产品中8-羟基喹啉铜。木材样品经甲醇超声提取两次,以反相C18柱为分离柱、甲醇与乙酸铵-乙酸缓冲溶液作为流动相进行洗脱,采用光电二极管阵列检测器在257nm处进行检测。8-羟基喹啉铜的质量浓度在0.1~10.0mg·L-1范围内与峰面积呈线性关系,检出限(3S/N)为0.06mg·kg-1。对空白样品进行加标回收试验,回收率在76.4%~94.2%之间,测定值的相对标准偏差(n=5)在3.2%~7.5%之间。     

Syntheses,structures, luminescent and magnetic properties of two coordination polymers based on a fl exible multidentate carboxylate ligand

Two coordination polymers,{[Cu_3(tci)_2(DMAc)_3]-6DMAc 2H_2O}_n(1) and {[Cu_3(tci)_2(tpt)_2(H_2O)_2].2DMAc-2H_2O}_n(2)(H_3tci = tris(2-carboxyethyI)isocyanurate,tpt = 2,4,6-tris(4-pyridyl)-l,3,5-triazine,DMAc = N,/V-dimethylacetamide),have been constructed under solvothermal conditions.Both polymers were structurally characterized by single crystal X-ray diffraction,elemental analyses,IR spectra,thermogravimetric(TG) analyses and powder X-ray diffraction(RXPD).1 shows a(3,4)-connected 2D layer structure comprising Cu_2(CO_2)4 paddle-wheel units,which are further bridged by C-H…O interactions to give a 3D supramolecular network.The introduction of tpt produces different framework for 2 that comprises a dinuclear and a mononuclear Cu(Ⅱ) building units,which are further bridged together by tci~(3-) and tpt ligands to give a 4-connected 2D topological net.Adjacent 2D layers are packed together via C-H…O interactions and π…π stacking interactions to form a 3D supramolecular structure.In addition,the luminescent properties and the solid-state UV-vis spectra of 1 and 2 were explored.Furthermore,antiferromagnetic exchange interactions were unveiled in the Cu_2(COO)_4 units of 1.     

Cu(Ⅱ)-catalyzed domino reaction of 2-halobenzamide and arylmethanamine to construct 2-aryl quinazolinone

A novel method for achieving a copper(II)-catalyzed domino reaction for the construction of 2-aryl quinazolinones,without the addition of any ligand and additive,has been developed.The domino reaction achieved N-(a-substituted)benzylation,benzylic C–H amidation,and C–C(or C–H) bond cleavage.