新型苝酰亚胺衍生物的合成及其光学性能

以3,4,9,10-苝四酸二酐为原料,设计并合成了三个新型的苝酰亚胺衍生物———N,N’-二(1-戊基己基)-3,4,9,10-苝四羧酸二酰亚胺,N,N’-二(1-戊基己基)-1,6,7,12-四(对叔丁基苯氧基)-3,4,9,10-苝四羧酸二酰亚胺和N,N’-二(4-六氟异丙醇基苯基)-1,6,7,12-四(对叔丁基苯氧基)-3,4,9,10-苝四羧酸二酰亚胺,其结构经1H NMR和MS表征。用UV-Vis和荧光光谱研究了他们的光学性质。     

Rhodium(III)-Catalyzed Asymmetric [4+1] and [5+1] Annulation of Arenes and 1,3-Enynes: A Distinct Mechanism of Allyl Formation and Allyl Functionalization

We report chiral Rh^III cyclopentadienyl-catalyzed enantioselective synthesis of lactams and isochromenes through oxidative [4+1] and [5+1] annulation, respectively, between arenes and 1,3-enynes. The reaction proceeds through a C−H activation, alkenyl-to-allyl rearrangement, and a nucleophilic cyclization cascade. The mechanisms of the [4+1] annulations were elucidated by a combination of experimental and computational methods. DFT studies indicated that, following the C−H activation and alkyne insertion, a Rh^III alkenyl intermediate undergoes δ-hydrogen elimination of the allylic C−H via a six-membered ring transition state to produce a Rh^III enallene hydride intermediate. Subsequent hydride insertion and allyl rearrangement affords several rhodium(III) allyl intermediates, and a rare Rh^III η⁴ ene-allyl species with π-agostic interaction undergoes SN₂′-type external attack by the nitrogen nucleophile, instead of C−N reductive elimination, as the stereodetermining step.     

Rh(III)-Catalyzed Annulative Coupling of Sulfoxonium Ylides with Allyl Acetates: Generation of Bicyclo[4.1.0]heptan-2-ones

A highly efficient Rhodium(III)-catalyzed annulative coupling was developed for generating bicyclo[4.1.0] heptan-2-ones from sulfoxonium ylides and allyl acetates under mild conditions. This cascade reaction is versatile to construct cyclopropanes, and the starting materials are stable and easily obtainable.     

新型氰基取代二苯乙烯衍生物的合成及其光学性质

以4-二乙氨基水杨醛和对硝基苯乙腈为原料,经Knoevenagel缩合反应和Williamson反应合成了一个新型的D-π-A型氰基取代二苯乙烯衍生物(M1);用Na₂S将M1硝基还原为氨基,合成了一个新型的D-π-A-D型氰基取代二苯乙烯衍生物(M2),其结构经¹H NMR, ¹³C NMR和FT-IR表征。采用量子化学计算法,UV-Vis和FL研究了M1和M2的光学性质。结果表明：M1具有较强的ICT和明显的溶剂生色性质;M1的HOMO和LUMO轨道电子云分离明显,带隙较窄。     

两个查尔酮衍生物的合成、理论计算及三阶非线性光学性质

合成了两个查尔酮类衍生物1-(4-甲基苯基)-3-(4-二甲氨基苯基)丙烯酮(1)和1-(4-甲基苯基)-3-(4-甲氧基苯基)丙烯酮(2),通过1H NMR、13C NMR、IR、HR-MS对其进行结构表征。采用4f相位相干成像技术测定了化合物1和2的三阶NLO性质,确定了相关参数:脉冲宽度4nm,激光波长分别为500和440nm,1:非线性吸收系数β=7.3×10-10m/W,非线性折射率n2=-3.6×10-17m2/W,三阶非线性极化率χ(3)=2.56×10-11esu;2:β=-4.8×10-10m/W,n2=2.0×10-17m2/W,χ(3)=1.45×10-11esu。测定了化合物紫外光谱,并通过DSC考察了化合物的热稳定性。采用密度泛函方法计算了化合物1和2的轨道能量和极化率,结果表明电子转移能在分子内部进行,显示出良好的非线性光学活性。     

Selective Rhodium(III)-Catalyzed Cross-Dehydrogenative Coupling of Furan and Thiophene Derivatives

A hot couple: An unprecedented rhodium(III)-catalyzed cross-dehydrogenative coupling (CDC) of various furan and thiophene derivatives leads to valuable 2,2'-bi(heteroaryl) products in good yields and selectivities. In addition, pyrroles and indoles can also be used as coupling partners, giving C3-arylated products.     

Iridium(III)-Catalyzed Intermolecular C(sp3)-H Amidation for the Synthesis of Chiral 1,2-Diamines

Chiral 1,2-diamines are privileged scaffolds among bioactive natural products, active pharmaceutical ingredients, ligands for transition-metal-based asymmetric catalysis and organocatalysts. Despite this interest, the construction of chiral 1,2-diamine motifs still remains a challenge. To address this, an iridium(III)-catalyzed intermolecular C(sp³)-H amidation reaction was developed. This method relies on the design of a new, cheap and cleavable exo-protecting/directing group derived from camphorsulfonic acid, which is directly installed from easily accessible precursors, and furnishes scalemic free 1,2-diamines upon cleavage of both nitrogen substituents. It was found applicable to both α-secondary and α-tertiary-1,2-diamines, for which a two-step protocol involving intermolecular olefin hydroamination and C(sp³)-H amidation was developed. Kinetic and computational studies provided insights into the observed reactivity difference between pairs of diastereoisomeric substrates.     

Ruthenium(II)-Catalyzed Double Annulation of Quinones: Step-Economical Access to Valuable Bioactive Compounds

Double ruthenium(II)-catalyzed alkyne annulations of quinones were accomplished. Thus, a strategy is reported that provides step-economical access to valuable quinones with a wide range of applications. C−H/N−H activations for alkyne annulations of naphthoquinones provided challenging polycyclic quinoidal compounds by forming four new bonds in one step. The singular power of the thus-obtained compounds was reflected by their antileukemic activity.     

Nitrogen-Doped Carbon Quantum Dots for Biosensing Applications: The Effect of the Thermal Treatments on Electrochemical and Optical Properties

The knowledge of the ways in which post-synthesis treatments may influence the properties of carbon quantum dots (CDs) is of paramount importance for their employment in biosensors. It enables the definition of the mechanism of sensing, which is essential for the application of the suited design strategy of the device. In the present work, we studied the ways in which post-synthesis thermal treatments influence the optical and electrochemical properties of Nitrogen-doped CDs (N-CDs). Blue-emitting, N-CDs for application in biosensors were synthesized through the hydrothermal route, starting from citric acid and urea as bio-synthesizable and low-cost precursors. The CDs samples were thermally post-treated and then characterized through a combination of spectroscopic, structural, and electrochemical techniques. We observed that the post-synthesis thermal treatments show an oxidative effect on CDs graphitic N-atoms. They cause their partially oxidation with the formation of mixed valence state systems, [CDs]⁰⁺, which could be further oxidized into the graphitic N-oxide forms. We also observed that thermal treatments cause the decomposition of the CDs external ammonium ions into ammonia and protons, which protonate their pyridinic N-atoms. Photoluminescence (PL) emission is quenched.     

对称排列的咔唑基树状分子的合成及其光物理性能和电化学性能(英文)

采用乌尔曼缩合反应合成了新型的咔唑基树状分子;利用核磁共振谱仪(1HNMR,13CNMR)和飞行时间质谱仪(MALDI-TOF-Mass)对其进行了表征;并评价了树状分子的荧光性能和电化学性能.结果表明,所合成的咔唑基树状化合物在394nm处发蓝光,同时具有低的HOMO能级.     

Chemo- and Regioselective Catalyst-Controlled Carbocyclization of Alkynyl Ketones: Rapid Synthesis of 1-Indanones and 1-Naphthols

A catalyst-controlled intramolecular carbocyclization of 2-alkynyl aryl ketones is presented. Under rhodium(III) catalysis, 1-indanones are formed through 5-exo-dig carbocyclizations with exclusive chemo-, regio- and stereoselectivity. When catalyzed by copper(I), 1-naphthols are obtained through 6-endo-dig carbocyclizations with exclusive chemo- and regioselectivity.     

Versatile Reaction Pathways of 1,1,3,3,3-Pentafluoropropene at Rh(I) Complexes [Rh(E)(PEt3)3] (E=H,GePh3, Si(OEt)3, F,Cl): C-F versus C-H Bond Activation Steps

The reaction of the rhodium(I) complexes [Rh(E)(PEt₃)₃] (E=GePh₃ ( 1 ), H ( 6 ), F ( 7 )) with 1,1,3,3,3-pentafluoropropene afforded the defluorinative germylation products Z/E-2-(triphenylgermyl)-1,3,3,3-tetrafluoropropene and the fluorido complex [Rh(F)(CF₃CHCF₂)(PEt₃)₂] ( 2 ) together with the fluorophosphorane E-(CF₃)CH=CF(PFEt₃). For [Rh(Si(OEt)₃)(PEt₃)₃] ( 4 ) the coordination of the fluoroolefin was found to give [Rh{Si(OEt)₃}(CF₃CHCF₂)(PEt₃)₂] ( 5 ). Two equivalents of complex 2 reacted further by C−F bond oxidative addition to yield [Rh(CF=CHCF₃)(PEt₃)₂(μ-F)₃Rh(CF₃CHCF₂)(PEt₃)] ( 9 ). The role of the fluorido ligand on the reactivity of complex 2 was assessed by comparison with the analogous chlorido complex. The use of complexes 1 , 4 and 6 as catalysts for the derivatization of 1,1,3,3,3-pentafluoropropene provided products, which were generated by hydrodefluorination, hydrometallation and germylation reactions.     

芳香查尔酮衍生物的合成、理论计算及三阶非线性光学性质

合成了2种新的具有潜在应用价值的非线性光学(NLO)有机材料芳香查尔酮衍生物1-(呋喃-2-基)-3-(4-甲氧基苯基)丙烯酮(1)和1-(噻吩-2-基)-3-(4-甲氧基苯基)丙烯酮(2),并对其进行了NMR、IR和HR-MS结构表征。 采用4f相位相干成像技术测定了化合物1和2的三阶NLO性质并确定了相关参数:脉冲宽度4 nm,激光波长440 nm,化合物1:非线性吸收系数β=5.5×10^-10 m/W,非线性折射系数n₂=-2.1×10^-17 m²/W,三阶非线性极化率χ⁽³⁾=1.58×10^-11 esu;化合物2:β=-2.4×10^-10 m/W,n₂=0.3×10^-17 m²/W,χ⁽³⁾=0.50×10^-11 esu;并测定了紫外光谱和DSC曲线。 采用密度泛函方法计算了化合物1和2的轨道能量和极化率,结果表明电子转移能在分子内部进行,说明比较易于极化,展示了良好的非线性光学性质。     

A New Class of C2-Symmetric Chiral Cyclopentadienyl Ligand Derived from Ferrocene Scaffold: Design,Synthesis and Application

A new class of C₂-symmetric, chiral cyclopentadienyl ligand based on planar chiral ferrocene backbone was developed. A series of its corresponding rhodium(I), iridium(I), and ruthenium(II) complexes were prepared as well. In addition, the rhodium(I) complexes were evaluated in the asymmetric catalytic intramolecular amidoarylation of olefin-tethered benzamides via C−H activation.     

Rainbow Perylene Monoimides: Easy Control of Optical Properties

Perylene dyes have been widely used as photoreceptors in organic photovoltaics because of their outstanding photo‐, thermal and chemical stability as well as their excellent photophysical properties. Herein we describe a novel generation of perylene dyes based on N‐(2,6‐diisopropylphenyl)‐perylene‐3,4‐dicarboximide. The optical properties of these novel perylenes can be finely tuned via the substituents in the 1‐, 6‐ and 9‐positions of the perylene core. The facile synthesis, tunable orbital and absorption properties, and electrochemical potentials help us to design efficient perylene sensitizers for solar‐cell applications.     

四(对己氧苯基)卟啉稀土配合物的合成,表征和电化学性质

合成了四种乙酰丙酮-meso-四(对己氧苯基)卟啉稀土配合物,LnT(p-C6H13O)PPacac(Ln:Y,Dy,Er,Yb;Hacac:乙酰丙酮),研究了其紫外-可见光谱、红外光谱、氢核磁共振谱和荧光光谱,对各个谱带进行了归属,并用循环伏安法对其电化学性质进行了研究.     

Solvent-dependent interconversions between Rh(I), Rh(II), and Rh(III) complexes of an aryl-monophosphine ligand

Reaction of the aryl-monophosphine ligand alpha(2)-(diisopropylphosphino)isodurene (1) with the Rh(I) precursor [Rh(coe)(2)(acetone)(2)]BF(4) (coe=cyclooctene) in different solvents yielded complexes of all three common oxidation states of rhodium, depending on the solvent used. When the reaction was carried out in methanol a cyclometalated, solvent-stabilized Rh(III) alkyl-hydride complex (2) was obtained. However, when the reaction was carried out in acetone or dichloromethane a dinuclear eta(6)-arene Rh(II) complex (5) was obtained in the absence of added redox reagents. Moreover, when acetonitrile was added to a solution of either the Rh(II) or Rh(III) complexes, a new solvent-stabilized, noncyclometalated Rh(I) complex (6) was obtained. In this report we describe the different complexes, which were fully characterized, and probe the processes behind the remarkable solvent effect observed.     

Functionalization of Piperidine Derivatives for the Site-Selective and Stereoselective Synthesis of Positional Analogues of Methylphenidate

Rhodium-catalyzed C−H insertions and cyclopropanations of donor/acceptor carbenes have been used for the synthesis of positional analogues of methylphenidate. The site selectivity is controlled by the catalyst and the amine protecting group. C−H functionalization of N-Boc-piperidine using Rh₂(R-TCPTAD)₄, or N-brosyl-piperidine using Rh₂(R-TPPTTL)₄ generated 2-substitited analogues. In contrast, when N-α-oxoarylacetyl-piperidines were used in combination with Rh₂(S-2-Cl-5-BrTPCP)₄, the C−H functionalization produced 4-susbstiuted analogues. Finally, the 3-substituted analogues were prepared indirectly by cyclopropanation of N-Boc-tetrahydropyridine followed by reductive regio- and stereoselective ring-opening of the cyclopropanes.     

新型萘四酰亚胺类长波长荧光染料的构建及其光谱调控

本文通过杂环胺类对二溴萘四酰亚胺的亲核反应,分别设计合成了8个未见报道的基于萘四酰亚胺母体的新型单取代或者双取代荧光染料.系统性光谱研究表明,胺类的推电子作用差异可以很好地调控其吸收和荧光波长,使之成为一类性能良好的可见或长波长荧光染料(最大吸收509—580 nm;最大发射565—638 nm;荧光量子效率0.21—0.54;Stokes位移36—77 nm).