Self-assembled coordination cage as a reaction vessel: triplet sensitized [2+2] photodimerization of acenaphthylene, and [4+4] photodimerization of 9-anthraldehyde

Inner cavity of Pd-nanocage has been used as a reaction vessel for performing triplet sensitized [2+2] photodimerization of acenaphthylene using water soluble xanthene dyes (Eosin Y and Rose Bengal) as sensitizers, and [4+4] photodimerization of 9-anthraldehyde. Although the [4+4] photodimerization of 9-anthraldehyde gave similar results to solution reaction, the xanthene dye sensitized [2+2] triplet state photodimerization of acenaphthylene encapsulated within Pd-nanocage yielded the syn dimer in quantitative yield. The results obtained from the triplet state [2+2] photodimerization of acenaphthylene within Pd-nanocage is remarkable given the fact that the photodimerization reaction when performed in methanol in the presence of Eosin Y and Rose Bengal gave the syn and anti dimers in the ratio 0.5 and 0.6, respectively. Preaggregation of molecules encapsulated inside Pd-nanocage in a syn fashion seems to be the governing factor for such a behavior.     

η6-苊烯三羰基铬配合物的合成、结构及光谱性质研究

采用苊烯配体与三胺基三羰基铬在四氢呋喃中回流反应,合成了η6-苊烯三羰基铬配合物.通过元素分析、IR、1HNMR、13CNMR、MS和X射线单晶衍射对其结构进行了表征,比较了标题配合物与其自由配体的光物理行为.晶体结构分析表明,标题配合物属单斜晶系,空间群P21/c,Z=4,a=0.8719(7)nm,b=1.2436(10)nm,c=1.1504(9)nm,β=111.835(13)°,Cr(CO)3基团可与苊烯配体中的2个苯环中的任意一个配位,形成2个异构体(R,S),并以1:1的比例在其晶胞单元中反向面对面堆积,这种异构体共存于晶体中归属于Cr(CO)3基团在配体芳环之间的配位移动重排(IRHRs).     

Selective determination of acenaphthylene by flow injection analysis with tris(2,2'-bipyridine)ruthenium(II) chemiluminescence detection

A simple, rapid flow injection chemiluminescence (FI-CL) method has been developed for selective determination of acenaphthylene (ACY), based on the CL produced in the reaction of tris(2,2′-bipyridine)ruthenium(III) (Ru(bipy)₃³⁺) and ACY in an acidic buffer solution. Under the optimum experimental conditions, the calibration curve was linear over the range 5.0 × 10⁻³ to 4.0 × 10⁻⁷ mol L⁻¹ for ACY. The detection limit (S/N = 3) was 2.0 × 10⁻⁷ mol L⁻¹ and the relative standard deviation of 10 replicate measurements was 2.3% for 5.0 × 10⁻⁵ mol L⁻¹ of ACY. Selectivity of CL reaction of ACY from other 15 polycyclic aromatic hydrocarbons (PAHs) was investigated by flow injection method. The method was applied to determine the ACY content in soil.     

One-step synthesis of diazadihydroacenaphthylene derivatives with an isoxazoline ring, starting from 1-benzylamino-1-methylsulfanyl-2-nitroethenes

At low temperature in trifluoromethanesulfonic acid, 1-benzylamino-1-methylthio-2-nitroethene derivatives form hydroxynitrilium ions (or O-protonated nitrile oxides) observed by NMR. Quenching with water leads to the formation of a reactive nitrile oxide, dipole which undergoes an unexpected INOC reaction leading to new 3-methylsulfanyl-8a,8b-dihydro-5H-1-oxa-2,4-diazaacenaphthylenes.     

痕量芴、苊、蒽和(艹北)的同时偏振-同步荧光分析

本文建立了痕量芴、苊、蒽和(艹北)的同时偏振-同步荧光分析法.该法能有效地抑制同步扫描过程中散射光的影响,从而提高测定的灵敏度.芴、苊、蒽和(艹北)的检测限分别为(ng/mL):1.1、10.0、1.8、0.26,相对标准偏差不大于4.2％.     

Synthesis and properties of π-extended fluoranthene derivatives from 1,2-diarylacenaphthylene derivatives

Acenaphthylene units work as a useful platform for the synthesis of polycyclic aromatic hydrocarbons (PAH). Three 1,2-diarylacenaphthylene derivatives (9-phenanthryl, 7-t-butyl-2-pyrenyl and 2-naphthyl) were prepared by Suzuki-Miyaura coupling of 1,2-dibromoacenaphthylene with the corresponding boronic acids and ester. The Scholl reaction of the phenanthryl derivative affords a donor-acceptor type fluoranthene derivative possessing a hemi-coronene structure by forming two CC bonds between phenanthryl groups. The reaction of the pyrenyl derivative allows one CC bond formation to give a helicene-type fluoranthene derivative. The reaction of the naphthyl derivative provides an asymmetric fluroranthene derivative having an anthracene unit accompanied with one CC bonding reaction, while a photochemical cyclization followed by dehydroaromatization reaction of the compound gives a symmetric fluoranthene derivative with a [5]helicene structure.     

The activation and transformations of acenaphthylene by osmium carbonyl cluster complexes

The reaction of Os₃(CO)₁₀(NCMe)₂ (1) with an excess of acenaphthylene at room temperature provided the complex Os₃(CO)₁₀(μ-H)(μ-η²-C₁₂H₇) (2). Compound 2 contains a σ-π coordinated acenaphthyl ligand bridging an edge of the cluster. Compound 2 was converted to the complex Os₃(CO)₉(μ-H)₂(μ₃-η²-C₁₂H₆) (3) when heated to reflux in a cyclohexane solution. Compound 3 contains a triply bridging acenaphthyne ligand. Compound 3 reacts with acenaphthylene again at 160 °C to yield four new cluster complexes: Os₄(CO)₁₂(μ₄-η²:η²-C₁₂H₆) (4); Os₂(CO)₆(μ-η⁴-C₂₄H₁₂) (5); Os₃(CO)₉(μ-H)(μ₃-η⁴-C₂₄H₁₃) (6); and Os₂(CO)₅(μ-η⁴-C₂₄H₁₂)(η²-C₁₂H₈) (7). All compounds were characterized crystallographically. Compound 4 is a butterfly cluster of four osmium atoms bridged by a single acenaphthyne ligand. Compounds 5 and 7 are dinuclear osmium clusters containing metallacycles formed by the coupling of two equivalents of acenaphthyne. Compound 6 is a triosmium cluster formed by the coupling of an acenaphthyne ligand to an acenapthyl group that is coordinated to the cluster through a combination of σ and π-bonding.     

N-乙烯基咔唑标记甲基丙烯酸-苊烯共聚物的荧光特性

合成了苊烯(ACE)含量依次为4.3、7.5、15.1及20.8 mol％的N 乙烯基咔唑(NVCz)标记甲基丙烯酸(MAA) 苊烯共聚物(PMAA ACE/NVCz）和ACE含量仅为0.5 mol％的ACE MAA共聚物（PMAA ACE）,研究了各共聚物在稀水溶液中的荧光行为和pH、表面活性剂等对共聚物荧光特性的影响.实验发现:在酸性介质中共聚物的压缩线团构象使激发态缔合物荧光相对增强,ACE到NVCz能量转移效率增加;碱性介质中共聚物构象相对松散,ACE到NVCz能量转移效率降低,因此荧光光谱中NVCz特征几乎消失.阴离子表面活性剂十二烷基磺酸钠(SDS),阳离子表面活性剂十六烷基三甲基溴化铵(AHTB)以及中性表面活性剂吐温80的引入使共聚物在酸性介质中的单体荧光特征增强,ACE到NVCz的能量转移效率下降;在碱性介质中引入AHTB部分中和了共聚物链上的负电荷,使共聚物构象重新卷曲,ACE到NVCz的能量转移效率提高,荧光光谱中NVCz特征重新出现,ACE单体荧光特征相应减少;在碱性介质中引入SDS以及吐温80对共聚物荧光光谱影响不大.     

Studies on the conformational behavior of acenaphthylene-labeled poly(acrylamide-<Emphasis Type="BoldItalic">co</Emphasis>-acryloyl-6-deoxy-6-amino-β-cyclodextrin)

An acenaphthylene (ACE)-labeled, β-cyclodextrin (β-CD)-modified poly(acrylamide) (PAM), (P(AM-co-β-CD)/ACE), was prepared in the present study. The conformational behavior of the ACE-labeled polymer in aqueous solution was studied by employing various fluorescence techniques, including fluorescence anisotropy and fluorescence quenching with different quenchers. It was demonstrated that the copolymer is partially hydrolyzed even though the charge density of the copolymer might be low, and the intra- and intermolecular complexation occurs in the copolymer solution due to the host–guest interaction between β-CD and ACE appended on the polymer backbone. The supramolecular interaction also exists in solid state as confirmed by the studies of the solid samples, which were obtained by freeze–drying the solution samples, by using powder X-ray diffraction (XRD) and scanning electron microscopy (SEM) techniques. It is expected that this kind of copolymers may be used as building blocks for the construction of novel supramolecular structures and for the preparation of smart soft solid like stimuli-responsive hydrogels.     

Crystal Structure of 4,7-Dichloro-1,2,3,5,6,8-hexakis-(4-methoxy-phenylsulfanyl)-acenaphthylene

Abstract  The title compound was prepared from the reaction of perchloroacenaphthylene with an excess of sodium salt of 4-methyloxythiophenol in toluene/ethanol (1:1) solvent and structurally characterized by single-crystal X-ray diffraction. The compound crystallizes in the Monoclinic space group P2(1) with the parameters: a = 10.351(1) ?, b = 20.453(3) ?, c = 12.1837(16) ?, β = 105.584(3)°, V = 2484.5(6) ?³, with Z = 2 formula units. Graphical Abstract   The title compound 4,7-dichloro-1,2,3,5,6,8-hexakis-(4-methoxy-phenylsulfanyl)-acenaphthylene was synthesized from perchloroacenaphthylene C ₁₂ Cl ₈ with an excess of 4-methoxybenzene thiolate in toluene/ethanol (1:1) .