Two methods for the resolution of 10,10′-dihydroxy-9,9′-biphenanthryl

Two methods for the resolution of 10,10′-dihydroxy-9,9′-biphenanthryl were developed. The first involved salt formation with (−)-strychnine via its cyclic diester with phosphoric acid. The second method involved the formation of diastereomers (R)- and (S)-9,9′-biphenanthryl-10,10′-diyl N-((−)-α-methylbenzyl)phosphoroamidates.     

10,10′-二甲基-3,3′二氨基-9,9′-双吖啶电致化学发光行为及机理研究

研究了10,10′-二甲基-3,3′-二氨基-9,9′-双吖啶(简称DMDABA)的电致化学发光(ECL)行为.考察了电化学参数、反应介质以及pH值等条件对DMDABA电致化学发光信号的影响.结果表明:在玻碳电极上施加适当电压时,该新试剂DMDABA在KNO3乙醇溶液中产生很强的电致化学发光信号,于最优化条件下,发光强度的自然对数与DMDABA浓度的自然对数在2.16×10-5~2.16×10-8mol/L范围内呈良好的线性关系,检出限可达5.2×10-9mol/L.还用循环伏安法、电致化学发光光谱以及荧光光谱研究了DMDABA的电致化学发光机理.     

9,9′-螺双芴的光电性能

采用密度泛函理论(DFT)-B3LYP/6-31G(d)方法对9,9'-螺双芴低聚物[(SBF)_n(n=1-4)]体系进行全优化,得到各分子的最高占据轨道(HOMO)和最低空轨道(LUMO)能量及HOMO-LUMO能隙,结果表明各分子整体表现出很好的共轭性质.并在分子的阳离子和阴离子状态的优化结构基础上,计算得到电离势(IP)、电子亲和势(EA)、空穴抽取能(HEP)、电子抽取能(EEP)和重组能等相关能量.利用单激发组态相瓦作用(CIS)/3-21G方法优化得到9,9'-螺双芴单体的S_1激发态的几何构型.用含时密度泛函理论(TD-DFT)方法计算得到了分子吸收光谱和荧光光谱的相关数据.随着聚合长度的增加,能隙变窄,空穴注入和电子转移的能力都相应提高,吸收光所需能量减小,吸收强度(f)增大,光谱红移.采用线性外推法,利用低聚物分子的各种性质与聚合度n之间的关系,得到高聚物的相应性质.为考察9位螺芴化的影响,将(SBF)_n的相关性质与母体芴的低聚物[(FL)_n(n=1-4)]进行比较,由两者的计算结果对比显示,在芴的9位螺芴化可以提高电子和空穴的传输能力,并同时保留芴优良的发光性质.     

Resonance CARS spectra of 9,9′-bianthryl in the excited states

Resonance CARS spectra of 9,9′-bianthryl in the twisted intramolecular charge-transfer (TICT), locally excited (LE)-S₁ and T₁ states were obtained in solution at room temperature. Observed Raman frequencies were compared with those of the S₀ state, the values of anthracene in the S₁, T₁ and radical ion states. The results show those vibrational modes of bianthryl not only in the S₀ state but also in the LE-S₁, TICT and T₁ states more or less consist of those of anthracene moieties. The inter-moiety CC stretching vibrational mode was not observed in the excited states.     

Synthesis of 2,2′-diamino-7-tert-butyl-9,9′-spirobifluorene starting from 4,4′-di-tert-butylbiphenyl

Abstract  

A novel spirobifluorene diamine monomer, 2,2′-diamino-7-tert-butyl-9,9′-spirobifluorene, was obtained starting from the readily available reagent 4,4′-di-tert-butylbiphenyl. The key step of the synthesis is the introduction of a nitro group into the 2-position of the spirobifluorene through the loss of tert-butyl at the 2-position.     

THE CRYSTAL STRUCTURES OF 10,10′-BIS(PHENOXARSINE) OXIDE AND SELENIDE

Abstract

The reaction between 10,10′-bis(phenoxarsine) oxide (I) and HI gives 10-iodophenoxarsine. The latter, on treatment with H₂Se give 10,10′-bis(phenoxarsine) selenide (II). The crystal structures of I and II have been determined from single crystal X-ray data. The unit cell for I is monoclinic, P2₁/c (No. 14) with a = 15.976(3) Å, b = 10.582(2) Å, c = 12.581(2) Å, β = 111.70(1)° V = 2018.6 ų; d(calc.) = 1.65Mg/m³ at 23°C for four molecules per unit cell. From 3279 reflections for which I>0.5σ(I), F>σ(F), R = 0.041 with anisotropic thermal parameters for all non-hydrogen atoms and with fixed positions and thermal parameters for hydrogens. One of the phenoxarsina rings deviates from planarity by approximately 5° while the other deviates by more than 24°. The (As[sbnd]O) distances are 1.810(3) and 1.821(3) Å for the flat and bent ring and the (As[sbnd]O[sbnd]As) angle is 122.3(1)°. The bond distances to As and O from C are nearly the same for both rings, but the bond angles with As and the ring O as the apex are systematically larger for the flat ring. For II the unit cell is triclinic, P1 (No. 2) with a = 9.368(1) Å, b = 14.089 Å, c = 9.269(2) Å, α = 111.37(2), β = 113.11(2), γ = 74.76(1); V = 1037.5 ų, d(calc) = 1.81 Mg/m³ for two molecules per unit cell at 23°C. From 2945 reflections for which I > 0.5σ(I), F > σ(F), R = 0.055 with anisotropic thermal parameters for all non-hydrogen atoms and with fixed positions and thermal parameters for hydrogen. One of the phenoxarsina rings deviates by 3° from planarity and the other by 8°. The (As[sbnd]Se) bond distances are 2.416(1) and 2.406(1) Å. The (As[sbnd]Se[sbnd]As) bond angle is 96.66(4)° and the corresponding (As[sbnd]C) and (C[sbnd]C) distances in the two rings are nearly the same. In comparison with I, the angles with As or O as the central atoms are about the same in both rings of II.     

10,10’-二烃基-9,9’-联二吖啶烯的电荷转移光谱和氧化反应研究

研究了10,10'-二烃基-9,9'-联二吖啶烯的DDQ的电荷转移光谱,用两种方法计算出了它们的电离热(I_p)值,并研究了该系列化合物与DDQ、TCNE和CA的氧化反应,其氧化结果和用HNO₃氧化所得到的10,10'-烃基-9,9'-联二吖啶硝酸盐结果一致。在DDQ、TCNE和CA中,只有DDQ可以和该系列化合物形成CTC,其原因是DDQ有弱的氧化能力而有强的络合能力。     

Experimental and theoretical investigations of absolute stereochemistry and chiroptical properties of enantiopure 2,2′-substituted 9,9′-bianthryls

The absolute stereochemistry of axially chiral 2,2′-X₂-9,9′-bianthryls (X=COOH, COOMe, and Cl) was determined by X-ray analysis of the (+)-quinidine salt of the diacid to be (M)-(−) or (P)-(+). The M isomers of these compounds showed specific rotations of −115, −123, and −32, respectively, in acetone. The circular dichroism (CD) as well as UV spectra of the two M isomers (X=COOMe and Cl) were investigated with the aid of theoretical calculations by the time-dependent DFT (TDDFT) method. The calculations reasonably reproduced the observed CD bands, and suggested a correlation between the signs of p or β′ bands and the absolute stereochemistry.     

对位取代酚钾与10′10′-二烃基-9,9′-联二吖啶盐电荷转移光谱的研究

10,10′-二烃基-9, 9′-联二吖啶盐有很强的荧光, 在光学材料^[1]和重金属离子的分析^[2]中有重要的应用价值。     

10,10’-二甲基-3,3’-二磺酸基-9,9’-双吖啶的电致化学发光行为

研究了新试剂10,10'-二甲基-3,3'-二磺酸基-9,9'-双吖啶(简称DMDSBA)的电致化学发光(ECL)行为. 考察了电化学参数、反应介质以及pH等条件对DMDSBA电致化学发光信号的影响. 结果表明, 在玻碳电极上施加适当电压时, DMDSBA在KNO₃溶液介质中产生很强的电化学发光信号, 于优化的实验条件下, 发光强度的自然对数与DMDSBA浓度的自然对数在1.0×10^-5-1.0×10^-8 mol·L^-1范围内呈良好的线性关系,检出限可达2.3×10^-9 mol·L^-1. 并用循环伏安法、电致化学发光光谱以及荧光光谱, 研究了DMDSBA的电致化学发光机理.     

Study of the fluorescence of 9,9′-bianthryl in polyvinylalcohol and in polyvinylchloride at 300 K and 80 K

By UV-vis spectroscopy and use of the polarization of the emission, we show that the 9,9′-bianthryl (9,9′BA) symmetrical molecule exhibits an induced fluorescence in polyvinylalcohol (PVA) by hydrogen bonding of the type OH⋯π which depends on considered temperature. This anomalous behaviour does not occur when this molecule is included in a polyvinylchloride, aprotic polymer.     

9,9-二辛基芴的电化学聚合

在三氟化硼乙醚(BFEE)中, 9,9-二辛基芴可以直接阳极氧化制备高质量聚(9,9-二辛基芴)膜, 其电导率为1×10^－2 S/cm. 9,9-二辛基芴在BFEE中的起始氧化电位为1.25 V vs. SCE, 低于单体在0.1 mol/L Bu₄NBF₄的乙腈溶液体系中的起始氧化电位(1.52 V vs. SCE). BFEE中获得的聚(9,9-二辛基芴)膜具有良好的电化学性质. 聚合物部分溶于氯仿、四氢呋喃、二甲基亚砜等极性溶剂. FTIR和¹H NMR表明聚合反应主要发生在2,7位. 荧光光谱表明聚合物是一种良好的蓝色荧光物质.     

Synthesis, characterization, and optical properties of 2-amino-4-aryl-6-(9,9′-spirobifluoren-2-yl)pyrimidines

Abstract  

A series of 2-amino-4-aryl-6-(9,9′-spirobifluoren-2-yl)pyrimidines have been synthesized by the reaction of guanidine and chalcones under basic conditions. The physical and optical properties indicated that these compounds generally show good blue light emissions and excellent thermal stabilities. Intermolecular hydrogen bonds and interactions have strong influences on their properties.     

2,7-二乙烯吡啶基-9,9′-二乙基芴纳米颗粒的粒度测量及荧光光谱的研究

利用二次沉淀法制备出不同粒径(101.6~516.9nm)的2,7-二乙烯吡啶基-9,9′-二乙基芴有机纳米微粒。通过激光粒度仪测试发现:其平均粒度和多分散指数(PDI)值随着放置时间的增长、有机分子浓度的增大而增加;随放置温度的升高、表面活性剂的加入而减小。利用荧光光谱仪测试2,7-二乙烯吡啶基-9,9′-二乙基芴的氮甲基吡咯烷酮(NMP)溶液和2,7-二乙烯吡啶基-9,9′-二乙基芴纳米微粒体系的荧光激发和发射光谱,发现纳米微粒体系的荧光激发光谱和发射光谱分别在403、530nm附近出现新的电荷转移(CT)峰。     

结构规整有序的寡聚噻吩修饰9,9′-螺二芴衍生物的光物理性质及其电化学聚合(英文)

研究了结构规整有序的寡聚噻吩修饰的9,9′-螺二芴衍生物在溶液中和在固体膜状态下的光物理性质,发现在四氢呋喃的稀溶液中,随着有效共轭长度的增加这些化合物的最大吸收峰和发射峰发生了明显的红移.实验结果表明,9,9′-螺二芴骨架中的9位螺碳原子明显地阻断了二个共轭片段的共轭效应,使它们成为了二个独立的共轭链节.此外,还进一步研究了这些化合物的电化学聚合性质.     

Etude de la fluorescence du 9,9′-bianthryl en solutions liquides et en milieux polymériques rigides à la température ambiante

The fluorescence of 9,9′-bianthryl (9,9′BA) is very sensitive to the polarity of the solvent. This molecule exibits an intramolecular charge transfer state in polar medium. The study of the fluorescence of 9,9′BA, in liquid solutions, shows a strong dependency of the Stokes shift versus the dipole moment m of the aprotic lowly viscous solvent. Moreover, this compound exhibits in polyvinylacohol (PVA) an original anomalous behaviour.     

Theoretical and Experimental Study of Photophysical Characteristics between Poly(9,9-dioctyl°uorene) and Poly(9,9-dioctyl°uorene-co-benzothiadiazole)

The photo-physical characteristics of semiconductor polymer are systematically stud-ied through comparing poly (9,9-dioctylfluorene) (PFO) and poly (9,9-dioctylfluorene-co-benzothiadiazole) (F8BT). The quantum chemical calculation shows that the introduction of benzothiadiazole unit facilitates the intrachain charge transfer (ICT) and modulates the electronic transition mechanism of polymer. The transient absorption measurement exhibits that intrachain exciton relaxation is dominant in the decay of excited PFO in a monodis-perse system and intrachain exciton interaction could appear at high excitation intensity. In F8BT solution, the ICT state exists and participates in the relaxation of excited state. The relaxation processes of PFO and F8BT in the condensed phase both accelerate and show obvious exciton-exciton annihilation behavior at high excitation intensity. At the same excitation intensity, the mean lifetime of F8BT is longer than that of PFO, which may be assigned to the excellent delocalization of charge.     

6,6′-Dibromo-3,3′-dimethoxy-2,2′-dihydroxy-1,1′-biphenyl: preparation and resolution

A pratical route to prepare the title biphenyl 1 starting from 3,3′,2,2′-tetramethoxy-1,1′-biphenyl 2 is described. Resolution of 1 was achieved by its conversion into the corresponding diastereomeric menthyldicarbonate. The absolute configuration of (P)-(+)-1 was confirmed by X-ray analysis of the related diastereomer.