Intervalence transitions in the mixed-valence monocations of bis(triarylamines) linked with vinylene and phenylene-vinylene bridges

(E)-4,4'-Bis[bis(4-methoxyphenyl)amino]stilbene, 1, (E,E)-1,4-bis[4-[bis(4-methoxyphenyl)amino]styryl]benzene, 2, and two longer homologues, (E,E,E)-4,4'-bis[4-[bis(4-methoxyphenyl)amino]styryl]stilbene, 3, and (E,E,E,E)-1,4-bis(4-[4-[bis(4-methoxyphenyl)amino]styryl]styryl)benzene, 4, have been oxidized to their mono- and dications using tris(4-bromophenyl)aminium hexachloroantimonate. The intervalence charge-transfer (IVCT) band of 1(+) is narrow and asymmetric and exhibits only weak solvatochromism. Analysis of this band indicates that 1(+) is a class-III or class-II/III borderline mixed-valence species. In contrast, a broad, strongly solvatochromic IVCT band is observed for 2(+), indicating that this species is a class-II mixed-valence species. The assignment of 1(+ ) and 2(+) as symmetric class-III and unsymmetric class-II species, respectively, is also supported by AM1 calculations. Hush analysis of the IVCT bands of both 1(+) and 2(+) gives larger electronic couplings, V, than for their analogues in which the double bonds are replaced with triple bonds. The diabatic electron-transfer distance, R, in 1(+) can be estimated by comparison of the V estimated by Hush analysis and from the IVCT maximum; it is considerably less than the geometric N-N separation, a result supported by quantum-chemical estimates of R for 1(+)-4(+). In 3(+) and 4(+), the IVCT is largely obscured by an intense absorption similar to a band seen in the corresponding dications and to that observed in the monocation of a model compound, (E,E,E)-1-[bis(4-methoxyphenyl)amino]-4-[4-[4-(4-tert-butylstyryl)styryl]styryl]benzene, 5, containing only one nitrogen redox center; we attribute this band to a bridge-to-N(+) transition. The corresponding dications 1(2+)-4(2+) show a complementary trend in the coupling between redox centers: the shortest species is diamagnetic, while the dication with the longest bridge behaves as two essentially noninteracting radical centers.     

一类新型的双β-氨基醇的合成及催化硼烷对芳酮的不对称还原反应

以L-半胱氨酸盐酸盐出发，经与二卤代烷偶联，成酯和格氏反应制得三种双手性β-氨基醇，1,2-双[R-2-氨基-3-羟基-3,3-二苯基丙硫基]乙烷(4a)，1,3-双[R-2-氨基-3-羟基-3,3-二苯基丙硫基]丙烷(4b)，1,4-双[R-2-氨基-3-羟基-3,3-二苯基丙硫基]丁烷(4c)。将此类双手性β-氨基醇与硼烷在THF溶液中反应，in situ制备双手性恶唑硼烷催化硼烷对芳酮的不对称还原，产物苯乙醇的光学收率达72.8%、α-溴代苯乙醇的光学收率达91.4%。     

新型芳并吡喃类多环化合物的合成与光谱性质研究

本文设计并经由分子内碳-碳偶联反应合成了一系列基于芳并吡喃供电子功能片段的有机功能小分子,包括萘并[2,1-b：6,5-b’]二苯并吡喃4a,萘并[2,1-b：6,5-b’]二萘并吡喃4b,萘并[2,1-b：6,5-b’]二[2-（5-己基噻吩基）]苯并吡喃4c。通过紫外光谱和荧光光谱研究表明,这类化合物在370~400 nm波长范围内具有最大紫外吸收,在417~462 nm波长范围内具有最大荧光发射。说明随着共轭平面的增大或共轭链长度的增加,化合物的吸收和荧光光谱均发生显著的红移,是一类具有丰富光电活性的有机功能分子。     

The water-soluble indolium-based fluorescence probes for detection of the extreme acidity or extreme alkalinity

In this work, 3,3′-(((1E,1′E)-(H,12H-5,11-methanodibenzo[b,f][1,5]diazocine-2,8-diyl)bis(ethene-2,1-diyl))bis(1,1-dimethyl-1H-benzo[e]indole-3-ium-2,3-diyl))bis(propane-1-sulfonate) (1), 3,3’-(((1E,1′E)-(6H,12H-5,11-methanodibenzo[b,f][1,5]diazocine-2,8-diyl)bis(ethene-2,1-diyl))bis(3,3-dimethyl-3H-indole-1-ium-2,1-diyl))bis(propane-1-sulfonate) (2), 2,2’-((1E,1′E)-(6H,12H-5,11-methanodibenzo[b,f][1,5]diazocine-2,8-diyl)bis(ethene-2,1-diyl))bis(1,3,3-trimethyl-3H-indol-1-ium) iodide (3) and 2,2’-((1E,1′E)-(6H,12H-5,11-methanodibenzo[b,f][1,5]diazocine-2,8-diyl)bis(ethene-2,1-diyl))bis(1,1,3-trimethyl-1H-benzo[e]indol-3-ium) iodide (4) were designed and synthesized by ethylene bridging of the N-substituted indolium salts and the Tröger’s Base (TB) framework. The probes exhibited a longer absorption and emission wavelength and the emission wavelength of them in dichloromethane (DCM) was more than 600 nm, performed a red fluorescence. All of the probes could work on the extreme acidic and the extreme alkaline environments and showed a good liner response in the working pH range. Especially, 2 and 4 were soluble in water and manifested a good pH sensing in a water system. Also, ¹H NMR analysis illustrated how these dyes worked as the pH-sensitive fluorescence probes. In addition, they performed excellent reversibility, high selectivity and good photostability.     

Rhenium tricarbonyl core complexes of thymidine and uridine derivatives

Thymidine and uridine were modified at the C2' and C5' ribose positions to form amine analogues of the nucleosides (1 and 4). Direct amination with NaBH(OAc)3 in DCE with the appropriate aldehydes yielded 1-{5-[(bis(pyridin-2-ylmethyl)amino)methyl]-4-hydroxytetrahydrofuran-2-yl}-5-methyl-1H-pyrimidine-2,4-dione (L1), 1-{5-[(bis(quinolin-2-ylmethyl)amino)methyl]-4-hydroxytetrahydrofuran-2-yl}-5-methyl-1H-pyrimidine-2,4-dione (L2), and 1-[3-(bis(pyridin-2-ylmethyl)amino)-4-hydroxy-5-(hydroxymethyl)tetrahydrofuran-2-yl]-1H-pyrimidine-2,4-dione (L5), while standard coupling procedures of 1 and 4 with 5-(bis(pyridin-2-ylmethyl)amino)pentanoic acid (2) and 5-(bis(quinolin-2-ylmethyl)amino)pentanoic acid (3) in the presence of HOBT-EDCI in DMF provided a second novel series of bifunctional chelators: 5-(bis(pyridin-2-ylmethyl)amino)pentanoic acid [(3-hydroxy-5-(5-methyl-4-oxo-3,4-dihydro-2H-pyrimidin-1-yl)tetrahydrofuran-2-yl)methyl] amide (L3), 5-(bis(quinolin-2-ylmethyl)amino)pentanoic acid [(3-hydroxy-5-(5-methyl-4-oxo-3,4-dihydro-2H-pyrimidin-1-yl)tetrahydrofuran-2-yl)methyl] amide (L4), 5-(bis(pyridin-2-ylmethyl)amino)pentanoic acid [2-(2,4-dioxo-3,4-dihydro-2H-pyrimidin-1-yl)-4-hydroxy-5-(hydroxymethyl)tetrahydrofuran-3-yl] amide (L6), and 5-(bis(quinolin-2-ylmethyl)amino)pentanoic acid [2-(2,4-dioxo-3,4-dihydro-2H-pyrimidin-1-yl)-4-hydroxy-5-(hydroxymethyl)tetrahydrofuran-3-yl] amide (L7). The rhenium tricarbonyl complexes of L1-L4, L6, and L7, [Re(CO)3(LX)]Br (X=1-4, 6, 7: compounds 5-10, respectively), have been prepared by reacting the appropriate ligand with [NEt4][Re(CO)3Br3] in methanol. The ligands and their rhenium complexes were obtained in good yields and characterized by common spectroscopic techniques including 1D and 2D NMR, HRMS, IR, cyclic voltammetry, UV, and luminescence spectroscopy and X-ray crystallography. The crystal structure of complex 6.0.5NaPF6 displays a facial geometry of the carbonyl ligands. The nitrogen donors of the tridentate ligand complete the distorted octahedral spheres of the complex. Crystal data: monoclinic, C2, a = 24.618(3) A, b = 11.4787(11) A, c = 15.5902(15) A, beta = 112.422(4) degrees , Z = 4, D(calc) = 1.562 g/cm3.     

Bis[bis-(4-alkoxyphenyl)amino] derivatives of dithienylethene, bithiophene, dithienothiophene and dithienopyrrole: palladium-catalysed synthesis and highly delocalised radical cations

Five diamines with thiophene-based bridges--(E)-1,2-bis{5-[bis(4-butoxyphenyl)amino]-2-thienyl}ethylene (1), 5,5'-bis[bis(4-methoxyphenyl)amino]-2,2'-bithiophene (2), 2,6-bis[bis(4-butoxyphenyl)amino]dithieno[3,2-b:2',3'-d]thiophene (3), N-(4-tert-butylphenyl)-2,6-bis[bis(4-methoxyphenyl)amino]dithieno[3,2-b:2',3'-d]pyrrole (4 a) and N-tert-butyl-2,6-bis[bis(4-methoxyphenyl)amino]dithieno[3,2-b:2',3'-d]pyrrole (4 b)--have been synthesised. The syntheses make use of the palladium(0)-catalysed coupling of brominated thiophene species with diarylamines, in some cases accelerated by microwave irradiation. The molecules all undergo facile oxidation, 4 b being the most readily oxidised at about -0.4 V versus ferrocenium/ferrocene, and solutions of the corresponding radical cations were generated by addition of tris(4-bromophenyl)aminium hexachloroantimonate to the neutral species. The near-IR spectra of the radical cations show absorptions characteristic of symmetrical delocalised species (that is, class III mixed-valence species); analysis of these absorptions in the framework of Hush theory indicates strong coupling between the two amine redox centres, stronger than that observed in species with phenylene-based bridging groups of comparable length. The strong coupling can be attributed to high-lying orbitals of the thiophene-based bridging units. ESR spectroscopy indicates that the coupling constant to the amino nitrogen atoms is somewhat reduced relative to that in a stilbene-bridged analogue. The neutral species and the corresponding radical cations have been studied with the aid of density functional theory and time-dependent density functional theory. The DFT-calculated ESR parameters are in good agreement with experiment, while calculated spin densities suggest increased bridge character to the oxidation in these species relative to that in comparable species with phenylene-based bridges.     

Speciation of uranyl complexes in ionic liquids by optical spectroscopy

Uranyl complexes dissolved in room-temperature ionic liquids have diagnostic absorption and emission spectra which reflect the molecular symmetry and geometry. In particular, the characteristic vibrational fine structure of the absorption spectra allows identification of the molecular symmetry of a uranyl complex. The concept of speciation of uranyl complexes is illustrated for the hydrated uranyl ion, the tetrachloro complex [UO2Cl4]2-, the trinitrato complex [UO2(NO3)3]-, the triacetato complex [UO2(CH3COO)3]-, and the crown ether complex [UO2(18-crown-6)]2+ in imidazolium and pyrrolidinium bis(trifluoromethylsulfonyl)imide ionic liquids. The competition between 18-crown-6 and small inorganic ligands for coordination to the uranyl ion was investigated. The crystal structures of the hydrolysis product [(UO2)2(mu2-OH)2(H2O)6] [UO2Br4](18-crown-6)4 and imidazolium salt [C6mim]2[UO2Br4] are described.     

Spectroscopic behavior on the formation complex of three double-armed calix[4]arene derivatives with lanthanoid nitrates in acetonitrile

The complexation spectroscopic behavior of three p-tert-butylcalix[4]arene Schiff bases i.e. 5,11,17,23-tetra-tert-butyl-25,27-bis[2-[N-(3-nitrobenzylidene)amino]ethoxy]-26,28-dihydroxycalix[4]arene (1), 5,11,17,23-tetra-tert-butyl-25,27-bis[2-[N-(2-hydroxybenzylidene)amino]ethoxy]-26,28-dihydroxycalix[4]arene (2), and 5,11,17,23-tetra-tert-butyl-25,27-bis[2-[N-(2-hydroxy-3-methoxybenzylidene)amino]ethoxy]-26,28-dihydroxycalix[4]arene (3) with lanthanoid nitrates (Tb3+ and Eu3+) has been investigated in anhydrous acetonitrile at 25 degrees C by using UV-vis and FT-IR as well as fluorescence spectra. The results obtained indicated that the spectroscopic behavior of compounds 1-2 upon complexation with lanthanoid ions did not show any significant larger difference in comparison with free compounds 1 and 2, which may be contributed to the poor binding ability. Contrary to compounds 1 and 2, the lower rim functional groups in compound 3 can form two large pi electron conjugate system with lanthanide ion and encapsulate lanthanide ions tightly, displaying the novel spectroscopic behavior upon complexation with lanthanide ions. As compared with compound 3, the formation complexes of compound 3 with Tb3+ and Eu3+ showed new broad intense absorption at 398 nm, respectively, and IR spectra showed that O-H stretching vibration at 3413.40 cm(-1) displayed a large drop. It is interestingly noted that the narrow emission line spectra were observed only for 3 complex with Tb3+, but did not for 3-Eu3+ complex. In the 3-Eu3+ complex, the broad-band emission at lambda(max) = 534 nm was obtained at the excitation of 398 nm. The spectroscopic behavior of three calix[4]arene derivatives upon complexation with lanthanoids was discussed from the relationship between the host structure and the properties of guest lanthanide ions.     

2,4和8-支噁二唑衍生物的三光子吸收和三光子上转换荧光

用飞秒Ti:sapphire激光测定了3个对称噁二唑衍生物4-{N,N-双[4-(4-[5-(4-叔丁基苯基)-1,3,4-噁二唑-2]苯乙烯基)苯基]氨基}苯甲醛(Bis-oxa)、2,5-双{4-[2-N,N-双(4-{4-[5-(4-叔丁基苯基)-1,3,4-噁二唑-2]苯乙烯基}苯基)氨基苯乙烯基]苯基}-1,3,4-噁二唑(Quadri-oxa)和2,5-双(4-{2-N,N-双[({3,5-二[5-(4-叔丁基苯基)-1,3,4-噁二唑-2]苯基}乙烯基)苯基]氨基苯乙烯基}苯基)-1,3,4-噁二唑(Octu-oxa)的三光子吸收谱和三光子荧光光谱. 在1260 nm飞秒激光激发下, 2,4和8-支噁二唑衍生物的三光子吸收系数分别为5.0×10^-5, 10.0×10^-5和10.0×10^-5 cm³/GW², 三光子频率上转换荧光发射波长分别为533, 544和551 nm. 研究了多支化合物线性吸收和透过、单光子荧光及量子产率、荧光寿命、多光子荧光光谱和三光子吸收系数谱. 对称多支噁二唑衍生物具有很强的三光子吸收和上转换荧光性质.     

Fiber optic sodium and potassium sensing by using a newly synthesized squaraine dye in PVC matrix

In recent years squarines received attention as fluorescent labels. Their very promising spectral properties such as long wavelength absorption and emission, high extinction coefficients and quantum yields could lead novel sensing technologies. In this work newly synthesized fluoroinophores named bis[4-N-(1-aza-4,7,10,13-tetraoxacyclopentadecyl)-3,5-dihydroxyphenyl]squaraine, azacrown-1 and 2 bis[4-N-(1-aza-4,7,10,13,16-pentaoxacyclooctadecyl)-3,5-dihydroxyphenyl]squaraine, azacrown-2 have been used for sodium and potassium sensing in plasticized PVC matrix. The squaraine derivatives exhibited fluorescence emission based optical responses to sodium and potassium with a detection limit of 1.10(-9) M. The sensor compositions exhibited wide response ranges between 10(-9) and 10(-5) M Na(+)or K(+), and, therefore, may be an alternative method to flame emission spectroscopy. The sensor is fully reversible within the dynamic range and the response time is 3 min under batch conditions. Cross sensitivity to pH is negligible in the pH range of 6.2-7.3. Throughout fiber optic based studies a relative signal change of 54-56% has been achieved. The azacrown dyes have the advantage that they can be excited with long wavelength light and, are, therefore, LED compatible. The cross sensitivity of azacrown-1 and -2 to Ba(2+), Ca(2+) and NH(4)(+)were also tested in separate solutions.     

一种环金属铱、铂双核配合物的合成及光电性能

设计合成了一种双核环金属铱,铂配合物二[N,N-2-(2,4-二氟苯基吡啶)C3,N1](吡啶甲酸)合铱(Ⅲ)-C₆-[苯基吡啶-C3,N1](吡啶甲酸)合铂(Ⅱ)(FIrPPyPt)。 通过核磁共振仪、元素分析仪、紫外-可见吸收光谱仪和光致发光光谱仪对其结构和性能进行了表征。 结果表明,配合物FIrPPyPt的紫外-可见吸收位于250~450 nm之间,荧光发射峰位于465和493 nm。 将配合物FIrPPyPt以质量分数1%~8%掺杂到主体材料聚乙烯基咔唑(PVK)+2-(联苯-4-芳基)-5-(4-叔丁基苯)-1,3,4-噁二唑(PBD)(30%)中制作了电致发光器件,在不同电压下电致发光光谱中,显现出铱配合物和铂配合物的特征峰,波峰位于400、500和530 nm蓝绿光区发射区。 该双核配合物用于单掺杂有机白光电致发光器件具有制作简单、色稳定性和重复性好等特点,为单掺杂白光发光器件提供了一种好的思路。     

双(1,2-二苯基环戊二烯基)二氯化锆化合物发光光谱行为及取代基效应

以干燥的正己烷为溶剂, 在N2气保护下, 研究了金属有机化合物双(1,2-二苯基环戊二烯基)二氯化锆(2)、 双(4-甲基-1,2-二苯基环戊二烯基)二氯化锆(3)和双(1,2,4\|三苯基环戊二烯基)二氯化锆(4)的发光光谱行为. 研究结果表明, 该系列化合物具有良好的发光性能, 且荧光光谱的发射波长可通过改变环戊二烯基4位上的取代基R进行调节. 发射光波长大小顺序为Ph>CH3>H.     

A stable chiral diaminocyclopropenylidene

The chiral carbene bis[bis(R-1-phenylethyl)amino]cyclopropenylidene 2 and its dicarbene-silver complex [Ag(2)2]BF4 (3) have been isolated in good yields from the reactions of bis[bis(R-1-phenylethyl)amino]cyclopropenylium tetrafluoroborate (1)BF4 with potassium bis(trimethylsilyl)amide or with Ag2O, respectively; the molecular structures of (1)ClO4, 2 and 3 have been determined by X-ray diffraction analyses.     

对称4-枝和8-枝噁二唑衍生物的合成与荧光性质

采用Wittig-Horner和Heck反应合成了3个对称多枝[1,3,4]-噁二唑衍生物2,5-双{4-{4-[N,N-二(4-溴苯基)-氨基] 苯乙烯基}苯基}-1,3,4-噁二唑(BrPASPO), 2,5-双{4-{4-{N,N-二{4-{4-[5-(4-叔丁基苯基)-1,3,4-噁二唑基-2-]苯乙烯基}苯基}氨基}苯乙烯基}苯基}-1,3,4-噁二唑(TPASPO)和2,5-双{4-{4-{N,N-二{4-{3,5-二[5-(4-叔丁基苯基)-1,3,4-噁二唑基-2]-苯乙烯基}苯基}氨基}苯乙烯基}苯基}-1,3,4-噁二唑(OPASPO). 目标化合物的结构经过红外光谱、核磁共振氢谱、质谱和熔点确认. 在CH2Cl2溶液中三者的最大吸收波长分别在403 (BrPASPO), 408 (TPASPO)和409 nm (OPASPO), 荧光发射峰分别为495 (BrPASPO), 509 (TPASPO)和506 nm (OPASPO). 化合物TPASPO和OPASPO在CH2Cl2溶液中的荧光量子产率分别为0.47和0.45. 8枝化合物的荧光寿命高于4枝化合物. 对称多枝化合物具有很强的分子内电荷转移能力和荧光发射能力.     

嘧啶基双光子荧光染料的设计合成与生物成像

生理条件下光学性质稳定的双光子荧光染料在生物成像领域具有广阔的应用前景。我们使用2,4-二甲基-6-羟基嘧啶与4-(N,N-二甲氨基)苯甲醛进行缩合反应,设计合成了具有双光子荧光性质的化合物2-[(1E)-2-[4-(二甲氨基)苯基]乙烯基]-6-甲基-4(3H)-嘧啶(NHP)。通过质谱(MS)、核磁共振波谱(NMR)、紫外可见吸收光谱和荧光发射光谱等技术手段表征了其结构,研究了其光物理性质,以及外部环境改变对其发射光谱的影响。结果表明,化合物NHP的最佳吸收峰位于400 nm,最佳发射峰位于540 nm左右,且荧光发射不受金属离子、氨基酸和pH等环境因素的影响。生物实验结果表明,化合物NHP细胞毒性较小,且具有很好的活细胞和果蝇脑组织成像效果,是一种较为理想的双光子荧光生物成像染料。     

Synthesis and structural characterisation of polynuclear cobalt complexes with partially-deprotonated Bis-tris

The synthesis and crystal structures of [Co4Na2(HL)2(H2L)2(MeOH)4] and [Co5(HL)2(H2L)2] are reported as the first examples of polynuclear transition metal complexes assembled using partially-deprotonated Bis-tris {2-[bis(2-hydroxyethyl)amino]-2-(hydroxymethyl)propane-1,3-diol, H5L}.     

Synthesis,characterization, and electroluminescence of polyfluorene copolymers containing T‐shaped isophorone derivatives

We have successfully synthesized a series of new fluorene‐based copolymers, poly[(9,9‐bis(4‐octyloxy‐phenyl)fluorene‐2,7‐diyl)‐co‐[2(3{2[4(2{4[bis(bromophenyl‐4yl) amino]phenyl}vinyl)‐2,5‐bisoctyloxyphenyl]vinyl}‐5,5‐dimethyl‐cyclohex‐2‐enylidene)malononitrile] (PFTBMs), with varying molar ratios of the low‐energy band gap comonomer, 2(3{2[4(2{4[bis(4‐bromophenyl)amino]phenyl}vinyl)‐2,5‐bisoctyloxyphenyl]vinyl}‐5,5‐dimethyl‐cyclohex‐2‐enylidene)malononitrile (BTBM). To prepare BTBM (which has a T‐shaped structure) from triphenylamine, dialkoxy phenyl, and isophorone, we introduced three individual segments of an isophorone derivative containing two cyanide groups at the carbonyl position, a dialkoxy phenyl group for increased solubility, and a triphenyl amine for effective charge transfer. Furthermore, we introduced vinyl linkages between each segment to increase the length of π‐conjugation. The synthesized polyfluorene copolymers with the BTBM, PFTBMs, were synthesized via palladium‐catalyzed Suzuki coupling reactions. The photoluminescence emission spectra of the synthesized polymers in solution did not show significant energy transfer from PBOPF segments to the BTBM units. Light‐emitting devices based on these polymers were fabricated with an indium tin oxide/poly(3,4‐ethylene dioxythiophene):poly(styrene sulfonate) (PEDOT:PSS)/polymers/Balq/LiF/Al configuration. Examination of the electroluminescence emission of the synthesized polymers showed that the maximum wavelength shifted continuously toward long wavelengths with as the number of BTBM units in the polymer main chain was increased. In particular, a device using PFTBM 05 exhibited a maximum brightness of 510 cd/m² and a maximum current efficiency of 0.57 cd/A. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 82–90, 2010     

Developing the {M(CO)3}+ core for fluorescence applications: Rhenium tricarbonyl core complexes with benzimidazole, quinoline, and tryptophan derivatives

Tridentate ligands derived from benzimidazole, quinoline, and tryptophan have been synthesized, and their reactions with [NEt4]2[Re(CO)3Br3] have been investigated. The complexes 1-4 and 6 and 7 exhibit fac-{Re(CO)3N3} coordination geometry in the cationic molecular units, while 5 exhibits fac-{Re(CO)3N2O} coordination for the neutral molecular unit, where N3 and N2O refer to the ligand donor groups. The ligands bis(1-methyl-1H-benzoimidazol-2-ylmethyl)amine (L1), [bis(1-methyl-1H-benzoimidazol-2-ylmethyl)amino]acetic acid ethyl ester (L2), [bis(1-methyl-1H-benzoimidazol-2-ylmethy)amino]acetic acid methyl ester (L3), [bis(quinolin-2-ylmethyl)amino]acetic acid methyl ester (L4), 3-(1-methyl-1H-indol-3-yl)-2-[(pyridin-2-ylmethyl)amino]propionic acid (L5), 2-[bis(pyridin-2-ylmethyl)amino]-3-(1-methyl-1H-indol-3-yl)propionic acid (L6), and 2-[bis(quinolin-2-ylmethyl)amino]-3-(1-methyl-1H-indol-3-yl)propionic acid (L7) were obtained in good yields and characterized by elemental analysis, 1D and 2D NMR, and high-resolution mass spectrometry (HRMS). The rhenium complexes were obtained in 70-85% yields and characterized by elemental analysis, 1D and 2D NMR, HRMS, IR, UV, and luminescence spectroscopy, as well as X-ray crystallography for [Re(CO)3(L1)]Br (1), {[Re(CO)3(L2)]Br}2.NEt4Br . 8.5H2O (3(2).NEt4Br . 8.5H2O), [Re(CO)3(L4)]Br (4), and [Re(CO)3(L6)]Br (6). Crystal data for C21H19BrN5O3Re (1): monoclinic, P2(1)/c, a = 13.1851(5) A, b = 16.1292(7) A, c = 10.2689(4) A, beta = 99.353(1) degrees , V = 2154.8(2) A3, Z = 4. Crystal data for C56H73Br3N11O18.50 Re2 (3(2).NEt4Br . 8.5H2O): monoclinic, C2/c, a = 34.7760(19) A, b = 21.1711(12) A, c = 20.3376(11) A, beta = 115.944(1) degrees , V = 13464.5(1) A3, Z = 8. Crystal data for C26H21BrN3O5Re (4): monoclinic, P2(1)/c, a = 16.6504(6) A, b = 10.1564(4) A, c = 14.6954(5) A, beta = 96.739(1) degrees , V = 2467.9(2) A3, Z = 4. Crystal data for C27H24BrN4O5Re (6): monoclinic, P2(1), a = 8.7791(9) A, b = 16.312(2) A, c = 8.9231(9) A, beta = 90.030(1) degrees , V = 1277.8(2) A3, Z = 2.     

3,3-二{2,2-二[4-(N,N-二取代氨基)苯基]乙烯基}-4,5,6,7-四氯-2-苯并[c]呋喃酮的合成

在对甲苯磷酸存在下,采用1,1-二[4-(N,N-二取代氨基)苯基]乙烯(3)和四氯苯酐在乙酸酐溶液中的缩合反应合成了3,3-二{2,2-二[4-(N,N-二取代氨基)苯基]乙烯基}-4,5,6,7-四氯-2-苯并[c]呋喃酮(4),产率89～93％。3由4,4＇-二(N,N-二取代氨基)二苯甲酮(1)与甲基碘化镁进行Grignard反应的产物经水解再脱水制得,产率85％～88.5％(以1为基准)。     

Regioselective Photocyclizations of Di(quinolinyl)arylamines and Tri(quinolinyl)amine with Emission Color Changes and Photoreaction‐Induced Self‐Assemblies

Bis[2,4‐di(trifluoromethyl)quinoline‐7‐yl]amine ( 1 ), bis[2,4‐di(trifluoromethyl)quinoline‐7‐yl]methylamine ( 2 ), bis[2,4‐di(trifluoromethyl)quinoline‐7‐yl]phenylamine derivatives, Q₂NPhX; X=NO₂ ( 3 a ), I ( 3 b ), H ( 3 c ), OMe ( 3 d ), and NH₂ ( 3 e ), tris[2,4‐di(trifluoromethyl)quinoline‐7‐yl]amine ( 4 ), and bis[2,4‐di(pentafluoroethyl)quinoline‐7‐yl]‐4‐nitrophenylamine ( 5 ) were prepared as functional fluorophores. On irradiating the solution samples, 1 showed no noticeable alteration, whereas 2 , 3 a – d , and 4 showed emission color changes from yellowish green to blue, indicating that a photoreaction took place. Analyses of the photoproduct based on absorption and emission spectra, ¹H NMR spectra, and X‐ray crystallography indicated that photocyclization reactions occurred regioselectively and quantitatively to form bent–bent dipyridocarbazoles. In 3 a – d , the reaction rates depended on the solvent polarity and the substituent on the benzene ring. The photoreactions were accelerated with decreasing solvent polarity and with increasing electron‐withdrawing character of the substituents. The photocyclization of triquinolineamine 4 was faster than that of 3 a in all solvents. The results of semiempirical quantum‐chemical PM6 calculations suggested that the observed regioselective photocyclization could be explained by stabilization of the excited triplet transition state for the bent–bent form because of the molecular geometry with the CH?NQ hydrogen bonds. The solution of 5 in MeOH displayed photoreaction‐induced self‐assembly behavior to form twisted tape‐like fibers of width 200 nm, as determined by TEM imaging.