含吡啶端基9,10-双芳基蒽共轭分子的合成、聚集诱导荧光增强及双光子诱导荧光

通过Heck反应合成了2个以吡啶为端基的9,10-双芳基蒽共轭分子9,10-二{4-{4-[N,N-二(4-吡啶乙烯基)苯基]氨基}苯乙烯基}蒽(4Py-PAA)和9,10-二{4-{4-[N,N-二(2-吡啶乙烯基)苯基]氨基}苯乙烯基}蒽(2Py-PAA),化合物结构经过1H NMR,13C NMR,HRMS-MALDI-TOF确证.测定了化合物在不同极性溶剂中的紫外吸收光谱、荧光光谱、荧光寿命及量子产率,测算了4Py-PAA和2Py-PAA的偶极矩.通过循环伏安法研究了它们的前线轨道能级.测定了4Py-PAA和2Py-PAA的固体荧光光谱、固体荧光量子产率及在不同含水量的水/THF混合溶液中的荧光光谱.实验发现4Py-PAA在THF溶液中发出蓝绿色荧光,固体时发出红色荧光,在含水量为70%的水/THF混合溶剂中发出黄色荧光,荧光强度是纯四氢呋喃(THF)的3倍,呈现聚集荧光增强性质.在800 nm飞秒激光下采用双光子诱导荧光参比法测定了4Py-PAA和2Py-PAA在THF溶液中的双光子吸收截面分别为193和101 GM.实验结果表明含有2位和4位吡啶端基9,10-双芳基蒽共轭分子具有良好的荧光发射性能及双光子吸收性质.     

“马鞍型”环八四噻吩-三嗪体系的合成与聚集诱导发光(AIE)性质研究

以"马鞍型"环八四噻吩(COTh)与1,3,5-三嗪为构筑模块,通过Kumada类型反应有效地制备了三种分别含有1~3个COTh结构单元的环八四噻吩-三嗪衍生物,即2,4-二甲氧基-6-(5,8,11-三甲基硅基)-环八[1,2-b:4,3-b':5,6-b':8,7-b'']四噻吩-1,3,5-三嗪(1),2-甲氧基-4,6-二{(5,8,11-三甲基硅基)-环八[1,2-b:4,3-b':5,6-b':8,7-b'']四噻吩}-1,3,5-三嗪(2)和2,4,6-三{(5,8,11-三甲基硅基)-环八[1,2-b:4,3-b':5,6-b':8,7-b'']四噻吩}-1,3,5-三嗪(3).理论计算表明了该类化合物的长波长的两个吸收峰来自于分子内的电荷转移(CT)吸收.在溶液相它们发射分子内电荷转移(ICT)态荧光,峰位在560~570nm.而在冻结态下呈双荧光发射,即短波长的环八四噻吩本征态发光(400 nm)与长波长的ICT发光(480~500 nm).在四氢呋喃(THF)-H2O二元溶剂体系中,该类化合物产生聚集诱导发光(AIE)现象,可能与化合物分子同时受分子内旋转受阻(RIR)与分子内振动受阻(RIV)机制控制有关.单晶数据表明,化合物1分子内噻吩环与三嗪环之间呈现近平面构象.相邻分子之间噻吩环上的碳原子与三嗪环上的碳原子存在C-C相互作用,制约着连接分子内噻吩环与三嗪环之间单键的自由旋转,从而一定程度上制约了非辐射失活过程,有利于AIE现象的产生.     

9,10⁃二(N⁃苯基吲哚⁃3⁃乙烯基)蒽的合成及聚集诱导荧光和压致荧光变色性质

通过简单的Wittig反应合成了一个荧光化合物9,10-二(N-苯基吲哚-3-乙烯基)蒽(IA-Ph); 通过核磁共振和质谱对其结构进行了确认; 利用荧光发射光谱和紫外吸收光谱对其光物理性质进行了表征. 结果表明, 化合物IA-Ph兼具聚集诱导荧光(AIE)和压致荧光变色性质, 在相同浓度下, 该化合物在THF/H₂O(体积比1∶9)混合溶液中的荧光强度比在纯四氢呋喃(THF)溶液中增加了12倍, 具有明显的AIE效应. 通过简单而有效的机械力研磨, 化合物可以从初始的发绿光转变为研磨后的橙红光, 光谱红移约68 nm; 而且在加热或溶剂熏蒸条件下, 化合物的颜色可以回复到起始的绿光, 具有完全可逆性.     

meso-三嗪取代苯基卟啉的简单一锅合成

报道一种以羟基卟啉与三嗪和其它亲核试剂为原料一锅法高产率合成不对称多取代三嗪卟啉化合物的简单方法. 研究了2,4,6-三氯三嗪与羟基卟啉、醇和胺通过分级亲核取代反应合成不对称2,4,6-取代三嗪卟啉的方法和反应条件. 以2,4,6- 三氯三嗪和5-(4-羟基)苯基-10,15,20-三苯基卟啉反应生成卟啉单取代二氯三嗪, 然后进一步与醇或胺反应合成了7个三嗪卟啉新化合物, 产物经元素分析, MS, 1H NMR和UV-Vis进行结构表征.     

均三嗪衍生物的合成及光谱性质研究

以乙腈、乙醇、氯化氢、冰乙酸等为原料,用苯作溶剂,制得三甲基均三嗪,再分别与α-萘甲醛、β-萘甲醛反应,得目标产物2,4,6-三(1-萘乙基)均三嗪、2,4,6-三(2-萘乙基)均三嗪衍生物,用IR,MS(MALDI-TOF),氢谱等现代分析手段确认目标化合物的结构,研究目标化合物的紫外吸收光谱、荧光光谱等性质。为均三嗪衍生物光电性能的开发利用提供新的功能材料和理论基础。     

含甲氧基四苯乙烯咪唑化合物的合成、光物理性质、理论计算及细胞成像北大核心CSCD

通过一步法合成了一例含甲氧基四苯乙烯咪唑化合物4,5-双-4-甲氧基苯基-2-(4-(1,2,2-三苯基乙烯基)苯基)-1-咪唑(BTI),通过核磁共振波谱仪(NMR)、质谱(MS)和元素分析等技术手段对BTI进行了全面的表征,解析了化合物的单晶结构,通过紫外-可见吸收光谱和荧光发射光谱研究了BTI的光物理性质,借助理论计算对化合物的激发态性质进行了阐述,最后研究了化合物BTI在细胞成像方面的应用。结果表明,该化合物表现出明显的分子内电荷转移(ICT)型聚集诱导发光(AIE)性质,光谱实验数据与理论计算结果吻合较好。细胞成像研究显示化合物BTI可以很好地穿越人肝癌细胞(HepG2)的细胞膜,并可进行单、双光子激发共聚焦荧光显影。     

2,4,6-三(对甲氧基苯乙烯基)-1,3,5-均三嗪光转换剂的合成

合成了新化合物2,4,6-三(对甲氧基苯乙烯基)-1,3,5-均三嗪(TMST);利用红外光谱、元素分析和核磁共振(1 H NMR)分析了化合物的组成和结构,利用紫外和荧光光谱分析了其光谱特征.结果表明,在375nm的紫外光激发下,化合物在410～480nm区域发出较强的蓝光,对应于叶绿素a的主吸收峰;这表明其可望作为一种新的蓝光光转换剂而应用于农用薄膜.     

不对称卟啉体系中的弱相互作用

采用¹H NMR、紫外-可见(UV-Vis)吸收光谱、荧光光谱和分子模拟方法研究了5-邻咪唑甲基苯基-10,15,20-三对叔丁基苯基卟啉(化合物1)和5-对咪唑甲基苯基-10,15,20-三苯基卟啉(化合物2)在氯仿中的弱相互作用. ¹H NMR研究表明, 相对于自由咪唑而言, 化合物1和2的侧链咪唑的质子化学位移均向高场移动, 说明两种化合物中存在弱相互作用; 对UV-Vis光谱的研究发现, 与在丙酮中相比, 化合物1在氯仿中的Soret带裂分, 说明在化合物1中存在的是分子内的弱相互作用; 而化合物2的Soret带则发生27 nm的红移, 说明在化合物2中存在的是分子间弱相互作用. 对荧光发射光谱的研究支持上述结论. 对分子的最低能量构象分析得到了与光谱研究一致的结果.     

基于2,4,6-三苯基-1,3,5-三嗪和芴单元的激基缔合物主体材料的制备与应用（英文）

设计合成了三种基于2,4,6-三苯基-1,3,5-三嗪和芴单元的双极性主体材料FTRZ, p TFTRZ和mTFTRZ.分别研究了它们的热稳定性、光物理性能、电化学性质和电致发光器件性能与分子的拓扑结构之间的关系.FTRZ,p TFTRZ和mTFTRZ的热分解温度均在400℃以上,p TFTRZ和mTFTRZ的玻璃化转变温度分别是103和120℃.化合物FTRZ,p TFTRZ和mTFTRZ在甲苯溶液中的光学带隙分别为3.24,3.29和3.24eV,它们的三重态能级分别为3.04,3.11和3.05 eV.由于2,4,6-三苯基-1,3,5-三嗪平面间的π-π作用,化合物FTRZ, p TFTRZ和mTFTRZ在薄膜状态下形成激基缔合物,荧光发射光谱明显红移.最后研究了FTRZ, p TFTRZ和mTFTRZ作为客体发光分子2,4,5,6-四(9-咔唑基)-间苯二腈的主体材料在绿色热活化延迟荧光电致发光器件中的应用.以化合物FTRZ作为主体材料的绿色有机电致发光器件(OLED)表现出更好的电致发光性能,最大电流效率为6.7cd/A,最大外量子效率为2.07%,最大亮度为35718 cd/m~2,远优于以p TFTRZ和mTFTRZ作为主体材料的绿光器件.     

肽核酸骨架分子键联卟啉的合成及结构表征

以5,10,15-三苯基-20-(4-羧基苯基)卟啉和5,10,15-三苯基-20-(4-羟基苯基)卟啉为原料, 分别与N-(Boc-氨乙基)甘氨酸乙酯(3)及其衍生物4作用, 得到了两种肽核酸骨架分子键联卟啉化合物6和8. 中间体和目标化合物均由紫外-可见光谱、红外光谱、核磁共振光谱、质谱及元素分析所确证. 目标化合物的荧光光谱测试结果表明, 肽核酸单元分子的链接对卟啉分子的荧光波长和强度影响不大.     

A comparative study of crystal structures and inclusion properties of fluorinated triazines

Three perfluorinated host compounds of the triazine type, namely 2,4,6-tris(pentafluorophenoxy)-1,3,5-triazine (1), 2,4,6-tris(pentafluorothiophenoxy)-1,3,5-triazine (2) and 2,4,6-tris(pentafluorophenamin)-1,3,5-triazine (3), were synthesized differing only in the linking heteroatom (O, S and NH) between the triazine core and the pentafluorophenyl groups. The crystal structures involving compounds 1, 2 and their inclusion compounds are dominated by a variety of fluorine interactions (phenyl-perfluorophenyl, C-H?F, F?F, C-F?π_F). However, in the structure of 3, possessing additional hydrogen atoms of the linkage NH-groups, the formation of hydrogen bonds is favoured, whereas fluorine contacts are less apparent. Investigations by powder X-ray diffraction and thermogravimetric analysis revealed substantial differences in the host-guest interactions of the inclusion compounds.     

Synthesis and photophysical properties of hyperbranched polyfluorenes containing 2,4,6-tris(thiophen-2-yl)-1,3,5-triazine as the core

A series of new hyperbranched polymers containing a 2,4,6-tris(thiophen-2-yl)-1,3,5-triazine core unit and polyfluorene chain arms have been synthesized via Suzuki coupling, and characterized by NMR, IR and GPC. All the polymers exhibit good thermal stability with a high decomposition temperature. By changing the 2,4,6-tris(thiophen-2-yl)-1,3,5-triazine/fluorene ratio the UV-vis absorption and emission spectra can be partially tuned. It has been found that the polymers containing a low ratio of 2,4,6-tris(thiophen-2-yl)-1,3,5-triazine units (P1-P3) have an absorption maximum around 385 nm, localized in the polyfluorene chain, and a shoulder around 425 nm ascribable to a charge transfer state involving the fluorene and the 2,4,6-tris(thiophen-2-yl)-1,3,5-triazine core. Increasing the molar ratio of the 2,4,6-tris(thiophen-2-yl)-1,3,5-triazine unit enhances the charge transfer band which becomes dominant for P4. The LUMO level of these polymers is relatively low due to the electron affinity of the triazine group. The polymers show dual emission, with a structured band in the blue (410-440 nm), attributed to the polyfluorene, and a broad band in the red (470-500 nm) associated with the charge transfer state. All the polymers exhibit two-photon absorption activity in the range of 660 to 900 nm with the maximum two-photon absorption (TPA) cross-section red-shifted from the corresponding linear absorption. The values of the TPA cross-sections vary from 1000 to 5000 GM, following the 2,4,6-tris(thiophen-2-yl)-1,3,5-triazine/fluorene ratio.     

Thermodynamic stability of 2,4,6-tris(nitromethyl)-1,3,5-triazine: an experimental and theoretical study

The molecular geometries and electronic structures of 2,4,6-tris(nitromethyl)-1,3,5-triazine isomers were investigated by the density functional method DFT/B3LYP/6-311++G** to elucidate the structural factors responsible for the stability of these systems. It was shown that a characteristic feature of the nitromethyl tautomer (1) of 2,4,6-tris (nitromethyl)-1,3,5-triazine consists in nonvalence interactions between an oxygen atom of nitro group and a carbon atom of triazine ring, which are probably due to Coulomb attraction between them. The tautomer with the 2,4,6-tris (nitromethylene)-hexahyrdo-1,3,5-triazine structure (2) is stabilized trough direct polar conjugation between the amino and nitro groups at the double bond. Structural strain of the molecule with the 2,4,6-tris(aci-nitromethyl)-1,3,5-triazine structure (3) is the reason for its thermodynamic instability. X-ray data indicate that the compound under study exists in the triazine tautomeric form 1 and the distances between oxygen atoms of nitro group and carbon atom of the triazine ring are shortened. NMR data suggest the existence of triazine in the nitromethyl form 1 in acetonitrile and acetone and a tautomeric equilibrium between the nitromethyl and nitromethylene forms in a more polar solvent (DMSO). The results obtained suggest a Coulomb-type stabilization of the 2,4,6-tris(nitromethyl)-1,3,5-triazine molecule in the gas phase, in the crystal, and in nonpolar solvents.     

An efficient and facile one-pot synthesis of structurally unique 2,4,6-tris(arylchalcogeno)-1,3,5-triazine and 1,3,5-tris(arylchalcogeno)-2,4,6-trimethylbenzene

An efficient one-pot synthesis of a novel class of 2,4,6-tris(arylchalcogeno)-1,3,5-triazine (sulfur, selenium and tellurium) and 1,3,5-tris(arylchalcogeno)-2,4,6-trimethylbenzene (sulfur and selenium)-containing ligands has been developed based on the reaction of 2,4,6-trichloro-1,3,5-triazine and 1,3,5-tris(bromomethyl)-2,4,6-trimethylbenzene with the corresponding arylchalcogenide anions generated in aqueous tetrahydrofuran.     

Synthesis and characterisation of 3-armed dendritic molecules with triphenylbenzene or triphenyltriazine as core and triphenylene derivative as shells

Two series 3-armed dendritic molecules with their 1,3,5-tris(4-methyloxyphenyl) benzene or 2,4,6-tris(4- hydroxylphenyl)-1,3,5-s-triazine core and triphenylene derivative shells connected by soft hydrocarbon chains have been synthesised and fully characterised. Whether liquid crystal (LC) or photoluminescence materials have been tuned by changing the length of the soft chain and they have been studied by POM, DSC, XRD, UV-Vis and PL. The results show that all the new dendritic compounds display UV to blue fluorescence in solvents such as DCM, THF and acetone. The TC3 compound bearing 1,3,5-tris(4-hydroxylphenyl) benzene core exhibits LC property with rectangular columnar phase (Col_r) on cooling.     

Heterogeneous photocatalytic transformations of s-triazine derivatives

Photocatalytic processes arising from irradiated semiconductor oxide suspensions containing 1,3,5-triazine (s-triazine) derivatives are described. Whereas unsubstituted 1,3,5-triazine undergoes hydrolysis, irrespective of the presence of the photocatalyst, other chloro-, amino-, mercapto-, allyloxo-, carboxy- derivatives give rise, in the presence of band-gap excited semiconductor oxide, to nearly stoichiometric formation of 2,4,6-trihydroxy-1,3,5-triazine (cyanuric acid). This last compound is stable toward photocatalytic conditions as well as to ^·OH chemically generated in homogeneous solution (H₂O₂/UV or Fenton's reagent). Only partial conversion in cyanuric acid is observed for 2,4,6-tris(2-pyridyl)-1,3,5-triazine and possible explanation is given. The formation of inorganic species (nitrate, chloride, sulfate and ammonium ions) is reported and the mechanism of their evolution presented.     

Trisubstituted 1,3,5-Triazines. 6. Synthesis of 2,4,6-Tris(acetonyl)-1,3,5-triazine

Acylation of 2,4,6-tris(tert-butoxycarbonylmethyl)-1,3,5-triazine with acetic anhydride in the presence of lithium hydride with subsequent removal of the tert-butoxycarbonyl groups with trifluoroacetic acid leads to 2,4,6-tris(acetonyl)-1,3,5-triazine, the cyclic analog of -cyanoacetone. The special spectral features of this compound compared with triazines obtained previously are discussed.     

Nitromethyl derivatives of 1,3,5-triazine. Synthesis and properties

The destructive nitration of 2,4,6-tris[di(carboxy)methylene]hexahydro-1,3,5-triazine and its esters has been investigated. A first representative of the nitromethyl derivatives of 1,3,5-triazine, viz. 2,4,6-tris(nitromethyl)-1,3,5-triazine, has been synthesized.Deceased.N. D. Zelinskii Institute of Organic Chemistry, Russian Academy of Sciences, Moscow 117913. Institute of Chemical Physics in Chernogolovka, Russian Academy of Sciences, Chernogolovka 142432. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 9, pp. 1254–1259, September, 1997.     

The structure of 2,4,6-tris[di(tert-butoxycarbonyl)methylidene]-hexahydro-1,3,5-triazine

The structure of 2,4,6-tris[di(tert-butoxycarbonyl)methylidene]hexahydro-1,3,5-triazine was studied by quantum chemistry, NMR and IR spectroscopy, and X-ray diffraction. This compound exists exclusively in the hexahydro-1,3,5-triazine form both in solution and in the solid phase, although due to the loss of the aromatization energy, this structure should be less stable than a 1,3,5-triazine structure. The formation of strong intramolecular hydrogen bonds confirmed by NMR and IR spectroscopy and X-ray diffraction data may be a main reason for stabilization of the hexahydro-1,3,5-triazine isomer. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1022–1026, June, 2006.     

The synthesis and characterization of 2,4,6-tris(3,4-dihydroxybenzimino)-1,3,5-triazine and its [salen/salophenFe(III)] and [salen/salophenCr(III)] capped complexes

Four new trinuclear Fe(III) and Cr(III) complexes involving tetradentate Schiff bases N,N′-bis(salicylidene)ethylenediamine-(salenH₂) or bis(salicylidene)-o-phenylenediamine-(salophenH₂) with 2,4,6-tris(3,4-dihydroxybenzimino)-1,3,5-triazine have been synthesized and characterized by means of elemental analysis, ¹H N.M.R., FT-IR spectroscopy, thermal analyses and magnetic susceptibility measurements. The complexes have also been characterized as low-spin distorted octahedral Fe(III) and Cr(III) bridged by catechol group.