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<正>自1999年烯类单体的双光子聚合方法被发现以来[1],其产物在光开关制备[2]、光子晶体[3]、微机械[4]及三维微加工[5]等领域得到了广泛的应用.由此,烯类双光子聚合机理也成为人们研究的焦点[6].到目前为止,研究者们普遍认为烯类单体的双光子聚合反应属于自由基历程,各种利用双光子 相似文献
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采用非线性透过率法测定了多枝[1,3,4]-噁二唑衍生物的双光子吸收性质. 测定了化合物的单光子荧光光谱和双光子荧光光谱, 在800 nm波长的激光激发下, 9-乙基-3,6-双{5-(4-叔丁基苯基)-[1,3,4] 噁二唑-2-苯乙烯基}-咔唑(3)和三-{5-(4-叔丁基苯基)-[1,3,4] 噁二唑-2-苯乙烯基-4-苯基}-胺(4)能够发出很强的蓝色和黄绿色双光子上转换荧光, 荧光峰分别位于485和547 nm. 这些多枝结构化合物的双光子吸收截面较大(数值超过104 GM), 并具有很强的光限幅效应. 多枝分子中重复单元的推拉电子结构和协同效应有效地增强了分子的双光子吸收性质. 相似文献
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2,4,5-三苯基咪唑类化合物发现具有消炎、二阶非线性光学活性、化学荧光等性能和应用.我们发现,2,4,5-三苯基咪唑类化合物的结构与具有双光子吸收性质的多分枝结构十分类似[1,2].具有双光子吸收(TPA)的有机化合物在光电材料方面有多方面的应用:如光限幅[3]、三维结构微加工[4]、三维光信息存储、频率上转换激光[5],制造用于生物学领域的双光子聚焦显微镜.我们合成了2-芳基-4,5-二噻吩基咪唑类化合物,试图将咪唑环的4,5位上的苯环换成噻吩杂环后,研究其结构变化对双光子吸收等一系列物理光谱特性的影响. 相似文献
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采用非线性透过率法研究了以N为耦合中心的多枝化合物N-[4-{2-(3,5-二-[5-(4-叔丁基苯基)-1,3,4-噁二唑-2-]苯基}-1-乙烯基}苯基}-N,N-二苯胺(BPODPA), N,N-双[4-{2-(3,5-二-[5-(4-叔丁基苯基)-1,3,4-噁二唑-2-]苯基}-1-乙烯基}苯基}-N-苯胺(BBPOPA)和N,N,N-三[4-{2-(3,5-二-[5-(4-叔丁基苯基)-1,3,4-噁二唑-2]苯基}-1-乙烯基}苯基}胺(TBPOA)的双光子吸收性质, 测定了化合物的单光子荧光光谱和双光子上转换荧光光谱, 研究了多枝化对三苯胺分子双光子吸收和双光子激发荧光性质的影响.在800 nm波长的激光激发下,化合物BPODPA、BBPOPA和TBPOA在二氯甲烷溶液中发出很强的蓝绿色双光子上转换荧光, 荧光峰分别位于502、515 和518 nm. 这些多枝结构化合物的双光子吸收截面较大, 双光子吸收增强来源于多枝分子中扩展的π共轭体系和重复单元的协同效应. 相似文献
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通过无溶剂反应,合成了四种具有D-π-D(D-供体,π-共轭体系)结构的光聚合引发剂,即4,4′-双[2-(4-N,N-二乙胺基)-苯乙烯基]联苯(BDEVB)、4,4′-双[2-(4-N,N-二丙胺基)-苯乙烯基]联苯(BDPVB)、4,4′-双[2-(4-N,N-二丁胺基)-苯乙烯基]联苯(BDBVB)和4,4′-双[2-(4-N-甲基-N-羟乙基胺基)-苯乙烯基]联苯(BMHVB),并利用1HNMR,IR和元素分析进行了表征,同时研究了它们在不同溶剂中的单光子和双光子荧光.实验结果表明:不同的电子供体使其单光子荧光和双光子吸收截面具有不同的变化趋势. 相似文献
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用飞秒Ti∶sapphire激光研究了3个树枝分子1,2,4,5-四(4-N,N-二苯氨基苯乙烯基)苯(TPAB)、1,2,4,5-四[4-N,N-二(4-溴苯基)氨基苯乙烯基]苯(TPAB-Br)和1,2,4,5-四{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}苯乙烯基}苯(TPAB-OXA)的多光子吸收及上转换荧光性质.在二氯甲烷溶液中3个生色团分子TPAB,TPAB-Br和TPAB-OXA在800 nm飞秒光激发的双光子荧光发射波长分别为569,535和621 nm,在1300 nm飞秒光激发的三光子频率上转换荧光发射波长分别为566,534和610 nm,采用非线性透过率法测得在四氢呋喃(THF)溶液中TPAB,TPAB-Br和TPAB-OXA在800 nm和150fs激光激发下双光子吸收截面分别为61.86×10-50,6.19×10-50和65.98×10-50 cm4.s/photon;在1300 nm和80 fs激光激发下三光子吸收截面分别为3.88×10-79,7.76×10-79和27.17×10-79 cm6.s2.树枝分子具有很强的多光子吸收和上转换荧光发射能力,多光子荧光发射波长位于500~600 nm. 相似文献
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本文运用激光微细加工技术,通过对不同浓度引发剂的甲基丙烯酸类树脂的聚合行为进行评价,研究了1-甲基-2-[2-(9-戊基-咔唑-3-基)-乙烯基]-3,3-二甲基吲哚碘盐(I)作为双光子光引发剂的聚合特性,结果表明该化合物在扫描速度为44μm/s时,双光子聚合阈值为139kJ/cm2;当激光能量密度为286kJ/cm2时,引发聚合的曝光时间阈值为0.7ms.实验结果为进一步作为双光子聚合三维结构的微细加工提供了可靠依据. 相似文献
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An efficient approach to the synthesis of highly congested di, penta and hexacyclic pyrazoles as well as imidazole fragment containing novel heterocyclic molecule has been developed through a carbanion induced transformation of suitably functionalized 2H-pyran-2-ones, benzo[h]chromene and thiochromeno[4,3-b]pyrans. Due to the presence of fluorescence, we report their prime application metal sensor as off/on switching in ferric ions. 相似文献
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Uroš Grošelj Mojca Žorž Amalija Golobič Branko Stanovnik Jurij Svete 《Tetrahedron》2013,69(52):11092-11108
A new and simple synthesis of novel N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates, which exist in equilibrium with their 4-oxo tautomers, has been developed in two steps starting from N-protected α-amino acids. The key intermediates are enaminones, which can also be isolated, characterized, and used for the construction of other functionalized heterocycles, before they spontaneously decompose to pyrrole products. 4-Hydroxypyrroles are prone to partial aerial oxidation but can be efficiently alkylated or reduced to stable polysubstituted pyrrolidine derivatives. 相似文献
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The chemoselectivity in the intramolecular CH insertion of various diazosulfonamides has been experimentally studied. The results reveal that the aliphatic 1,4-, 1,5-, or 1,6-C(sp3)?H insertions of diazosulfonamides are not accessible, while the aromatic 1,5-C(sp2)?H insertion can be realized specifically by adjusting the diazo-adjacent group. In addition, the general chemoselectivities in the intramolecular CH insertions of diazosulfonyl compounds are summarized. Generally, diazosulfones undergo both aromatic 1,5-C(sp2)?H and aliphatic 1,5- and 1,6-C(sp3)?H insertions, while diazosulfonates undergo aliphatic 1,5- and 1,6-C(sp3)?H insertions. However, diazosulfonamides only undergo aromatic 1,5-C(sp2)?H insertion. 相似文献
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N-Heterocyclic carbene-palladacyclic complexes 3 were successfully achieved in a one-pot procedure under mild conditions. The structure of 3a was unambiguously confirmed by X-ray single crystal diffraction and it was an active catalyst in the Buchwald-Hartwig amination and α-arylation of ketones even at very low catalyst loadings (0.01?mol%). 相似文献
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An efficient tandem approach for the selective synthesis of 4,5-dihydroimidazo[1,5-a]quinoxalines 6a–g and imidazo[1,5-a]quinoxalines 7a–h by the reaction of 2-imidazolyl anilines 4a–c with aryl aldehydes 5a–k under mild reaction conditions is described. Introduction of electron releasing alkyl groups in substrates 4a–b was found to be instrumental for the success of the reaction. 相似文献
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The Diels-Alder reactivity of 1,2-heteroborines (H4C4B(H)X, X?=?NH, PH, AsH; O, S, Se) has been computationally explored by means of Density Functional Theory (DFT) calculations. The influence of the HB?=?X fragment on the reactivity of the system has been quantitatively analyzed in detail by means of the so-called Activation Strain Model (ASM) of reactivity. It is found that the interaction between these species and the dienophile is significantly stronger than that computed for their all-carbon isoelectronic counterpart, benzene. In addition, the strain energy plays a key role in the observed reactivity trends. The role of the aromaticity strength of these heteroarenes on the reactivity is also assessed. 相似文献
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Xi-Liu YunWen-Ying Bi Jian-Hui HuangYu Liu Daisy Zhang-NegrerieYun-Fei Du Kang Zhao 《Tetrahedron letters》2012,53(38):5076-5080
A variety of N-aryl and N-alkyl carbazolones were conveniently achieved in good to high yields via Pd2(dba)3-mediated intramolecular coupling of N-substituted α-iodo enaminones under microwave irradiation. The Pd(0)-catalyzed cyclization was found to proceed favorably with the more electron-deficient phenyl ring during the reactions involving unsymmetrical N,N-diaryl α-iodo enaminones. This unique property enables the construction of carbazolone skeleton containing nitro substituted benzenoid ring. 相似文献
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Shashikant U. Dighe Surya K. Samanta Shivalinga Kolle Sanjay Batra 《Tetrahedron》2017,73(17):2455-2467
An efficient iodine-mediated oxidative Pictet-Spengler reaction in dimethyl sulphoxide (DMSO) using terminal alkynes as the 2-oxoaldehyde surrogate for the synthesis of aryl (9H-pyrido[3,4-b]indol-1-yl)methanones is described. The scope of the protocol includes the total synthesis of Fascaplysin, Eudistomins Y1 and Y2. The methodology is extended for preparing pyrrolo[1,2-a]-quinoxaline and indolo[1,5-a]quinoxaline derivatives. The utility of 1-aroyl-β-carbolines was demonstrated by performing palladium-catalyzed β-carboline directed ortho-C(sp2)-H functionalization of the phenyl ring with thiomethyl (SMe) group using DMSO as source and for accessing 4-aryl-canthin-6-ones. 相似文献
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In this Letter, we described a facile method for constructing fused bicyclic 1-arylpyrazol-5-one ring system. We employed various methylene-containing carboxylic acids as the substrates and proved that the pyrazolone ring closure requires activated methylene group in intermediate II. Accordingly, a series of structurally diversified, fused bicyclic 1-arylpyrazol-5-ones was prepared in moderate to high yields using the requisite substrates. 相似文献
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Both substituted 2,4,5,6-tetrahydrocyclopenta[c]pyrazoles and 2,4,5,6-tetrahydropyrrolo[3,4-c]pyrazoles have been synthesized by the 3+2 intramolecular dipolar cycloaddition of nitrilimines to alkynes. This cyclization has been extended to more versatile 3-bromo derivatives by the use of alkynylbromides as dipolarophiles. 相似文献