球形主体分子的包结性能及其在制备有机非线性光学材料中的应用  

Inclusion Properties of Ball-Shaped Clathrate Hosts and Its Application to Preparing Organic Non-Linear Optical Materials

作　　者：郭文生[1] 郭放[1] 邓敏[1] 葛春华[1] 刘祁涛[1] 花晓晴[2] 白吉玲[2] 田之悦[3] 王树春[3] 郑启泰[3] 

机构地区：[1]辽宁大学化学科学与工程学院,沈阳110036 [2]中国科学院大连化学物理研究所分子反应动力学国家重点实验室,大连116023 [3]中国医学科学院药物研究所,北京100050

出　　处：《化学学报》2001年第2期284-290,共7页Acta Chimica Sinica

基　　金：国家自然科学基金 ( 697780 2 2 );辽宁省自然科学基金( 9810 30 10 0 1)资助项目

摘　　要：提出了球形主体分子的设计思想 ,把具有球形结构的分子柏木醇 ( 1)、马钱子碱 ( 2 )、三乙烯二胺 ( 1,4-二氮-二环 [2 .2 .2 ]辛烷 ) ( 3 )作为主体分子 ,把酚类化合物 ,诸如苯酚 ( 4)、邻甲苯酚 ( 5 )、间甲苯酚 ( 6)、对甲苯酚 ( 7)、对氯苯酚 ( 8)和对硝基苯酚 ( 11)等作为客体分子 ,进行了主客体分子相互作用实验 .采用粉末X射线衍射、1HNMR等分析手段确认了包结化合物的形成及主客体分子的摩尔比 .摩尔比 (H/G)分别为 ( 1) + ( 4) 1∶1,( 1) + ( 5 ) 1∶1,( 1) +( 6) 1∶1,( 1) + ( 7) 1∶1,( 1) + ( 11) 1∶2 ;( 2 ) + ( 11) 1∶1;( 3 ) + ( 4) 1∶2 ,( 3 ) + ( 5 ) 1∶3 ,( 3 ) + ( 6) 1∶2 ,( 3 ) + ( 7) 1∶2 ,( 3 )+ ( 8) 1∶2 ,( 3 ) + ( 11) 1∶2 .对典型包结化合物的单晶 ,诸如柏木醇和邻甲苯酚、马钱子碱和对硝基苯酚以及三乙烯二胺和对硝基苯酚 ,进行了四圆X射线衍射结构分析 ,结果表明 ,包结化合物的堆砌结构特征随主体分子的体积大小而改变 ,从隧道型如 ( 1) + ( 5 )和 ( 2 ) + ( 11)转变为夹层型如 ( 3 ) + ( 11) .用Nd :YAG激光测试晶体的SHG效应 ,结果表明 。This paper introduces design idea of spherical clathrate hosts which uses cedrol (1), brucine(2), 1,4 - diazabicyclo[2.2.2] octane (3) endowed of ball - shaped rigid molecular backbone as host molecules and phenol - type molecules such as phenol (4), o - cresol (5), m - cresol (6), p - cresol (7), 4 chrolophenol (8), 4 - methoxyphenol (9), 4 - hydroxylbenzaldehyde (10), 4 - nitrophenol (11) and maleicanhydride (12) used as guest molecules. We have carried out inclusion experiment using these hosts with phenol- type compounds. The formation of inclusion compounds were confirmed by means of powder XRD, and the molar ratios of inclusion compounds were determined by H-1 NMR, (1) + (4) 1:1,(1) + (5) 1:1, (7) 1:2, (3)+(8) 1:2, (3)+(9) 1:2, (3) + (11) 1:2 as results. The single crystal structure of a few typical. inclusion compounds was determined by X- ray diffraction analysis and showed that the variation of architectural structure characteristic of inclusion compounds depends on the volume size of the host molecules from channel type as with (1) + (5) and (2) + (11) to intercalate as with (3) + (11). The SHG effect of the inclusion compound crystals was inspected by Nd: YAG laser and the results showed that a mass of prepared inclusion crystals exhibits non - linear optical property.

关 键 词：笼状包结化合物 球形主体分子 酚类客体化合物 SHG效应 有机非线性光学材料 包结性能 非线性光学性质 

分 类 号：O621[理学—有机化学]