I两个银配合物的合成及其荧光性能的研究上海理工大学王凯摘要:本论文以超分子化学和晶体工程理论为研究基础,用醋酸银和硝酸银与含膦配体N-二苯基膦甲基-对氨基吡啶自组装,合成了一个一维双链配合物1和二维结构的配位聚合物。该配合物的晶体结构是运用X-射线单晶衍射仪得到的,并进行了元素分析、红外光谱等表征,以及研究了它的荧光性能。关键词:醋酸银;硝酸银;含膦配体;合成;表征;荧光性质IISynthesisandcharacterizationoftwoAgcompoundandstudyofphotoluminescencepropertiesAbstract:Basedonsupermolecularchemistryandcrystalengineeringtheory,weselectedCH3COOAg,AgNO3toreactwithN-diphenylphosphanylmethyl-4-aminopyridine,whichgavea1Ddoublechaincoordinationpolymeranda2Dsupermolecular.Thetwocompoundswerecharacterizedbyelementalanalysisandinfraredspectroscopy,anditscrystalstructurebyasingle-crystalX-raydiffractionanalysishasbeenconfirmed.Andwefurtherinvestigatedtheirphotoluminescenceproperties.Keywords:CH3COOAg;AgNO3;P-containingligand;Synthesis;Characterization;Photoluminescenceproperties目录摘要··································································································ⅠAbstract····························································································Ⅱ1前言·································································································12实验部分···························································································22.1仪器与试剂·····················································································22.2合成······························································································22.3晶体结构的测定···············································································23实验结果与讨论·················································································33.1红外光谱分析··················································································33.2晶体结构························································································43.3荧光性能的研究···············································································64结论································································································7参考文献·····························································································7致谢···································································································811.前言众所周知,配位聚合物在磁性,荧光,催化及吸附等很多物理性能方面表现非常新颖而奇特的特性和潜在的应用价值,因此在光,电,磁,催化,吸附等领域具有非常广泛的应用前景。因此,配位聚合物的研究迅速发展成为无机化学、固体化学和材料化学等多学科领域的研究的热点[1-2]。当今,我们的研究领域主要是合成结构新颖的配位聚合物,然后分析其结构特点,探讨它们功能和结构的关系,进而发掘并发展它们潜在的应用价值。结构决定性质,不同的配体结构、不同金属离子物理和化学性能能够直接影响目标产物的结构及性能。所以,有机配体的选择对来合成配合物显得尤为重要。实验表明,影响配位聚合物的合成的因素很多,不但包括选择金属离子的配位构型,有机配体的结构,合适的反应条件(溶剂体系),甚至是反应环境的微小变化(例如,溶剂、温度、pH值、投料比、投料顺序、反应时间等),都可能造成构造基元组装成的有序拓扑结构或小分子单元发生翻天覆地的变化[3-7]。由于有机配体与金属离子组装的配位聚合物的特点及性质大部分是由有机配体的结构决定的。因此,有效合理的选择或者合理的设计合成有机配体也是合成具有良好性能配位聚合物的重要任物之一近几十年来,过渡金属与有机膦配体反应生成的配合物化学在国际上迅速发展以及形成的配合物在有机催化反应过程中的重要应用引起化学家们的广泛关注,同时有机磷配合物也在吸附、磁学、光学、非线性光学等领域具有巨大潜在应用前景,它的这些优越的性能越来越受到化学和材料领域研究的广泛关注。如:2009年,Tanase等研究者通过直线型的四齿膦配体和金盐反应,结果依次得到了四核和八核的配合物,作者也进一步研究了他们的荧光性质,研究得结果表明这两个四核金配合物和八核金配合物在溶液中都有非常强和明显的荧光[8-9]。虽然配位聚合物的具有非常广阔无限的前景,但是目前人们对配合物的认识还处在初级阶段,对此类金属-有机超分子配合物的设计合成还不够成熟和精确,对于影响配合物结构的细微因素没能有得到深入的认识,某些配合物尚不能按照人们的想法准确的合成得到我们所需结构的目标产物,距人们所期盼的定向确定的合成结构并应用,这对我们化学家都是巨大的挑战,我们还有很长的路要走。本论文用含N,P的配体N-二苯基膦甲基-对氨基吡啶dppmpy与醋酸银及硝酸银自组装能合成了两个配合物,并对它们进行了红外,元素分析,X-射线单晶2衍射的表征,并进一步测试了它们的荧光性能。2.实验部分2.1试剂和仪器实验中所用的化学试剂,药品都并没有作进一步处理,都是在正规的试剂公司购买的。药品的称量在FA2004型电子天平(上海良平仪器仪表有限公司)上进行。红外光谱在NicoletAvatar360傅里叶红外光谱仪上用溴化钾压片测定(4000-400cm-1)。在Carlo-ErbaCHNO-S元素分析仪上测得碳、氢、氮的含量。在RigakuMercuryCCDX射线单晶衍射仪上测定晶体的结构。2.2化合物{[Ag2(CH3COO)2(dppmpy)2]·2MeOH}n(1)的合成将配体N-二苯基膦甲基-对氨基吡啶(25mg,0.1mmol)和醋酸银(18mg,0.1mmol)加入到三氯甲烷(10ml)和MeOH(10ml)的混合溶剂中,之后对溶液进行搅拌,时间为3小时,最后把混合溶液通过过滤步骤得到清液。用玻璃管把得到的清液加入其中,之后把无水乙醚加入其中,最后依次进行最后的实验过程密封,静置,然后在进行固定。通过14天的等待得到了生成物1,然后进行过滤的步骤将其收集并且用化学试剂乙醚进行洗涤。产量:27mg(产率65%basedonAg)。化合物[Ag4(NO3)2(dppmpy)4](NO3)2·MeOH(2)的合成将配体N-二苯基膦甲基-对氨基吡啶(28mg,0.1mmol)和AgNO3(17mg,0.1mmol)分别溶解在甲醇(5ml)中,进行混合,通过不断搅拌,5小时后过滤得到清液,之后向此清液上层缓慢地加入30ml的无水乙醚,密封,静置固定。最终得到无色的块状晶体2,过滤收集,并且使用化学试剂乙醚进行洗涤。产量:36mg(产率78%basedonAg)。2.3晶体结构的测试选出大小合适的单晶,在RigakuMercuryCCD衍射仪上收集衍射数据,最终所有的计算均由SHELXTL程序包在acer计算机上完成。表1为配位聚合物1-2的部分晶体学参数。表1化合物1-2的部分晶体学参数Table1Partofthecrystalparametersofcompound1-2______________________________________________________________________________Complex123______________________________________________________________________________EmpiricalFormulaC21H24AgN2O3PC73H72Ag4N12O13P4FormulaWeight491.261880.79CrystalSystemtriclinictriclinicSpaceGroupPīPīa/Å9.901(2)9.6270(19)b/Å9.941(2)13.720(3)c/Å12.109(2)15.055(3)α/°78.99(3)101.44(3)β/°74.01(3)91.20(3)γ/°78.43(3)102.51(3)V/Å31109.7(4)1898.4(8)Z21Dc(g·cm–3)1.4701.645μ/mm–11.0111.176F(000)500.0946.0Reflectionscollected906113188UniqueReflections48706620No.Observations(I2.00(I))36695009No.Variables260520R1andwR20.0302,0.06930.0489,0.1020GOF0.9761.046Largestresidual0.434/-0.4010.772/-0.528peaksandholes(e·Å–3)______________________________________________________________________________3结果与讨论3.1合成与测试用N-二苯基膦甲基-对氨基吡啶与醋酸银以1:1的摩尔比在三氯甲烷/甲醇混合溶剂中,与硝酸银在甲醇溶剂中,得到配位聚合物1(产率为65%),配位聚4合物2(产率为78%)。化合物1和2不溶于常规的有机溶剂,在红外光谱中,化合物1在1619cm-1处出现了羧酸根的特征峰。化合物2在1334cm-1出现了NO3-的特征峰。3.2.1化合物1的晶体结构化合物1属于三斜晶系Pī空间群。每个单元