CN105566358B - 环状氮杂环卡宾金属配合物在芳香族化合物选择性识别中的应用 - Google Patents
环状氮杂环卡宾金属配合物在芳香族化合物选择性识别中的应用 Download PDFInfo
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Abstract
本发明公开了环状氮杂环卡宾金属配合物作为主体在芳香族化合物选择性识别方面的应用。在25℃下，将作为客体的不同芳香族化合物溶解在有机溶剂中，在一定浓度下，将主体溶液分别与不同的客体溶液混合，测定其荧光光谱，找出主体能够识别的客体。对于主体能够识别的客体，用不同的浓度的客体对主体进行滴定，测定其荧光光谱。芳香族化合物溶液的浓度范围为0‑50.0×10‑5 mol/L。每次添加后，8‑10分钟达到反应平衡测定相应的荧光强度。本发明作为主体的环状氮杂环卡宾银配合物对芳香族化合物的荧光感光效果明显，可以用来制作荧光探针，有望在荧光化学领域得到应用。
Description
关于资助研究或开发的声明
本发明是在国家自然科学基金（基金号为21172172和21572159），天津市自然科学基金（基金号为11JCZDJC22000），天津市高等学校创新团队培养计划（基金号为TD12-5038）和天津师范大学应用开发研究基金(基金号：52XK1202) 资助下进行的。
技术领域
本发明属于金属有机化学技术领域，涉及通过烷基桥联的双咪唑盐作为前体的氮杂环卡宾金属配合物，更具体的说是一种环状氮杂环卡宾金属配合物及其制备方法，以及环状氮杂环卡宾金属配合物荧光识别性能的研究。
背景技术
自20世纪末期Arduengo首次分离得到了稳定的游离N-杂环卡宾(NHC)以后，N-杂环卡宾金属络合物的研究得到广泛关注且发展迅猛。周期表中许多金属的N-杂环卡宾络合物都有报道。近十几年来，N-杂环卡宾逐渐成为金属有机化学的研究热点，被广泛应用于有机合成、高分子化学及催化等领域。N-杂环卡宾配体与金属间的配位方式与有机膦配体虽然十分相似，但是卡宾与金属的配合物对水，热和空气得良好稳定性是膦配体金属配合物所无法比拟的。近年来N-杂环卡宾金属配合物被广泛应用于各种催化反应，例如烯烃复分解、共轭加成、芳胺化、氢化反应等。由于N-杂环卡宾形成的卡宾-金属σ键，稳定性能高，结构容易被修饰，N-杂环卡宾配合物用作有机反应底物和催化剂的研究受到了人们的广泛关注。N-杂环卡宾配体在与金属配合时可以形成钳形，三角钳形，大环形以及槽装等多种结构，这些特殊的结构作为主体可以通过多种作用力与客体结合，因此N-杂化卡宾金属配合物在荧光分子探针领域具有良好的发展前景。
发明内容
本发明的目的在于提供环状氮杂环卡宾金属配合物作为主体在芳香族化合物（甲苯，氯苯，苯胺，苯酚，硝基苯，苯甲醚，苯甲醛，苯乙酮，邻二硝基苯）选择性识别方面的应用。
为完成上述各项发明目的，本发明技术方案如下：
本发明所述的有机溶剂选自甲醇、四氢呋喃、二氯甲烷、丙酮、乙醚、乙腈、二甲基亚砜中的一种或几种的混合物；其中以为乙腈为最优。
本发明进一步公开了典型的环状氮杂环卡宾金属银配合物：
典型的环状氮杂环卡宾银配合物的分子式为C80H68Ag2F12N8P2·3DMSO.
环状氮杂环卡宾银配合物的单晶数据如下：
环状氮杂环卡宾银配合物单晶的测定方法如下：
晶体数据和结构精修参数包含在支持性信息中。在Bruker SMART 1000 CCD衍射仪上进行，实验温度为113(2)K, 在50kV 和20mA下，用Mo-Kα 辐射(0.71073Å)操作，用SMART和SAINT软件进行数据收集和还原，θ的范围是 1.8 <θ< 25º。应用SADABS 程序进行经验吸收矫正。晶体结构由直接方法解出，用SHELXTL包对全部非氢原子坐标各向异性热参数进行全矩阵最小二乘法修正。
本发明一个优选的实施例为实例1.
本发明另一个优选的实施例为应用实例1。
本发明进一步公开了环状氮杂环卡宾金属配合物晶体在荧光识别领域中的应用。
实验证明：环状氮杂环卡宾金属配合物（特别是晶体）作为主体在芳香族化合物选择性识别方面的应用。它是将作为主体的环状氮杂环卡宾银配合物溶解在有机溶剂中，在25℃下，将作为客体的不同芳香族化合物溶解在有机溶剂中（不同芳香族化合物例如甲苯，氯苯，苯胺，苯酚，硝基苯，苯甲醚，苯甲醛，苯乙酮或邻二硝基苯），在一定浓度下，将主体溶液和分别和不同的客体溶液混合，测定其荧光光谱，找出主体能够识别的客体。对于主体能够识别的客体，用不同的浓度的客体对主体进行滴定，测定其荧光光谱。芳香族化合物溶液的浓度范围为0-50.0 × 10-5 mol/L。主体溶液的激发波长为253nm，发射光谱在375-530nm有发射峰。每次添加后，8-10分钟达到反应平衡测定相应的荧光强度。本发明作为主体的环状氮杂环卡宾银配合物（特别是晶体）对芳香族化合物的荧光感光效果明显，在荧光光谱中的380-500nm 有明显的荧光吸收（图2），可以用来制作荧光探针，有望在荧光化学领域得到应用。
本发明提出的环状氮杂环卡宾金属配合物晶体是一种在标准状态下可以稳定存在的高级荧光材料，具有荧光感光效果明显的优点，可以用来制作荧光分子识别体系，有望在荧光化学领域得到应用。
附图说明：
图1为含银配合物（实施例1）的晶体结构图；
图2为含银配合物（实施例1）在25℃下，乙腈溶液中加入不同类型的芳香族化合物溶液的荧光光谱图；
图3为含银配合物晶体（实施例1）在25℃下，乙腈溶液中加入不同浓度的邻二硝基苯的荧光滴定光谱图。
具体实施方式
以下结合较佳实施例，对本发明做进一步的描述，特别加以说明的是，制备本发明化合物的起始物质1,4-二[1-(9’-蒽甲基)-3-咪唑]正丁烷六氟磷酸盐可以容易地通过已知的方法制得。制备本发明化合物所用到的试剂全部来源于天津市科威化工有限公司，级别为分析纯。
另外需要加以说明的是：所有的实验操作运用Schlenk技术，溶剂经过标准流程纯化。所有用于合成和分析的试剂都是分析纯，并没有经过进一步的处理。熔点通过Boetius区截机测定。1H 和 13C{1H}NRM谱通过汞变量Vx400分光光度计记录，测量区间：400 MHzand 100 MHz。化学位移，δ，参考国际标准的TMS测定。荧光光谱通过Cary Eclipse荧光分光光度计测定。
实施例1
环状氮杂环卡宾银配合物晶体的制备：
将氧化银(0.059 g, 0.3 mmol)加入到1,4-二[1-(9’-蒽甲基)-3-咪唑]正丁烷六氟磷酸盐 (0.200 g, 0.2 mmol)的二氯甲烷溶液(30 mL)中，在40℃的条件下搅拌24小时，反应完全后将溶液进行抽滤，然后浓缩到5 mL然后加入乙醚出现黄色粉末沉淀，通过抽滤得到环状氮杂环卡宾银配合物。产率: 0.142 g (38%). 熔点: 262-264 ˚C 1H NMR (400MHz, DMSO-d 6): δ 0.90 (s, 8H, CH 2), 3.08 (s, 8H, CH 2), 5.93 (s, 8H, CH 2), 7.32(m, J = 7.2 Hz, 20H, ArH), 7.52 (s, 4H, ArH), 8.00 (d, J = 8.1 Hz, 8H, ArH),8.11 (d, J = 8.5 Hz, 8H, ArH), 8.65 (s, 4H, ArH). 13C NMR (100 MHz, DMSO-d 6 ):δ 27.0 (CH2), 30.3 (CH2), 35.3 (CH2), 45.4 (CH2), 50.2 (CH2), 120.2 (ArC),122.2 (ArC), 123.0 (ArC), 124.7 (ArC), 126.0 (ArC), 126.5 (ArC), 128.4 (ArC),128.5 (ArC), 129.5 (ArC), 130.5 (ArC), 161.9 (2-imiC).
晶体结构见说明书附图1：
实施例1银配合物的晶体结构参数
晶体数据和结构精修参数包含在支持性信息中。在Bruker APEX II CCD衍射仪上进行，实验温度为296(2)K, 在50kV 和20mA下，用Mo-Kα 辐射(0.71073Å)操作，用SMART和SAINT软件进行数据收集和还原，θ的范围是 1.8 < θ< 25º。应用SADABS 程序进行经验吸收矫正。晶体结构由直接方法解出，用SHELXTL包对全部非氢原子坐标各向异性热参数进行全矩阵最小二乘法修正。
应用实例1
在25℃下，在环状氮杂环卡宾金属配合物晶体的乙腈溶液中加入不同种类的芳香族化合物的溶液（甲苯，氯苯，苯胺，苯酚，硝基苯，苯甲醚，苯甲醛，苯乙酮或邻二硝基苯），测定其荧光光谱。
荧光滴定通过Cary Eclipse荧光分光光度计用1cm路径长的石英槽测定的。在滴定中使用的乙腈是用氢化钙脱水得到的除水乙腈。滴定的进行是将受体放入4 mL的比色皿中，并用微量注射器加入浓度逐渐增大的邻二硝基苯溶液(0-50.0 × 10-5 mol/L)（优选的浓度是20.0 × 10-5 mol/L）。主体溶液的激发波长为253 nm，发射光谱在375-530 nm有发射峰。每次添加后，8-10分钟达到反应平衡测定荧光强度。数据分析使用Origin 8.0。见附图3。
结论：
（1）作为主体的环状氮杂环卡宾银配合物在荧光光谱中的380-500 nm 处有明显的荧光吸收。
（2）在主体的溶液中加入不同的芳香族化合物（例如甲苯，氯苯，苯胺，苯酚，硝基苯，苯甲醚，苯甲醛，苯乙酮或邻二硝基苯）后，主体对邻二硝基苯具有良好的选择性，这表明该主体化合物通过荧光方法能够将邻二硝基苯与其它所述的芳香族化合物区分开来。
综上所述，本发明的内容并不局限在实例中，相同领域内的有识之士可以在本发明的技术指导思想之内可以轻易提出其他的实例，但这种实例都包括在本发明的范围之内。
Claims (1)
1.环状氮杂环卡宾金属配合物晶体在用于将邻二硝基苯与其它芳香族化合物加以区分方面的应用；其晶体结构参数如下：
所述的其它芳香族化合物指的是：甲苯，氯苯，苯胺，苯酚，硝基苯，苯甲醚，苯甲醛或苯乙酮；环状氮杂环卡宾金属配合物晶体的结构式如下：
。
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