CN106749349A - 基于混合n,o‑配体的过渡金属配合物的制备方法、晶体结构及其应用 - Google Patents
基于混合n,o‑配体的过渡金属配合物的制备方法、晶体结构及其应用 Download PDFInfo
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- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 4
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- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 3
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- YNPNZTXNASCQKK-UHFFFAOYSA-N Phenanthrene Natural products C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 1
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- SIOXPEMLGUPBBT-UHFFFAOYSA-N picolinic acid Chemical class OC(=O)C1=CC=CC=N1 SIOXPEMLGUPBBT-UHFFFAOYSA-N 0.000 description 1
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- C07F3/06—Zinc compounds
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
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Abstract
本发明涉及一种基于混合N,O‑配体的过渡金属配合物的制备方法、晶体结构及其应用。过渡金属配合物的分子式为[M(2‑NCP)(3‑pyc)]n。制备方法是将二价过渡金属盐、2‑HNCP和3‑Hpyc以物质的量的比为1:0.5～1.5:0.5～1.5进行混合,然后加入一定量的水搅拌一段时间后，用NaOH溶液调解pH在5～8之间,然后将混合溶液转移到内衬为聚四氟乙烯的反应釜中，在140～180℃范围内反应一段时间后，逐渐冷却至室温，用水洗涤产物后室温晾干得到块状晶体即为本发明所述的过渡金属配合物。本发明配合物应用于发光材料、磁性材料、催化合成，选择性吸附、分离H2、N2、CO2、CH4、O2等气体，以及选择性吸附、分离、光催化降解有机染料和酚类内分泌干扰物。
Description
技术领域
本发明属于配合物科学与技术领域，特别涉及一种基于2-(2-羧基苯基)咪唑并(4,5-f)(1,10)邻菲罗啉和吡啶-3-羧酸为混合N,O-配体的过渡金属配合物、制备方法、晶体结构及其应用。
背景技术
配合物多样性的结构和独特的功能特性，在光、电、磁、选择性催化、气体吸附与分离、气体储存等方面都有突出表现(G.Lu,J.T.Hupp，J.Am.Chem.Soc.2010,132,7832；Y.C.Pan,Z.P.Lai,Chem.Commun.2011,47,10275；H.Wang,W.T.Yang,Z.M.Sun,Chemistry2013,8,982；M.H.Zeng,Z.Yin,Y.X.Tan,W.X.Zhang,Y.P.He,M.Kurmoo,J.Am.Chem.Soc.2014,136,4680；R.Tania,V.D.Marion,G.P.Elena,S.C.Pablo,Z.Beatriz,K.Freek,G.Jorge,Adv.Funct.Mater.2014,24,249；N,L.Torad,M.Hu,S.Ishihara,H.Sukegawa,A.A.Belik,M.Imura,K.Ariga,Y.Sakka,Y.Yamauchi,Small 2014,10,2096)，因此受到科研工作者的广泛关注。
配合物的结构决定了配合物的性能，因此可通过调节有机配体的结构进而调控最终配合物功能材料的性能。近年来，含有N,O-配位原子的多功能配体在构筑过渡金属配合物方面得到了广泛的应用，这些含N,O-配位原子的配体包括烟酸(H.Sadeghzadeha,A.Morsali,CrystEngComm.2010,12,370)，异烟酸(H.Sadeghzadeh,A.Morsali,P.Retailleau,Polyhedron 2010,29,925)，4-(4-吡啶基)苯甲酸(M.H.Zeng,Z.Yin,Y.X.Tan,W.X.Zhang,Y.P.He,M.Kurmoo,J.Am.Chem.Soc.2014,136,4680)，吡啶-2-羧酸(A.Aslani,A.Morsali,M.Zeller,Solid State Sci.2008,10,1591)等。2-(2-羧基苯基)咪唑并(4,5-f)(1,10)邻菲罗啉(缩写为2-HNCP)作为该类配体中一个重要的多功能配体，因其含有可螯合配位的邻菲罗啉环上的两个N原子，既可螯合也可桥联配位的羧基氧原子，以及具有较大的共轭体系，是构建过渡金属配合物很好的配体。而将2-HNCP和另外一个含N,O-配位原子的多功能配体吡啶-3-羧酸(缩写为3-Hpyc)共同引入到过渡金属配合物中还未见报道。
发明内容
本发明要解决的技术问题是提供一种基于混合N,O-配体的过渡金属配合物的制备方法、晶体结构及其应用。过渡金属配合物具有三维超分子网络结构，表现出较好的光学、磁学、催化等性质，该合成方法具有重复性强、产率高、产品性能稳定的优点。
本发明的技术方案是：
基于混合N,O-配体的过渡金属配合物，分子式为[M(2-NCP)(3-pyc)]n，化学式为C26H15N5O4M，其中M为二价过渡金属离子，即：Mn2+、Fe2+、Co2+、Ni2+、Cu2+、Zn2+、Cd2+。2-NCP-、3-pyc-分别为去质子化的2-HNCP和3-Hpyc的阴离子配体。
本发明的有益效果是：
1.本发明过渡金属配合物具有三维超分子网络结构，表现出较好的光学、磁学、催化等性质，主要应用在发光材料、磁性材料、催化合成，选择性吸附、分离H2、N2、CO2、CH4、O2等气体，以及选择性吸附、分离、光催化降解有机染料和酚类内分泌干扰物。
2.本发明的合成方法具有重复性强、产率高、产品性能稳定等特点。
附图说明
图1是过渡金属Zn配合物的配位环境图。
图2是过渡金属Zn配合物的一维链状结构图。
图3是过渡金属Zn配合物通过π-π相互作用将配合物的一维链连接成为二维层状结构图。
图4是过渡金属Zn配合物通过π-π相互作用将配合物的二维层状结构连接成为三维超分子网络结构图。
图5是过渡金属Zn配合物的光致发光光谱。
具体实施方式
本发明所述过渡金属配合物可广泛应用在发光材料、磁性材料、催化合成，选择性吸附、分离H2、N2、CO2、CH4、O2等气体，以及选择性吸附、分离、光催化降解有机染料和酚类内分泌干扰物。
该系列过渡金属配合物的分子式为[M(2-NCP)(3-pyc)]n，化学式为C26H15N5O4M，其中M为二价过渡金属离子，即：Mn2+、Fe2+、Co2+、Ni2+、Cu2+、Zn2+、Cd2+中的一种。2-NCP-、3-pyc-分别为去质子化的2-HNCP和3-Hpyc的阴离子配体。
该系列过渡金属配合物的晶体结构是：所述配合物的晶体属于三斜晶系，空间群为P-1。在配合物的非对称单元里包含一个二价过渡金属离子M2+、一个2-NCP-配体和一个3-pyc-配体。中心金属离子M2+处于五配位的四方锥的配位环境中，M2+分别和来自于2-NCP-和3-pyc-配体中羧基上的2个O原子、另外一个2-NCP-配体上的2个N原子、以及另外一个3-pyc-配体上的1个N原子配位。每一个2-NCP-和3-pyc-配体分别和两个过渡金属离子M2+配位形成了一维双链结构。相邻的一维链通过3-pyc-配体之间的π···π相互作用形成了二维层状结构。相邻的二维层进一步通过2-NCP-配体上的吡啶环和苯环之间π···π相互作用最终形成了三维超分子网络结构。
该系列过渡金属配合物的制备方法是：将二价过渡金属盐(硝酸盐、盐酸盐、硫酸盐、醋酸盐)、2-HNCP和3-Hpyc以物质的量的比为1:0.5～1.5:0.5～1.5进行混合,然后加入一定量的水(水量没有限制)搅拌一段时间后，用NaOH溶液调解pH在5～8之间，然后将混合溶液转移到内衬为聚四氟乙烯的反应釜中，在140～180℃范围内反应一段时间后，逐渐冷却至室温，用水洗涤产物后室温晾干得到块状晶体即为本发明所述的过渡金属配合物。
实施例1：
本发明所述的化学式为C26H15N5O4Zn的配合物[Zn(2-NCP)(3-pyc)]n的制备方法如下：
向Zn(NO3)3·6H2O(0.0296g,0.1mmol)、2-HNCP(0.0170g,0.05mmol)和3-Hpyc(0.0123g,0.1mmol)的混合试剂中,加入去离子水10mL搅拌10min，用1mol/L NaOH溶液调至pH＝6.5，放在25mL聚四氟乙烯反应釜中，加热到170℃反应3天，逐渐冷却至室温，用去离子水洗涤室温晾干得到黄色块状晶体，即为过渡金属Zn配合物，产率为56％(基于金属Zn盐)。元素分析为：(理论值)：C 59.27，H 2.87，N 13.29；(实验值)：C 59.22，H 2.99，N 13.25。
配合物的相关表征
(1)过渡金属Zn配合物的晶体结构测定
配合物的衍射数据是在293K条件下Bruker SMART APEX II CCD衍射仪上收集，Mo-Kα射线使用技术扫描进行校正。晶体结构是通过SHELEXL-97程序以直接法解出，用全矩阵最小二乘法使用SHELEXL-97进行精修。非氢原子的温度因子用各向异性进行修正。详细的晶体测定数据见表1；重要的键长和键角数据见表2；晶体结构见图1-图4。
发明的过渡金属Zn配合物其特征在于所述配合物晶体属于三斜晶系，空间群为P-1，晶胞参数为α＝92.1600(10)°，β＝104.2720(10)°，γ＝103.0910(10)°，
配合物的配位环境如图1所示，在配合物的非对称单元里包含一个Zn2+金属离子、一个2-NCP-配体和一个3-pyc-配体。Zn2+处于五配位的四方锥的配位环境中，分别和来自于2-NCP-和3-pyc-配体中羧基上的2个O原子、另外一个2-NCP-配体上的2个N原子、以及另外一个3-pyc-配体上的1个N原子配位。每一个2-NCP-和3-pyc-配体分别和两个Zn2+配位形成了一维双链结构(图2)。相邻的一维链通过3-pyc-配体之间的π···π相互作用形成了二维层状结构(图3)。相邻的二维层进一步通过2-NCP-配体上的吡啶环和苯环之间π···π相互作用最终形成了三维超分子网络结构(图4)。
(2)配合物的光致发光性质研究(Perkin-Elmer LS55荧光光谱仪)
配合物在260nm激发波长下激发，得到了最大发射峰位在493nm的发射光谱，见图5(Perkin-Elmer LS55荧光光谱仪)。
实施例2：
本发明所述的化学式为C26H15N5O4Cu的配合物[Cu(2-NCP)(3-pyc)]n的制备方法如下：
向CuCl2·2H2O(0.0170g,0.1mmol)、2-HNCP(0.0340g,0.1mmol)和3-Hpyc(0.0123g,0.1mmol)的混合试剂中,加入去离子水12mL搅拌8min，用0.5mol/L NaOH溶液调至pH＝7，放在25mL聚四氟乙烯反应釜中，加热到160℃反应3天，逐渐冷却至室温，用去离子水洗涤室温晾干得到绿色块状晶体，即为过渡金属Cu配合物，产率为48％(基于金属Cu盐)。元素分析为：(理论值)：C,59.48；H,2.88；N,13.34。(实验值)：C,59.40；H,2.91；N,13.30。
过渡金属Cu配合物的晶体结构测定同过渡金属Zn配合物。详细的晶体学数据见表1；重要的键长和键角数据见表2；晶体结构与过渡金属Zn配合物相似。
发明的过渡金属Cu配合物其特征在于所述配合物晶体属于三斜晶系，空间群为P-1，晶胞参数为α＝91.639(2)°，β＝104.505(2)°，γ＝102.580(2)°，
表1：两种代表性配合物的主要晶体学数据
表2：配合物的主要键长和键角[°]*
*对称代码:过渡金属Zn配合物1：#1-x+2,-y+1,-z+2；#2-x+2,-y+1,-z+1；
过渡金属Cu配合物2：#1-x+1,-y,-z+1；#2-x+1,-y,-z+2。
Claims (5)
1.基于混合N,O-配体的过渡金属配合物，其特征在于：分子式为[M(2-NCP)(3-pyc)]n，化学式为C26H15N5O4M，其中M为二价过渡金属离子，即：Mn2+、Fe2+、Co2+、Ni2+、Cu2+、Zn2+、Cd2+,2-NCP-、3-pyc-分别为去质子化的2-HNCP和3-Hpyc的阴离子配体。
2.根据权利要求1所述的基于混合N,O-配体的过渡金属配合物，其特征在于：晶体属于三斜晶系，空间群为P-1，在配合物的非对称单元里包含一个二价过渡金属离子M2+、一个2-NCP-配体和一个3-pyc-配体，中心金属离子M2+处于五配位的四方锥的配位环境中，M2+分别和来自于2-NCP-和3-pyc-配体中羧基上的2个O原子、另外一个2-NCP-配体上的2个N原子、以及另外一个3-pyc-配体上的1个N原子配位，每一个2-NCP-和3-pyc-配体分别和两个过渡金属离子M2+配位形成了一维双链结构，相邻的一维链通过3-pyc-配体之间的π…π相互作用形成了二维层状结构，相邻的二维层进一步通过2-NCP-配体上的吡啶环和苯环之间π…π相互作用最终形成了三维超分子网络结构。
3.根据权利要求1所述的基于混合N,O-配体的过渡金属配合物的制备方法，其特征在于：将二价过渡金属盐、2-HNCP和3-Hpyc以物质的量的比为1:0.5～1.5:0.5～1.5进行混合,然后加入一定量的水搅拌一段时间后，用NaOH溶液调解pH在5～8之间,然后将混合溶液转移到内衬为聚四氟乙烯的反应釜中，在140～180℃范围内反应一段时间后，逐渐冷却至室温，用水洗涤产物后室温晾干得到块状晶体即为本发明所述的过渡金属配合物。
4.根据权利要求3所述的基于混合N,O-配体的过渡金属配合物的制备方法，所述的二价过渡金属盐为Mn2+、Fe2+、Co2+、Ni2+、Cu2+、Zn2+、Cd2+的硝酸盐或盐酸盐或硫酸盐或醋酸盐。
5.根据权利要求1所述的基于混合N,O-配体的过渡金属配合物，可应用在发光材料、磁性材料、催化合成，选择性吸附、分离H2、N2、CO2、CH4、O2等气体，以及选择性吸附、分离、光催化降解有机染料和酚类内分泌干扰物。
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