CN114805185B - 一种同质多晶材料及其制备方法和应用 - Google Patents

一种同质多晶材料及其制备方法和应用 Download PDF

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CN114805185B
CN114805185B CN202210505699.1A CN202210505699A CN114805185B CN 114805185 B CN114805185 B CN 114805185B CN 202210505699 A CN202210505699 A CN 202210505699A CN 114805185 B CN114805185 B CN 114805185B
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刘�东
李妮娅
姚涵
章赵薇
刘波
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Huaiyin Normal University
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    • C07D213/00Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
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Abstract

本发明公开了一种同质多晶材料及其制备方法和应用,其中同质多晶材料为[(1,2‑二(3‑吡啶基)‑乙烯)(5‑甲基‑1,3‑苯二甲酸根)镉]n,该化合物有两种晶型结构,分别为α型和β型。α型和β型是同质多晶体。α型配合物在高温的条件下可以完全转化为β型。由于α型和β型配合物中有机配体1,2‑二(3‑吡啶基)‑乙烯的空间取向和位阻不同,从而导致α型和β型配合物发生[2+2]光环加成反应时,生成的1,2,3,4‑四(3‑吡啶基)环丁烷是两种空间异构体。该种同质多晶材料的制备方法简单,反应条件温和,收率高。

Description

一种同质多晶材料及其制备方法和应用
技术领域
本发明属于无机-有机杂化材料技术领域,确切地说是一种同质多晶材料及其制备方法和应用。
背景技术
随着时代的进步,自然科学技术的飞速发展,新材料的开发和应用成为科学研究和工业化生产面临的重大问题,并有着极其重要的意义。近年来,配位聚合物和金属有机框架材料获得了迅猛的发展。配位聚合物是由金属盐和相应有机配体在适当反应条件下进行组装而构筑成的具有有序结构的晶态无机-有机杂化化合物。配位聚合物材料在光、电、磁、能源、环境、催化、吸附与分离等众多领域具有广泛的应用价值,因此这类具有特殊结构和功能的晶态物质备受科学家们的关注。通过金属离子与有机配体自组装可以形成拓扑结构多样的配位聚合物。配位聚合物具有合成方式简单、结构丰富多样和稳定性高等诸多优点。通过配位键使烯烃配体中的C=C双键固定,并控制它们之间的距离,因此配位聚合物可以作为研究[2+2] 环加成光反应的载体。
近几年来,随着结构表征技术的发展,国内外学者对配位聚合物中进行固相[2+2]环加成反应合成及其应用研究取得了一些令人振奋的成果,但总体来说,人们对该领域的研究成果仍然较少,设计该类反应的难度依然较大。固相[2+2]环加成反应仍然受到配位聚合物或金属有机框架的约束,而且已报道化合物的性能仍有很大的提升空间。这些不足说明,大量新反应及基于该类反应设计的新材料有待开发。因此,本发明致力于制备同质多晶体材料,并基于同质多晶材料研究区位专一的固相[2+2]环加成反应。
发明内容
本发明提供了一种同质多晶材料及其制备方法和应用。本发明同质多晶材料有两种晶型结构分别为α型和β型。α型配合物在高温条件下可以完全转化为β型。由于α型和β型配合物空间结构和位阻不同,从而导致α型和β型配合物发生[2+2]光环加成反应时,生成的[(1,2,3,4-四 (3-吡啶基)环丁烷)0.5(5-甲基-1,3-苯二甲酸根)镉]n是两种空间异构体。本发明同质多晶材料,合成步骤简单,反应条件温和,产率高。
本发明同质多晶材料,为[(1,2-二(3-吡啶基)-乙烯)(5-甲基-1,3-苯二甲酸根)镉]n,n为重复单元数,是任意正整数。该配合物有两种晶型结构,分别为α型和β型,它们互为同质多晶体。
所述α型晶体属于单斜晶系,空间群为C2/c,晶胞参数为 α=90°,β=135.806(16)°,γ=90°;
所述β型晶体属于单斜晶系,空间群为P21/c,晶胞参数为 α=90°,β=131.099(18)°,γ=90°。
本发明同质多晶材料的制备方法,包括如下步骤:
步骤1:α型配合物的合成
将1,2-二(3-吡啶基)-乙烯、5-甲基-1,3-苯二甲酸、四水合硝酸镉和去离子水置于反应釜中,恒温反应,反应结束后缓慢冷却至室温,过滤、洗涤、收集晶态化合物,可得α型配合物;
进一步的,所述1,2-二(3-吡啶基)-乙烯、5-甲基-1,3-苯二甲酸、四水合硝酸镉的摩尔比为 1~2:1~2:1~2,优选为1:1:1;
进一步的,所述反应温度为162-176℃,反应时间为36-48小时;优选的,反应温度172℃,反应时间40小时。
步骤2:β型配合物的合成
将α型配合物晶体置于高温下加热反应,α型配合物即可完全转化成β型配合物。
进一步的,所述反应温度为280-300℃,反应时间为30-40分钟;优选的,反应温度为 300℃,反应时间为30分钟。
本发明中,所述α型配合物中相邻的两个1,2-二(3-吡啶基)-乙烯分子,采用“交叉式”的排列方式,两个双键间的距离为其结构如下式:
本发明中,β型配合物中相邻的两个1,2-二(3-吡啶基)-乙烯分子,采用“平行式”的排列方式,两个双键间的距离为其结构如下式:
本发明中,α型和β型配合物的应用在于,在365nm紫外光的催化下,α型和β型配合物发生[2+2]环加成反应时,分别生成配合物[(rtct-1,2,3,4-四(3-吡啶基)环丁烷)0.5(5-甲基-1,3-苯二甲酸根)镉]n和配合物[(rctt-1,2,3,4-四(3-吡啶基)环丁烷)0.5(5-甲基-1,3-苯二甲酸根)镉]n。在这两种配合物中,1,2,3,4-四(3-吡啶基)环丁烷别为rtct型和rctt型,rtct型和rctt型1,2,3,4-四(3-吡啶基)环丁烷互为空间异构体。
[(rtct-1,2,3,4-四(3-吡啶基)环丁烷)0.5(5-甲基-1,3-苯二甲酸根)镉]n的晶体属于三斜晶系,空间群为Pī,α=96.32(3)°,β=97.06(3)°,γ= 92.51(3)°。
[(rctt-1,2,3,4-四(3-吡啶基)环丁烷)0.5(5-甲基-1,3-苯二甲酸根)镉]n的晶体属于三斜晶系,空间群为Pī,α=91.90(3)°,β=91.40(3)°,γ= 93.39(3)°。
其反应过程如下:
本发明生成的两种1,2,3,4-四(3-吡啶基)环丁烷中,rtct型中环丁烷基的四个碳原子不在同一平面上,而rctt型中环丁烷基的四个碳原子在同一平面上。
本发明制备方法工艺简单、反应条件温和,收率高。
附图说明
图1为α型配合物的晶体结构图。
图2为α型配合物中相邻的两个1,2-二(3-吡啶基)-乙烯分子的结构图,双键间的距离(紫色虚线表示)为
图3为α型配合物的拓扑结构图。
图4为β型配合物的晶体结构图。
图5为β型配合物中相邻两个1,2-二(3-吡啶基)-乙烯分子的结构图,双键间的距离(紫色虚线表示)为
图6为β型配合物的拓扑结构图。
图7为α型配合物发生[2+2]环加成反应后,生成的配合物的晶体结构图。
图8为α型配合物发生[2+2]环加成反应后,rtct-1,2,3,4-四(3-吡啶基)环丁烷的结构图。
图9为β型配合物发生[2+2]环加成反应后,生成的配合物的晶体结构图。
图10为β型配合物发生[2+2]环加成反应后,rctt-1,2,3,4-四(3-吡啶基)环丁烷的结构图。
具体实施方式
非限定实施例叙述如下:
1、α型配合物的制备
将1,2-二(3-吡啶基)-乙烯0.91g(5mmol),5-甲基-1,3-苯二甲酸0.90g(5mmol),四水合硝酸镉1.54g(5mmol)和去离子水(20mL)加入到40mL反应釜中,将反应釜密封并置于172℃恒温反应40小时,反应结束后缓慢冷却至室温,得到无色晶体,过滤、洗涤、收集晶态化合物,室温下晾干,可得α型配合物,产量:1.65g,产率:70%。其晶体学参数如下:
α型配合物的晶体学参数:C21H16N2O4Cd,Mr=472.77,monoclinic,space groupC2/c, α=90°,β=135.806(16)°,γ=90°,Z =8,Dc=1.545g cm-3,μ=1.102mm-1,37760reflections measured,4678unique reflections(Rint=0.0227),4261observed reflections(I>2σ(I)),254parameters,R1=0.0295,wR2=0.0722,S= 1.541。
α型配合物的X-射线单晶结构图见图1。
α型配合物中相邻的两个1,2-二(3-吡啶基)-乙烯分子的结构图,双键间的距离(紫色的虚线表示)为见图2。
α型配合物的拓扑结构图见图3。
2、β型配合物的制备
将α型配合物0.47g(1mmol)晶体置于300℃真空干燥箱内恒温加热反应30分钟,即可得β型配合物0.47g,收率为100%。其晶体学参数如下:
β型配合物的晶体学参数:C21H16N2O4Cd,Mr=472.77,monoclinic,space groupP21//c, α=90°,β=131.099(18)°,γ=90°,/> Z=4,Dc=1.570g cm-3,μ=1.120mm-1,31083reflectionsmeasured,3707unique reflections (Rint=0.0233),3433observed reflections(I>2σ(I)),254parameters,R1=0.0237,wR2=0.0496,S= 1.176。
β型配合物的X-射线单晶结构图见图4。
β型配合物中相邻两个1,2-二(3-吡啶基)-乙烯分子的结构图,双键间的距离(紫色的虚线表示)为见图5。
β型配合物的拓扑结构图见图6。
3、[(rtct-1,2,3,4-四(3-吡啶基)环丁烷)0.5(5-甲基-1,3-苯二甲酸根)镉]n配合物的制备
将α型配合物0.47g(1mmol)晶体置于发光波长为365nm的LED紫外灯(20W)下5cm距离处光照30分钟,即可得[(rtct-1,2,3,4-四(3-吡啶基)环丁烷)0.5(5-甲基-1,3-苯二甲酸根)镉]n配合物0.47g,收率为100%。
[(rtct-1,2,3,4-四(3-吡啶基)环丁烷)0.5(5-甲基-1,3-苯二甲酸根)镉]n配合物的晶体学参数: C42H32N4O8Cd2,Mr=945.54,triclinic,space group Pī, α=96.32(3)°,β=97.06(3)°,γ=92.51(3)°,/>Z=2,Dc=1.522g cm-3,μ=1.086mm-1,26097reflectionsmeasured,7277unique reflections(Rint=0.0343),5072observed reflections(I>2σ(I)),495parameters,R1=0.0743,wR2=0.2120,S=1.041。
[(rtct-1,2,3,4-四(3-吡啶基)环丁烷)0.5(5-甲基-1,3-苯二甲酸根)镉]n配合物的晶体结构图见图7。
(rtct-1,2,3,4-四(3-吡啶基)环丁烷的晶体结构图见图8。
4、[(rctt-1,2,3,4-四(3-吡啶基)环丁烷)0.5(5-甲基-1,3-苯二甲酸根)镉]n配合物的制备
将β型配合物0.47g(1mmol)晶体置于发光波长为365nm的LED紫外灯(20W)下5cm距离处光照30分钟,即可得[(rctt-1,2,3,4-四(3-吡啶基)环丁烷)0.5(5-甲基-1,3-苯二甲酸根)镉]n配合物0.47g,收率为100%。
[(rctt-1,2,3,4-四(3-吡啶基)环丁烷)0.5(5-甲基-1,3-苯二甲酸根)镉]n配合物的晶体学参数: C42H32N4O8Cd2,Mr=945.54,triclinic,space group Pī, α=91.90(3)°,β=91.40(3)°,γ=93.39(3)°,/>Z=2,Dc=1.557g cm-3, μ=1.111mm-1,18853reflectionsmeasured,6781unique reflections(Rint=0.0440),5407observed reflections(I>2σ(I)),460parameters,R1=0.1339,wR2=0.3020,S=1.171。
[(rctt-1,2,3,4-四(3-吡啶基)环丁烷)0.5(5-甲基-1,3-苯二甲酸根)镉]n配合物的晶体结构图见图 9。
rctt-1,2,3,4-四(3-吡啶基)环丁烷的晶体结构图见图10。

Claims (5)

1.一种同质多晶材料,其特征在于:
所述同质多晶材料为[(1,2-二(3-吡啶基)-乙烯)(5-甲基-1,3-苯二甲酸根)镉] n ,n为重复单元数,是任意正整数;
所述同质多晶材料有两种晶型结构,分别为α型和β型,它们互为同质多晶体;
所述α型晶体属于单斜晶系,空间群为C2/c,晶胞参数为a = 16.063(3)Å,b =17.284(3) Å,c =21.004(7)Å,α= 90˚,β =135.806(16)˚,γ = 90˚;
所述β型晶体属于单斜晶系,空间群为P21/c,晶胞参数为a = 11.544(2) Å,b = 14.241(3)Å,c = 16.144(5)Å,α= 90˚,β = 131.099(18)˚,γ = 90˚。
2.一种权利要求1所述的同质多晶材料的制备方法,其特征在于包括如下步骤:
步骤1:α型配合物的合成
将1,2-二(3-吡啶基)-乙烯、5-甲基-1,3-苯二甲酸、四水合硝酸镉和去离子水置于反应釜中,恒温反应,反应结束后缓慢冷却至室温,过滤、洗涤、收集晶态化合物,可得α型配合物;
步骤2:β型配合物的合成
α型配合物晶体置于高温下加热反应,α型配合物即可完全转化成β型配合物;
步骤1中,反应温度为162-176℃,反应时间为36-48小时;
步骤2中,反应温度为280-300℃,反应时间为30-40分钟。
3.根据权利要求2所述的制备方法,其特征在于:
步骤1中, 1,2-二(3-吡啶基)-乙烯、5-甲基-1,3-苯二甲酸、四水合硝酸镉的摩尔比为1~2:1~2:1~2。
4.一种权利要求1所述的同质多晶材料的应用,其特征在于:
α型同质多晶材料在365nm紫外光的催化下,发生[2+2]环加成反应,生成的配合物为[(rtct-1,2,3,4-四(3-吡啶基)环丁烷)0.5(5-甲基-1,3-苯二甲酸根)镉] n ,n为重复单元数,是任意正整数;
所述[(rtct-1,2,3,4-四(3-吡啶基)环丁烷)0.5(5-甲基-1,3-苯二甲酸根)镉] n 配合物的晶体属于三斜晶系,空间群为Pī,晶胞参数为a = 11.628(2)Å,b =12.037(2) Å,c =14.971(3) Å,α= 96.32(3)˚,β =97.06(3)˚,γ = 92.51(3)˚。
5.一种权利要求1所述的同质多晶材料的应用,其特征在于:
β型同质多晶材料在365nm紫外光的催化下,发生[2+2]环加成反应,生成的配合物为[(rctt-1,2,3,4-四(3-吡啶基)环丁烷)0.5(5-甲基-1,3-苯二甲酸根)镉] n ,n为重复单元数,是任意正整数;
所述[(rctt-1,2,3,4-四(3-吡啶基)环丁烷)0.5(5-甲基-1,3-苯二甲酸根)镉] n 配合物的晶体属于三斜晶系,空间群为Pī,晶胞参数为a = 11.248(2)Å,b =12.641(3) Å,c =14.222(3)Å,α= 91.90(3)˚,β =91.40(3)˚,γ = 93.39(3)˚。
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