CN111154111A - 一种基于锌(ⅱ)的五核金属有机配合物及其制备方法 - Google Patents
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Abstract
本发明提供一种基于锌(Ⅱ)的五核金属配位聚合物,所述的基于锌(Ⅱ)的五核金属配位聚合物具有化学式为[Zn5(oba)4(dmbpy)(OH)2]n的重复单元,其中,oba为4,4'‑二苯醚二甲酸,dmbpy为3,3’‑二甲基‑4,4’‑联吡啶,所述的锌(Ⅱ)金属有机配合物具有三维二重穿插微孔结构。本发明所述的锌(Ⅱ)金属配位聚合物能发射蓝色荧光,可用于荧光材料的制备。
Description
技术领域
本发明涉及金属有机配合物领域,具体涉及一种基于锌(Ⅱ)的五核金属有机配合物及其制备方法。
背景技术
金属有机配合物是一种由金属离子与有机配体在一定条件下通过自组装合成的具有一维、二维或者三维结构的金属有机框架材料。金属有机配合物作为一种新型功能材料,具有孔隙率高、结构可塑、孔径大小均匀等特点。由于独特的多孔结构以及制备方法简便易行等特点,使其在荧光、磁性、吸附和载药等领域具有潜在的应用价值。
含有共扼电子效应的有机配体与含有d10电子构型的Zn2+和Cd2+等金属结合的金属有机配合物都可以发光,并且具有重复结构单元的金属有机配合物往往能够发出较强的荧光。金属有机配合物可通过改变金属配位来影响配合物的发光性能,在制备新型发光材料方面具有重要的应用价值。具有荧光特性的基于4,4'-氧联苯二甲酸和3,3'-二甲基-4,4'-联吡啶含氮有机配体的锌(Ⅱ)金属有机配合物的报道十分少见。
发明内容
针对上述问题,本发明提供一种基于锌(Ⅱ)的五核金属有机配合物及其制备方法。
本发明的目的采用以下技术方案来实现:
一种基于锌(Ⅱ)的五核金属有机配合物,所述金属有机配合物具有化学式为[Zn5(oba)4(dmbpy)(OH)2]n的重复单元,其中,oba为4,4'-氧联苯二甲酸基,dmbpy为3,3'-二甲基-4,4'-联吡啶;所述的金属有机配合物具有三维二重穿插微孔结构,所述金属有机配合物属于正交晶系,P2/n空间群,晶胞参数分别为a=1.09243(9)nm,b=2.7533(2)nm,c=1.19071(10)nm,β=103.105(3)°;
所述金属有机配合物的红外光谱数据(KBr)为:3449(vs),3151(s),1683(m),1605(vs),1559(m),1506(m),1398(vs),1307(m),1262(s),1159(s),1104(w),1080(w),1010(w),873(w),853(w),778(s),692(m),658(m),617(w),501(w),443(w),418(w)cm-1。
所述金属有机配合物中,oba配体存在两种配位方式:一种桥连方式连接四个锌(II)离子,另一种桥连模式连接三个锌(II)离子;羟基氧原子(O6)连接三个锌(II)离子,而dmbpy配体也采用桥连方式连接两个锌(II)离子;基于上述连接方式,八个oba2-阴离子和两个桥连羟基氧配体连接5个锌(II)离子构筑成类似汉堡式的五聚体(Zn5O30N2)二级构筑单元,这些五聚体的二级构筑单通过dmbpy连接成一维链状结构,最后,这些一维链状结构被oba2-阴离子进一步连接成具有sxd拓扑结构的三维二重穿插网络结构;所述锌(Ⅱ)金属有机配合物在常温下为无色单晶,其重复结构单元中含有5个Zn2+阳离子,4个oba2-阴离子,一个dmbpy配体和2个羟基配体;Zn1和Zn2均为四配位的四面体几何构型,其中Zn1由三个不同的oba配体中的三个羧酸氧原子和一个侨联氧原子配位,而Zn2由两个不同的oba配体中的两个羧酸氧原子,一个dmbpy配体上的氮原子和一个桥连氧原子配位;Zn3由五个不同的oba配体上的五个羧酸氧原子和一个桥连氧原子配位形成六配位,为八面体几何构型。
本发明还提供了所述基于锌(Ⅱ)的五核金属有机配合物的制备方法,本发明所提供的制备方法采用本领域常用的水热反应法,将4,4'-氧联苯二甲酸和3,3'-二甲基-4,4'-联吡啶与Zn(NO3)2·6H2O混合后在水热反应条件下得到,具体包括以下步骤:
S1、将H2oba溶解分散在热水中,用NaOH溶液将pH调至7.0~8.0,得到配体溶液;
S2、在配体溶液中加入等摩尔量的Zn(NO3)2·6H2O和dmbpy,混合;然后将混合溶液加入到23mL聚四氟乙烯反应釜中,自生压力下保持130℃反应72h;
S3、将S2得到的产物过滤,收集晶体,并用无水乙醇洗涤后干燥,得到所述的基于锌(Ⅱ)的五核金属配合物。
本发明的有益效果为:
(1)本发明产物原料来源广泛,容易获得;
(2)本发明产物合成方法的反应条件温和,纯度高,无毒无害,做到了绿色化学,无需惰性气体保护;
(3)所述锌(Ⅱ)金属有机配合物表现出良好的荧光特性,能发射明亮的蓝色荧光,可应用于制备荧光材料。
附图说明
利用附图对本发明作进一步说明,但附图中的实施例不构成对本发明的任何限制,对于本领域的普通技术人员,在不付出创造性劳动的前提下,还可以根据以下附图获得其它的附图。
图1为该配合物中Zn2+离子的配位环境图;
图2为oba和dmbpy配体的配位模式图;
图3为汉堡式五聚体(Zn5O30N2)单元图;
图4为本发明所述锌金属有机配合物的一维链状结构图;
图5为配合物的三维网络图;
图6为配合物的二重穿插结构图;
图7为配合物的sxd型拓扑结构图;
图8为配合物的固体荧光谱图。
具体实施方式
结合以下实施例对本发明作进一步描述。
实施例1
一种基于锌(Ⅱ)的五核金属有机配合物,其制备方法包括以下步骤:
(1)制备pH=7-8的热碱水,量取10mL;
(2)称量0.3mmol H2oba(4,4'-氧联苯甲酸)和0.3mmol dmbpy(3,3'-二甲基-4,4'-联吡啶)一同加入上述热碱水溶液中;再称量加入0.3mmol Zn(NO3)2·6H2O;
(3)将混合溶液体系移入23mL聚四氟乙烯反应釜中,在自生压力下保持130℃恒温反应72小时,以5℃·h-1降温到室温;
(4)将产物过滤,收集晶体,干燥,获得无色晶体。
根据H2oba计算得到产率为65%。
实施例1的产物鉴定
鉴定方法包括元素分析、IR光谱和X-射线单晶衍射分析鉴定。
(1)元素分析
C68H46O22N2Zn5;理论值:C,51.98;H,2.93;N,1.78;实验值:C,52.29;H,2.26;N,2.01。
(2)红外光谱(KBrpellet)
光谱数据为3449(vs),3151(s),1683(m),1605(vs),1559(m),1506(m),1398(vs),1307(m),1262(s),1159(s),1104(w),1080(w),1010(w),873(w),853(w),778(s),692(m),658(m),617(w),501(w),443(w),418(w)cm-1。
(3)X-射线单晶衍射
晶体学参数和部分键长如表1和表2所示。X-射线单晶衍射结果表明,上述锌(Ⅱ)金属有机配合物中的重复单元为不对称单元,其重复结构单元中含有5个Zn2+阳离子,4个oba2-阴离子,一个dmbpy配体和2个羟基配体。Zn1和Zn2均为四配位的四面体几何构型,参见图1,其中Zn1由三个不同的oba配体中的三个羧酸氧原子和一个侨联氧原子配位,而Zn2由两个不同的oba配体中的两个羧酸氧原子,一个dmbpy配体上的氮原子和一个桥连氧原子配位;Zn3由五个不同的oba配体上的五个羧酸氧原子和一个桥连氧原子配位形成六配位,为八面体几何构型。
表1.[Zn5(oba)4(dmbpy)(OH)2]n的晶体学参数
R=∑(‖Fo︱-︱Fc‖)/∑︱Fo︱.wR=[∑w(Fo 2–Fc 2)2/∑w(Fo)2]1/2.
表2.[Zn5(oba)4(dmbpy)(OH)2]n的部分键长键角
Zn1-O1 | 1.902(10) | Zn1-O4 | 1.958(10) |
Zn2-O5 | 1.933(9) | Zn2-N2 | 2.047(11) |
Zn2-O6 | 2.001(9) | Zn2-O7 | 1.972(11) |
Zn3-O10 | 2.034(14) | Zn3-O8<sup>i</sup> | 2.08(2) |
O1-Zn1-O9 | 116.7(5) | O1-Zn1-O4 | 99.9(5) |
O9-Zn1-O6 | 112.8(5) | O5-Zn2-O6 | 103.0(4) |
O5-Zn2-O7 | 113.6(5) | O5-Zn2-N1 | 105.2(4) |
O10<sup>i</sup>-Zn3-O10 | 173.4(9) | O8-Zn3-O10 | 102.1(9) |
O6<sup>i</sup>-Zn3-O6 | 91.6(4) | O6-Zn3-O10<sup>i</sup> | 88.4(5) |
Zn1-O1 | 1.902(10) | Zn1-O4 | 1.958(10) |
操作对称代码:1.5-x,y,1.5-z.
通过元素分析、IR光谱和X-射线单晶衍射分析鉴定,实施例1所制得的无色晶体为基于4,4'-氧联苯二甲酸和3,3'-二甲基-4,4'-联吡啶的锌(Ⅱ)金属有机配合物,其重复单元的分子式为[Zn5(oba)4(dmbpy)(OH)2]n。
实施例2
采用实施例1得到的基于4,4'-氧联苯二甲酸和3,3'-二甲基-4,4'-联吡啶的锌(Ⅱ)金属有机配合物进行荧光性能研究:
(1)荧光性能测试:在室温下测量基于4,4'-氧联苯二甲酸和3,3'-二甲基-4,4'-联吡啶的锌(Ⅱ)金属有机配合物在300-600nm范围内的固体荧光光谱。
(2)实验结果
固体荧光光谱结果见图8,本发明所述的基于4,4'-氧联苯二甲酸和3,3'-二甲基-4,4'-联吡啶的锌(Ⅱ)金属有机配合物可发射明亮的蓝色荧光,在365nm激发波长下的最大荧光发射波长为482nm。
最后应当说明的是,以上实施例仅用以说明本发明的技术方案,而非对本发明保护范围的限制,尽管参照较佳实施例对本发明作了详细地说明,本领域的普通技术人员应当理解,可以对本发明的技术方案进行修改或者等同替换,而不脱离本发明技术方案的实质和范围。
Claims (4)
1.一种基于锌(Ⅱ)的五核金属有机配合物,其特征在于,所述金属有机配合物具有化学式为[Zn5(oba)4(dmbpy)(OH)2]n的重复单元,其中,oba为4,4'-氧联苯二甲酸基,dmbpy为3,3'-二甲基-4,4'-联吡啶;所述的金属有机配合物具有三维二重穿插微孔结构,所述金属有机配合物属于正交晶系,P2/n空间群,晶胞参数分别为a=1.09243(9)nm,b=2.7533(2)nm,c=1.19071(10)nm,β=103.105(3)°。
2.根据权利要求1所述的一种基于锌(Ⅱ)的五核金属有机配合物,其特征在于,所述金属有机配合物的红外光谱数据(KBr)为:3449(vs),3151(s),1683(m),1605(vs),1559(m),1506(m),1398(vs),1307(m),1262(s),1159(s),1104(w),1080(w),1010(w),873(w),853(w),778(s),692(m),658(m),617(w),501(w),443(w),418(w)cm-1。
3.根据权利要求1所述的一种基于锌(Ⅱ)的五核金属有机配合物的制备方法,其特征在于,包括以下步骤:
S1、将H2oba溶解分散在热水中,用NaOH溶液将pH调至7.0~8.0,得到配体溶液;
S2、在配体溶液中加入等摩尔量的Zn(NO3)2·6H2O和dmbpy,混合;然后将混合溶液加入到聚四氟乙烯反应釜中,自生压力下保持130℃反应72h;
S3、将S2得到的产物过滤,收集晶体,并用无水乙醇洗涤后干燥,得到所述的基于锌(Ⅱ)的五核金属配位聚合物。
4.根据权利要求1或2所述的一种基于锌(Ⅱ)的五核金属有机配合物作为荧光物质的应用。
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