CN112010909B - 一种钴簇合物及其制备方法 - Google Patents
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- UBHDUFNPQJWPRQ-UHFFFAOYSA-N (5-methyl-1h-imidazol-3-ium-4-yl)methanol;chloride Chemical compound Cl.CC=1NC=NC=1CO UBHDUFNPQJWPRQ-UHFFFAOYSA-N 0.000 claims abstract description 9
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- 238000003756 stirring Methods 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- AXJZCJSXNZZMDU-UHFFFAOYSA-N (5-methyl-1h-imidazol-4-yl)methanol Chemical compound CC=1N=CNC=1CO AXJZCJSXNZZMDU-UHFFFAOYSA-N 0.000 claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
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- -1 4-methyl-5-imidazolyl-methoxy Chemical group 0.000 claims description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 2
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- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/06—Cobalt compounds
- C07F15/065—Cobalt compounds without a metal-carbon linkage
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Abstract
本发明公开了一种钴簇合物及其制备方法,涉及簇合物技术领域。本发明公开的钴簇合物的制备方法包括钴盐溶液、4‑甲基‑5‑咪唑基‑甲醇盐酸盐溶液的制备,两种溶液混合后进行反应,静置2~3周后即可得到所述钴簇合物。本发明公开的方法简单,可一步合成两种新型立方烷型的多核多价态钴簇合物。
Description
技术领域
本发明涉及簇合物技术领域,尤其涉及一种钴簇合物及其制备方法。
背景技术
具有多个顺磁性金属中心的簇合物的合理设计与合成日益受到关注,科学家们对这些簇合物的兴趣不仅仅在于理解结构与化学性能间的关系,还因其作为功能材料在生物医药、磁学和催化领域中潜在应用。
含有钴的簇合物,尤其是立方烷型CoxOy的钴簇物因其在以下几个方面的领域的运用尤其引人关注:用作水氧化的光催化剂;生物无机领域合成的催化剂;构建分子磁体,如磁致冷等。
4-甲基-5-咪唑基-甲醇含有咪唑氮原子和醇羟基,易与金属离子以桥连方式发生配位,从而形成簇合物。通过文献检索,利用4-甲基-5-咪唑基-甲醇来合成多核钴簇合物还未见有报道,本文制备的两个钴簇合物中,钴离子有两种价态,而已报道的钴簇合物中,多数钴离子为+2价,具有混价态的簇合物非常少见,尤其是立方烷型的钴簇物具有+2,+3两种价态的钴簇合物更为少见。并且,通常情况下,多核簇合物的合成往往采用一种至上而下的方法,即先合成一个单核或者低核的配合物,以此为模板,引入其他试剂,继而获得多核或者高核的簇合物,制备工艺较为复杂。
发明内容
本发明的目的在于克服上述现有技术的不足之处而提供一种新型的、合成工艺简单的钴簇合物。
为实现上述目的,本发明所采取的技术方案为:一种钴簇合物,其化学式为[CoIII 2CoII 2(L)6(HL)2](ClO4)3Cl·H2O或[CoII 4CoIII 3(L)12](NO3)4.5Cl0.5·4.5H2O,所述HL为4-甲基-5-咪唑基-甲醇,所述L为HL脱去醇氧质子后的4-甲基-5-咪唑基-甲氧基。
同时,本发明公开了一种所述钴簇合物的制备方法,包括如下步骤:
(1)将钴盐溶解于溶剂A中,得到溶液A;
(2)将4-甲基-5-咪唑基-甲醇盐酸盐溶解在溶剂B中,得到溶液B;
(3)待步骤(1)、(2)完成后,将中和剂加入溶液B中,得到溶液C;
(4)待步骤(3)完成后,将溶液C加入溶液A中,搅拌、过滤,得到深色滤液;
(5)待步骤(4)完成后,将深色滤液于15-35℃下静置2~3周,得到所述钴簇合物。
中和剂不可直接与钴盐混合加入溶剂中,需要缓慢加入,避免与钴形成沉淀物。
本发明通过调控钴盐的阴离子,使不同钴盐与4-甲基-5-咪唑基-甲醇在室温下直接反应,一步法合成了两个核数不同的混价态钴簇合物,简化了合成过程,减少了中间产物。
优选地,所述钴盐为六水合高氯酸钴或六水合硝酸钴;所述溶剂A和溶剂B为甲醇或乙醇。本发明申请人通过实验研究发现,只有钴盐为六水合高氯酸钴和六水合硝酸钴时才可以通过上述方法合成钴簇合物,否则无法合成;并且由六水合高氯酸钴与六水合硝酸钴制备的钴盐的结构也存在天壤之别。
优选地,所述溶剂A与溶剂B的体积比为(18-22):5;所述钴盐在溶剂A中的浓度为0.023-0.027mmol/mL,4-甲基-5-咪唑基-甲醇盐酸盐在溶剂B中的浓度为0.08-0.12mmol/mL;所述步骤(2)中,溶剂B的添加量为5mL时,步骤(3)中,中和剂的添加量为0.8-1.2mmol。
优选地,所述钴盐、4-甲基-5-咪唑基-甲醇盐酸盐和中和剂的摩尔比为1:1:2。本发明申请人通过多次实验验证,以该配比合成所述钴簇合物的产率更高。
优选地,所述中和剂为三乙胺、四甲基氢氧化铵、三乙醇胺、乙醇胺、氢氧化钠、氢氧化钾中的至少一种。
优选地,如权利要求1所述的制备方法,其特征在于,所述步骤(4)中的搅拌时间为0.8-1.2h。
此外,本发明公开了所述钴簇合物在分子基磁材料领域、信息存储、催化领域的应用。
相比于现有技术,本发明的有益效果为:本发明公开了一种新型的钴簇合物及其制备方法,通过对阴离子进行调控,一步合成了两个核数不同的混价态钴簇合物,简化了合成过程,减少了中间产物。
附图说明
图1为HL和L的配位模式图;
图2为实施例1的分子结构图;
图3为实施例2的分子结构图;
图4为实施例2的χMT曲线图;
图5为实施例2在2K时的饱和磁化强度曲线图。
具体实施方式
为更好地说明本发明的目的、技术方案和优点,下面将结合附图和具体实施例对本发明作进一步说明。
实施例1
本发明所述钴簇合物的一种实施例,本实施例所述钴簇合物的制备方法包括如下步骤:
(1)将六水合高氯酸钴(0.183g,0.5mmol)溶解于20mL甲醇中,得到溶液A;
(2)将4-甲基-5-咪唑基-甲醇盐酸盐(0.074g,0.5mmol)溶解在5mL甲醇中,得到溶液B;
(3)将三乙胺(0.101g,1.0mmol)加入溶液B中,然后缓慢加入溶液A中,并搅拌溶液,搅拌1h后过滤,得到深红色滤液;
(4)将深红色滤液于25℃下放置2周,得到深红色块状四核钴簇合物,产率约为48%。
对上述四核钴簇合物进行红外光谱分析,结果为:IR(KBr,cm-1):3405w,3158m,2920m,1624m,1504w,1445w,1385m,1274w,1112s,1087s,1018w,788m,669w,626s,482m。对其进行元素分析,质量百分含量理论值为:C,28.96%;H,4.86%;N,13.51%;实验值为:C,28.81%;H,4.97%;N,13.42%。
对上述四核钴簇合物进行结构表征,分别在123K,293K条件下进行测试,X射线衍射数据是在Brucker Apex CCD面探测仪上,以Mo Kα辐射 以ω扫描方式收集并进行LP因子校正。利用SAINT+程序对数据进行还原,吸收校正用SADAB程序。用直接法解结构,然后用差值傅立叶法求出全部非氢原子坐标,并用理论加氢法得到氢原子位置用最小二乘法对结构进行修正。计算工作在PC机上用SHELXTL程序包完成。详细的晶体学和结构修正数据如表1所示。
实施例2
本发明所述钴簇合物的一种实施例,本实施例所述钴簇合物的制备方法包括如下步骤:
(1)将六水合硝酸钴(0.145g,0.5mmol)溶解于20mL甲醇中,得到溶液A;
(2)将4-甲基-5-咪唑基-甲醇盐酸盐(0.074g,0.5mmol)溶解在5mL甲醇中,得到溶液B;
(3)将三乙胺(0.101g,1.0mmol)加入溶液B中,然后缓慢加入溶液A中,并搅拌溶液,搅拌1h后过滤,得到深棕色滤液;
(4)将深棕色滤液于25℃下放置3周,得到深棕色针状七核钴簇合物,产率约为10%。
对上述七核钴簇合物进行红外光谱分析,结果为:IR(KBr,cm-1):3379m,3200w,3056vw,2911w,1615m,1534w,1445s,1385m,1334m,1283s,1146vw,1112vw,1087m,1027m,908m,848m,737vs,635s,592w,498m,456vw。对其进行元素分析,质量百分含量理论值为:C,42.93%;H,5.64%;N,22.94%;实验值为:C,42.86%;H,5.72%;N,22.86%。
对上述七核钴簇合物进行结构表征,测试方法与实施例1中的测试方法相同,详细的晶体学和结构修正数据如表1所示。
实施例3
本发明所述钴簇合物的一种实施例,本实施例所述钴簇合物的制备方法包括如下步骤:
(1)将六水合高氯酸钴(0.168g,0.46mmol)溶解于20mL甲醇中,得到溶液A;
(2)将4-甲基-5-咪唑基-甲醇盐酸盐(0.059g,0.4mmol)溶解在5mL甲醇中,得到溶液B;
(3)将三乙胺(0.081g,0.8mmol)加入溶液B中,然后缓慢加入溶液A中,并搅拌溶液,搅拌1h后过滤,得到深红色滤液;
(4)将深红色滤液于25℃下放置2周,得到深红色块状四核钴簇合物,产率约为23%。
实施例4
本发明所述钴簇合物的一种实施例,本实施例所述钴簇合物的制备方法包括如下步骤:
(1)将六水合高氯酸钴(0.198g,0.54mmol)溶解于20mL甲醇中,得到溶液A;
(2)将4-甲基-5-咪唑基-甲醇盐酸盐(0.089g,0.6mmol)溶解在5mL甲醇中,得到溶液B;
(3)将三乙胺(0.121g,1.2mmol)加入溶液B中,然后缓慢加入溶液A中,并搅拌溶液,搅拌1h后过滤,得到深红色滤液;
(4)将深红色滤液于25℃下放置2周,得到深红色块状四核钴簇合物,产率约为5%。
表1晶体学参数表
表1中,R1=∑||Fo|-|Fc||/∑|Fo|,wR2=[∑w(Fo 2-Fc 2)2/∑w(Fo 2)2,式中Fo和Fc分别为实验、理论计算所得的结构因子。由表1可知,实施例1制备的钴簇合物属于单斜晶系,P2(1)/n空间群,晶胞参数为: α=90.00°,β=101.209(4)°,γ=90.00°。实施例2制备的钴簇合物属于立方晶系,Pa-3空间群,晶胞参数为: α=90.00°,β=90.00°°,γ=90.00°。
HL在两个簇合物中有两种存在形式,一种是中性的HL,另一种是脱去质子的L。图1为HL、L的配位模式,从图1中可知,HL、L在两个簇合物中有三种配位模式,分别为二齿螯合和三齿螯合。
图2为实施例1的分子结构图,从图2中可知,实施例1由四核钴簇、ClO4 -、Cl-和溶剂水分子组成。钴簇合物由2个CoII离子,2个CoIII离子,6个去质子的L和2个HL组成,钴离子有2价、3价两种价态,这与相应钴离子的键长和配合物的电荷平衡相一致。4个钴离子通过2个μ3-O,4个μ2-O桥连在一起,形成了具有缺陷的Co4O6立方烷构型;2个L配体通过醇氧以μ3方式连接3个钴离子,4个L配体通过醇氧以μ2方式连接2个钴离子,2个HL以二齿螯合形式与钴离子配位。Co1与三个L配位,形成了[CoN3O3]的八面体配位几何构型,Co1离子是﹢3价的,电子是以低自旋态排列,其中Co1-N的键长为Co1-O的键长为与低自旋的Co3+键长相符合。Co2离子为﹢2价,Co2与4个L、1个HL配位,形成了[CoNO5]的八面体配位几何构型,Co2-N的键长为Co2-O的键长为 这些键长与文献所报道的八面体构型的Co(II)相近。四核钴簇内的Co…Co距离为和Co1-O-Co2的键角95.64-104.37°。
图3为实施例2的分子结构图,从图3中可知,实施例2由七核钴簇、NO3 -、Cl-和溶剂水分子组成。实施例2为混价态的七核钴簇合物,中心是一个﹢2价钴离子,外围6个钴离子中有3个是﹢3价的,形成了2个共边的具有缺陷的四核钴簇单元。钴离子的价态是根据价键理论、键长和价态平衡来确定的。整个分子呈圆盘状,所有的钴离子几乎都在同一个平面内。L以μ2、μ3桥连方式通过醇氧和七个钴离子桥连在一起,分子中有12个L配体,其中有6个为μ3桥连方式,6个为μ2桥连方式。中心的Co1离子为八面体配位构型,与6个μ3-O配体的醇氧配位(Co1-O=2.065,)。Co2与两个来自L配体的咪唑氮原子和两个μ2-O桥连的醇氧(Co2-O=1.898(8),),两个μ3-O的氧原子配位(Co2-O=1.912(8),),形成了CoN2O4的八面体配位构型。Co3离子的配位环境与Co2离子相似,其Co3-O的键长为Co3-N的键长为2.047(9),Co…Co间的距离为Co-O-Co的键角为94.08-105.93°。在已经报道的七核钴簇合物中,很少观察到与实施例2类似的混合价态簇合物。
对实施例2的磁学性质进行表征。利用SQUID磁性测量仪MPMS XL-7在1000e的外场下收集了实施例2在2-290K范围内变温摩尔磁化率。用Pascal’s常数对该配合物进行了抗磁校正。并以χmT对T作图,所得的曲线如图4所示。由图4可知,该七核钴簇在300K时的χMT值为6.72cm3·K·mol-1,与四个高自旋态的Co(II)的纯自旋值χMT值(χMT=1.87cm3·K·mol-1,S=3/2,g=2.0)之和相比略低,说明钴离子之间存在着反铁磁相互作用,当温度降至30K时,χMT值为6.27cm3·K·mol-1,再降至2K时,χMT值为8.82cm3 K mol-1。10K以下,χMT的升高是由分子间的铁磁相互作用所引起的。温度为2K时所测饱和磁化强度曲线如图5所示。由图5可知,在磁场强度为7T时,饱和磁化强度为7.2Nβ,没有达到饱和状态,这可能是因为存在着强的磁各向异性。由此可知,本发明提供的钴簇合物具有一定的磁学性能,在磁性材料领域具有一定的应用潜能。
最后所应当说明的是,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,但并不脱离本发明技术方案的实质和范围。
Claims (5)
1.一种钴簇合物,其特征在于,所述钴簇合物的化学式为[CoII 4CoIII 3(L)12](NO3)4.5Cl0.5·4.5H2O,所述L为4-甲基-5-咪唑基-甲氧基。
2.一种如权利要求1所述的钴簇合物的制备方法,其特征在于,包括如下步骤:
(1)将钴盐溶解于溶剂A中,得到溶液A;
(2)将4-甲基-5-咪唑基-甲醇盐酸盐溶解在溶剂B中,得到溶液B;
(3)待步骤(1)、(2)完成后,将中和剂加入溶液B中,得到溶液C;
(4)待步骤(3)完成后,将溶液C加入溶液A中,搅拌、过滤,得到深色滤液;
(5)待步骤(4)完成后,将深色滤液于15-35℃下静置2~3周,得到所述钴簇合物;
所述溶剂A和溶剂B为甲醇或乙醇;所述步骤(1)中,钴盐为六水合硝酸钴,钴盐在溶剂A中的浓度为0.023-0.027mmol/mL;所述步骤(2)中,4-甲基-5-咪唑基-甲醇盐酸盐在溶剂B中的浓度为0.08-0.12mmol/mL;溶剂B的添加量为5mL时,所述步骤(3)中,中和剂的添加量为0.8-1.2mmol;所述钴盐、4-甲基-5-咪唑基-甲醇盐酸盐和中和剂的摩尔比为1:1:2。
3.如权利要求2所述的制备方法,其特征在于,所述中和剂为三乙胺、四甲基氢氧化铵、三乙醇胺、乙醇胺、氢氧化钠、氢氧化钾中的至少一种。
4.如权利要求2所述的制备方法,其特征在于,所述步骤(4)中的搅拌时间为0.8-1.2h。
5.一种如权利要求1所述的钴簇合物在分子基磁材料领域的应用。
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