CN108299509A - 一种钌-二亚胺型配合物、制备方法及其用途 - Google Patents
一种钌-二亚胺型配合物、制备方法及其用途 Download PDFInfo
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Abstract
本发明涉及钌‑二亚胺型配合物、制备方法及其用途。方法涉及i、将2‑吡啶甲醛、2‑氨基屈溶解于无水乙醇并在氮气保护下加热搅拌；加入钌配合物前驱体Ru(bpy)2Cl2，在氮气保护下加热回流过夜；待原料转化完全后，停止加热，冷却到室温，浓缩；向浓缩溶液中加入六氟磷酸铵的甲醇饱和溶液，将反应混合物转移至砂板漏斗中抽滤，洗涤；粗品溶于丙酮中，使用正己烷作为扩散剂重结晶，得到钌‑二亚胺型配合物的纯品，本发明中的钌‑二亚胺型配合物其制备方法简单，产率和纯度较高，在配体合成后不需分离处理，可直接与钌前驱体反应制得目标产物。该钌‑二亚胺型配位化合物在催化、传感、分子识别等方面具有广泛的应用前景。
Description
技术领域
本发明涉及钌配合物的制备领域，具体涉及一种钌-二亚胺型配合物及其制备方法。
背景技术
作为d6过渡金属的代表，钌易于形成六配位的配合物且本身价态变化丰富，使其拥有了丰富的理化性质。钌配合物热力学稳定性好、光物理信息丰富、激发态反应活性高，荧光寿命长且发光性能良好。目前被广泛应用于化学发光，电子转移，非线性光学材料，分子光开关，分子识别，传感器等领域。同时钌配合物具有生物毒性低，易吸收并可很快排泄的特点，使其在抗肿瘤方面有着巨大的应用。此外钌配合物本身在催化方面也有着广泛的应用前景。因此长期以来钌配合物合成、性质与应用一直激发着人们的巨大研究兴趣。
从上世纪80年代起，人们发现某些钌配合物可以络合DNA，并以此为基础开展了很多包括结合力和DNA光开关等方面的研究。但时至今日，在钌配合物与DNA的络合机理、络合常数、配体修饰等方面仍有大量未探索的内容。对这一方向的新型钌配位化合物的研究有助于人们更深入地认识钌配合物的发光机理、电子传输等特性，也可能从中发现新的潜在应用价值，因此有着重要的理论意义和应用前景。
发明内容
本发明要解决的技术问题是：提出一种具有全新结构的钌-二亚胺型配合物、制备方法及其用途。
本发明为解决上述技术问题提出的技术方案(一)是：一种钌-二亚胺型配合物的制备方法，包括以下特征步骤：
i、将2-吡啶甲醛与无水乙醇混合并搅拌溶解，向该溶液中加入2-氨基屈并在氮气保护下加热搅拌；
ii、向步骤i结束后得到的溶液中加入钌配合物前驱体Ru(bpy)2Cl2，在氮气保护下加热回流过夜；
iii、待步骤ii中原料转化完全后，停止加热，冷却到室温，将反应溶液通过旋转蒸发仪浓缩；
iv、向浓缩溶液中加入六氟磷酸铵的甲醇饱和溶液，将反应混合物转移至砂板漏斗中抽滤，所得固体用冷却到0℃的乙醇洗涤3-5次；
v、将步骤vi中所得粗品溶于丙酮中，使用正己烷作为扩散剂重结晶，得到钌-二亚胺型配合物的纯品，其为暗红色晶体。
进一步的，所述钌配合物前驱体Ru(bpy)2Cl2是经由以下步骤制得：
a、将水合三氯化钌，置于圆底单口烧瓶中，加入DMF，搅拌溶解，再向此溶液中加入2-2’联吡啶和氯化锂；
b、将圆底烧瓶放置于电磁搅拌器上的油浴锅中，放入搅拌子，连好回流冷凝管，在双排管上抽真空-通氮气3个循环，以除尽反应器中的空气；
c、开启电磁搅拌器的加热功能，温度设定为110-120℃，加热搅拌过夜；
d、停止加热后冷却到室温，反应混合物用砂板漏斗抽滤，所得墨绿色固体用冷却的乙醇：正己烷＝2:1混合溶液洗涤3次，再用乙醚洗涤1次；
e、将步骤d结束时所得物质在乙醇中重结晶，真空干燥后得到纯品。
进一步的，所得钌-二亚胺型配合物的分子式为C40H30N6RuP2F12·2(H2O)。
本发明为解决上述技术问题提出的技术方案(二)是：一种钌-二亚胺型配合物，是通过上述方法制得。
本发明为解决上述技术问题提出的技术方案(三)是：前述钌-二亚胺型配合物在DNA络合或识别方面的应用。
本发明的有益效果是：
本发明中的钌-二亚胺型配合物具有配合构筑单元应用的广泛性和灵活性，其制备方法简单，产率和纯度较高，在配体合成后不需分离处理，可直接与钌前驱体反应制得目标产物。该钌-二亚胺型配位化合物在催化、传感、分子识别等方面具有广泛的应用前景，这种钌配合物的结构此前未见文献报道。并通过对其紫外、荧光、电化学等性质进行的探究，揭示出这一类新颖的结构在与DNA的络合或是识别等方面能够提供有价值的应用前景。
附图说明
下面结合附图对本发明的钌-二亚胺型配合物、制备方法及其用途作进一步说明。
图1是按照本发明的方法合成的钌-二亚胺型配合物分子结构示意图；
图2是本发明涉及的钌-二亚胺型配合物的合成反应示意图；
图3是本发明涉及的钌-二亚胺型配合物的紫外光谱图；
图4是本发明涉及的钌-二亚胺型配合物的荧光光谱图；
图5是本发明涉及的钌-二亚胺型配合物的电化学循环伏安图；
图6是本发明涉及的钌-二亚胺型配合物在加入DNA后的荧光光谱变化。
具体实施方式
实施例1
实施例中除特别注明之外的化学药品均为国产AR试剂。下列实施例中各物质的份量均可按不同实际情况所需进行适应性的增减。
实施例1：钌配合物前驱体Ru(bpy)2Cl2的合成
在分析天平上称取水合三氯化钌2.07g，置于50ml圆底单口烧瓶中，加入20mlDMF，搅拌使其溶解，向此溶液中加入精确称量的2-2’联吡啶3.15g，氯化锂0.5g。将圆底烧瓶放置于电磁搅拌器上的油浴锅中，放入四氟乙烯搅拌子，连好回流冷凝管，在双排管上抽真空-通氮气3个循环，以除尽反应器中的空气。开启电磁搅拌器的加热功能，温度设定为110℃，加热搅拌过夜。停止加热后冷却到室温，反应混合物用砂板漏斗抽滤，所得墨绿色固体用冷却的乙醇：正己烷＝2:1混合溶液洗涤3次，再用乙醚洗涤1次。进一步在乙醇中重结晶，真空干燥后得到纯品3.65g，产率70％。
实施例2：新型钌-二亚胺类配合物的合成
在分析天平上称取2-吡啶甲醛0.54g(5mmol)，置于150ml圆底两口烧瓶中，加入80ml无水乙醇，搅拌使其溶解，向此溶液中加入精确称量的2-氨基屈1.21g(5mmol)。在氮气保护下于60℃加热搅拌15分钟。加入按实施例1合成的Ru(bpy)2Cl2 2.5g(4.8mmol)，然后在氮气保护下加热回流过夜。经TLC监测原料转化完全后，停止加热，冷却到室温，反应溶液用旋转蒸发仪浓缩至50ml。加入六氟磷酸铵的甲醇饱和溶液5ml，充分搅拌后将反应混合物转移至砂板漏斗中抽滤，所得固体用冷却到0℃的乙醇洗涤3次，每次10ml。所得粗品溶于丙酮中，使用正己烷作为扩散剂重结晶，得到纯品为暗红色晶体。产率75％。元素分析结果(括号外为计算值，括号内为实测值)：分子式[C40H30N6RuP2F12·2(H2O)]，C 47.02(47.05),H 3.35(3.07),N 8.23(8.21)。核磁数据(400MHz,溶剂为CDCl3)：1H NMR:δ7.0(m,1H),7.3-8.5(m,24H),8.6(d,1H),8.9(t,2H),9.1(d,1H),9.6(s,1H)。
实施例3：新型钌-二亚胺配合物的紫外与荧光测试
在分析天平上称取采用本发明方法合成的新型钌-二亚胺配合物20mg，置于50ml容量瓶中，用新蒸的乙腈(光谱纯)溶解并定容。在紫外与荧光测试前用氩气驱除比色皿中的空气。紫外光谱数据显示，该配合物在270nm，320nm有强吸收峰，在426nm和490nm有较弱的吸收峰，如附图3所示。270nm的强吸收峰来自于内在二亚胺配体的电子跃迁，320nm的强吸收峰则是源于配体为中心的π→π*电子跃迁；426nm的吸收峰可以指认为从钌金属中心的d轨道到联吡啶配体的π*反键轨道的MLCT电子转移dπ(Ru)→π*(bpy)，490nm的吸收峰可以指认为从钌金属中心的d轨道到二亚胺配体的π反键轨道的MLCT电子转移即dπ(Ru)→π*(二亚胺)。新型钌-二亚胺配合物的室温溶液荧光光谱在相同的乙腈溶液中于298K测得，根据紫外光谱，将荧光激发波长设为460nm，在790nm检测到较强的单一荧光峰，根据与类似化合物的对比分析，此三线态荧光源于能量最低的从钌金属中心的d轨道到二亚胺配体的π反键轨道的MLCT电子转移dπ(Ru)→π*(二亚胺)，由于二亚胺的π*反键轨道能量比联吡啶的低，因此新型钌-二亚胺配合物的荧光峰位比最常见的钌联吡啶配合物[Ru(bpy)3]2+红移，且具有相对较短的荧光寿命。(如附图4所示)。
实施例4：新型钌-二亚胺配合物的电化学循环伏安测试
循环伏安扫描于室温下在CHI660E电化学工作站上进行，将适量钌-二亚胺配合物溶于含有0.1mol dm-3nBu4NPF6支持电解质的光谱纯乙腈中，测试使用三电极电解池，以玻碳为工作电极，铂丝为对电极，饱和甘汞为参比电极，扫描速率100mV s-1。循环伏安扫描结果显示，该配合物在+1.34V(相对于饱和甘汞电极，下同)处有一对氧化峰，与具有类似结构的其他钌配合物相似，可以指认为Ru(II)到Ru(III)的氧化。此外在–1.03V，–1.56V，–1.74V，–1.95V处分别出现4对还原峰，如附图5所示。经过与相关文献的对比分析，这四对还原峰分别源于下列反应：
实施例5：新型钌-二亚胺配合物络合DNA的测试
钌-二亚胺配合物与DNA的络合在含有5％甲醇的PH＝7缓冲溶液中进行，缓冲液的总离子浓度控制在20mmol。如附图6所示，室温下随着小牛胸腺DNA的加入，钌配合物的荧光强度稳定升高，达到最大值后不再变化，这是由于配合物与DNA的络合达到了饱和。小牛胸腺DNA对钌-二亚胺配合物荧光增强的最大值为初始荧光强度的1.5倍，此时DNA与配合物的摩尔比为3，说明每个配合物可以络合3个DNA分子。以DNA的加入量为横坐标，荧光强度的增强率为纵坐标作图并经曲线拟合，可以算得钌-二亚胺配合物与该DNA的络合常数为2.83×104dm3mol–1。
本发明的不局限于上述实施例，本发明的上述各个实施例的技术方案彼此可以交叉组合形成新的技术方案，另外凡采用等同替换形成的技术方案，均落在本发明要求的保护范围内。
Claims (5)
1.一种钌-二亚胺型配合物的制备方法，包括以下特征步骤：
i、将2-吡啶甲醛与无水乙醇混合并搅拌使其溶解，向该溶液中加入2-氨基屈并在氮气保护下加热搅拌；
ii、向步骤i结束后得到的溶液中加入钌配合物前驱体Ru(bpy)2Cl2，在氮气保护下加热回流过夜；
iii、待步骤ii中原料转化完全后，停止加热，冷却到室温，将反应溶液通过旋转蒸发仪浓缩；
iv、向浓缩溶液中加入六氟磷酸铵的甲醇饱和溶液，将反应混合物转移至砂板漏斗中抽滤，所得固体用冷却到0℃的乙醇洗涤3-5次；
v、将步骤vi中所得粗品溶于丙酮中，使用正己烷作为扩散剂重结晶，得到钌-二亚胺型配合物的纯品，其为暗红色晶体。
2.根据权利要求1所述钌-二亚胺型配合物的制备方法，其特征在于：所述钌配合物前驱体Ru(bpy)2Cl2是经由以下步骤制得：
a、将水合三氯化钌，置于圆底单口烧瓶中，加入DMF，搅拌溶解，再向此溶液中加入2-2’联吡啶和氯化锂；
b、将圆底烧瓶放置于电磁搅拌器上的油浴锅中，放入搅拌子，连好回流冷凝管，在双排管上抽真空-通氮气3个循环，以除尽反应器中的空气；
c、开启电磁搅拌器的加热功能，温度设定为110-120℃，加热搅拌过夜；
d、停止加热后冷却到室温，反应混合物用砂板漏斗抽滤，所得墨绿色固体用冷却的乙醇：正己烷=2:1混合溶液洗涤3次，再用乙醚洗涤1次；
e、将步骤d结束时所得固体在乙醇中重结晶，真空干燥后得到纯品。
3.根据权利要求1所述钌-二亚胺型配合物的制备方法，其特征在于：所得钌-二亚胺型配合物的分子式为C40H30N6RuP2F12•2(H2O)。
4.一种钌-二亚胺型配合物，其特征在于：是通过权利要求1或权利要求2中的方法制得。
5.根据权利要求4所述的钌-二亚胺型配合物在DNA络合或识别方面的应用。
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