CN111269268A - 具有双发射性质的Ru配合物、具有双发射性质含空白配位点的Ru配合物及双发射配合物 - Google Patents
具有双发射性质的Ru配合物、具有双发射性质含空白配位点的Ru配合物及双发射配合物 Download PDFInfo
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Abstract
本发明公开了一种具有双发射性质的Ru配合物,该配合物由一个金属Ru中心,两个2,2’‑联吡啶N^N辅助配体(bpy)和一个1,10‑菲罗啉‑4‑甲醛N^N配体(PhenCHO)组成,该配合物具有明显的双发射性质。此外,该配合物含有的甲醛基可作为反应的基团。因此,以该配合物为前驱体,可进一步与1,10‑菲罗啉‑5,6‑二酮缩合,制备的配合物RuPI保留双发射性质,并且具有空白配位点可以引入催化单元‑PtCl2,形成分子型光催化剂RuPt,仍然保留双发射性质,并用于光催化产氢领域。
Description
技术领域
本发明涉及功能配合物技术领域,尤其涉及一种具有双发射性质的Ru配合物、具有双发射性质含空白配位点的Ru配合物及双发射配合物。
背景技术
以Ru基配合物为主体的功能配合物提供可调节的光物理、光化学,以及氧化还原性质,可以简便地通过光谱分析方法追踪,从而提供有用的信息,因此在功能配合物领域得到了广泛关注。
具有双发射性质的Ru配合物提供了控制激发态通过非辐射失活的新途径。因此,该类配合物在太阳能电池敏化染料,光催化材料和新型双发射材料方面具有特殊的效应。但是迄今为止,具有双发射波长的Ru基配合物还是极其少见的。
发明内容
(一)发明目的
本发明的目的是提供一种具有双发射性质的Ru配合物、具有双发射性质含空白配位点的Ru配合物及双发射配合物,并通过该配合物构建分子型光催化剂RuPt,且仍保留双发射性质。
(二)技术方案
为解决上述问题,本发明的第一方面提供了一种具有双发射性质的Ru配合物,分子结构式为:
根据本发明的另一个方面,提供一种具有双发射性质的Ru配合物的制备方法,包括:将1,10-菲罗啉-4-甲基氧化为1,10-菲罗啉-4-甲醛;将所述1,10-菲罗啉-4-甲醛与Ru(bpy)Cl2反应,得到具有双发射性质的Ru配合物;
反应线路如下:
根据本发明的又一方面,提供一种具有双发射性质含空白配位点的Ru配合物,分子结构式为:
根据本发明的又一方面,提供一种具有双发射性质含空白配位点的Ru配合物的制备方法,所述Ru配合物将权利要求1所述的具有双发射性质的Ru配合物作为前驱体制备的。
根据本发明的又一方面,提供一种双发射配合物,分子结构式为:
根据本发明的又一方面,提供一种双发射配合物的制备方法,所述双发射配合物是将PtCl2引入权利要求3所述的具有双发射性质含空白配位点的Ru配合物制备得到的。
根据本发明的又一方面,提供一种催化剂,分子结构式为:
(三)有益效果
本发明的上述技术方案具有如下有益的技术效果:
本发明提供的具有双发射性质的Ru配合物、具有双发射性质含空白配位点的Ru配合物、双发射配合物及催化剂均具有双发射波长,其中,催化剂能用于光催化产氢。
附图说明
图1是根据本发明一可选实施方式的含1,10-菲罗啉-4-甲醛N^N配体(PhenCHO)的双发射Ru配合物的吸收、激发和发射光谱;其中,a1:吸收光谱;a2:611nm的激发光谱;a3:714nm的激发光谱;a4:450nm的发射光谱;a5:490nm的发射光谱。
图2是根据本发明一可选实施方式的RuPhenIp的吸收,激发和发射光谱;其中,b1:吸收光谱;b2:645nm的激发光谱;b3:690nm的激发光谱;b4:450nm的发射光谱;b5:490nm的发射光谱。
图3是根据本发明一可选实施方式的RuPt的吸收,激发和发射光谱;其中,c1:吸收光谱;c2:624nm的激发光谱;c3:700nm的激发光谱;c4:450nm的发射光谱;c5:490nm的发射光谱。
具体实施方式
为使本发明的目的、技术方案和优点更加清楚明了,下面结合具体实施方式并参照附图,对本发明进一步详细说明。应该理解,这些描述只是示例性的,而并非要限制本发明的范围。此外,在以下说明中,省略了对公知结构和技术的描述,以避免不必要地混淆本发明的概念。
显然,所描述的实施例是本发明一部分实施例,而不是全部的实施例。基于本发明中的实施例,本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例,都属于本发明保护的范围。
此外,下面所描述的本发明不同实施方式中所涉及的技术特征只要彼此之间未构成冲突就可以相互结合。
在本发明实施例的第一方面,提供了一种具有双发射性质的Ru配合物,分子结构式为:
该配合物由一个金属Ru中心,两个2,2’-联吡啶N^N辅助配体(bpy)和一个1,10-菲罗啉-4-甲醛N^N配体(PhenCHO)组成,该配合物具有明显的双发射性质。此外,该配合物含有的甲醛基可作为反应的基团。因此,以该配合物为前驱体,可进一步与1,10-菲罗啉-5,6-二酮缩合,制备的配合物RuPI保留双发射性质,并且具有空白配位点可以引入催化单元-PtCl2,形成分子型光催化剂RuPt,仍然保留双发射性质,并用于光催化产氢领域。
在本发明实施例的另一个方面,提供一种具有双发射性质的Ru配合物的制备方法,包括:将1,10-菲罗啉-4-甲基氧化为1,10-菲罗啉-4-甲醛;将所述1,10-菲罗啉-4-甲醛与Ru(bpy)Cl2反应,得到具有双发射性质的Ru配合物;
反应线路如下:
具体的,双发射Ru配合物的制备:104mg(0.2mmol)Ru(bpy)2Cl2·2H2O和44mg(0.22mmol)1,10-菲罗啉-4-甲醛放入三口瓶中,加入35mLCH3CH2OH/H2O(体积比4:1)作为溶剂,氮气保护下加热回流4小时。停止反应后冷却抽滤,浓缩滤液,加入饱和NH4PF6水溶液,析出红色沉淀。沉淀用乙腈/乙醚扩散重结晶,干燥后得到红色粉末71mg(51%)。
1H-NMR(CD3CN):10.6(s,1H),9.21(d,1H),8.67(d,1H),8.54(d,2H),8.49(dd,2H),8.41(dd,2H),8.13(m,2H),8.08(d,2H),8.0(m,4H),7.82(d,1H),7.79(dd,2H),7.48(m,4H),7.21(m,2H)。
在本发明实施例的又一方面,提供一种具有双发射性质含空白配位点的Ru配合物,分子结构式为:
在本发明实施例的又一方面,提供一种具有双发射性质含空白配位点的Ru配合物的制备方法,所述Ru配合物将权利要求1所述的具有双发射性质的Ru配合物作为前驱体制备的。
具体的,双发射配合物RuPI的制备:21mg(0.1mmol)1,10-菲罗啉-5,6-二酮和154mg(20mmol)醋酸铵置于三口瓶中,加入3mLHAc,在氮气保护下加热,将置于混合溶剂HAc+CH3CN(1mL+3mL)的92mg(0.1mmol)Ru(bpy)2phenCHO缓慢加入三口瓶中,加热回流24小时。停止反应后冷却抽滤,浓缩滤液,加入饱和NH4PF6水溶液,析出红色沉淀。沉淀用乙腈/乙醚扩散重结晶,根据1H-NMR谱进行下一步纯化。
1H-NMR(CD3CN):10.03(d,1H),9.23(m,2H),9.11(dd,1H),8.88(dd,1H),8.72(dd,1H),8.55(m,6H),8.36(d,1H),8.18(dd,1H),8.13(q,2H),8.01(t,2H),7.88(m,5H),7.67(d,1H),7.56(d,1H),7.48(m,2H),7.25(m,2H)。ESI-MS:959.9[M-PF6+3H]+, 406.6[M-2PF6]2+。
在本发明实施例的又一方面,提供一种双发射配合物,分子结构式为:
在本发明实施例的又一方面,提供一种双发射配合物的制备方法,所述双发射配合物是将PtCl2引入权利要求3所述的具有双发射性质含空白配位点的Ru配合物制备得到的。
具体的,双发射配合物RuPt的制备:将RuPI与Pt(DMSO)2Cl2以物质的量比1:4混合,以乙腈为溶剂,氮气保护下回流。停止反应后冷却抽滤,浓缩滤液,加入饱和NH4PF6水溶液,析出沉淀。所得沉淀依次用乙醇,蒸馏水洗。最后用乙腈/乙醚扩散重结晶。
1H-NMR(CD3CN):9.93(d,1H),9.51(m,2H),9.14(dd,1H),8.93(dd,1H),8.76(d,1H),8.68(d,1H),8.53(m,5H),8.44(d,1H),8.22(d,1H),8.15(m,3H),8.09(dd,1H),8.02(m,3H),7.9(d,1H),7.85(m,2H),7.57(d,1H),7.51(m,2H),7.28(m,2H)。MS:(Matrix:Dithranol)1079.3[M-2PF6+H]+
在本发明实施例的又一方面,提供一种催化剂,分子结构式为:
本发明旨在保护一种具有双发射性质的Ru配合物,该配合物由一个金属Ru中心,两个2,2’-联吡啶N^N辅助配体(bpy)和一个1,10-菲罗啉-4-甲醛N^N配体(PhenCHO)组成,该配合物具有明显的双发射性质。此外,该配合物含有的甲醛基可作为反应的基团。因此,以该配合物为前驱体,可进一步与1,10-菲罗啉-5,6-二酮缩合,制备的配合物RuPI保留双发射性质,并且具有空白配位点可以引入催化单元-PtCl2,形成分子型光催化剂RuPt,仍然保留双发射性质,并用于光催化产氢领域。
应当理解的是,本发明的上述具体实施方式仅仅用于示例性说明或解释本发明的原理,而不构成对本发明的限制。因此,在不偏离本发明的精神和范围的情况下所做的任何修改、等同替换、改进等,均应包含在本发明的保护范围之内。此外,本发明所附权利要求旨在涵盖落入所附权利要求范围和边界、或者这种范围和边界的等同形式内的全部变化和修改例。
Claims (7)
4.一种具有双发射性质含空白配位点的Ru配合物的制备方法,其特征在于,所述Ru配合物将权利要求1所述的具有双发射性质的Ru配合物作为前驱体制备的。
6.一种双发射配合物的制备方法,其特征在于,所述双发射配合物是将PtCl2引入权利要求3所述的具有双发射性质含空白配位点的Ru配合物制备得到的。
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