CN110372733B - 一种具有荧光性能的金属有机铜配合物及其制备方法 - Google Patents
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- 150000004699 copper complex Chemical class 0.000 title claims abstract description 24
- 239000002184 metal Substances 0.000 title claims abstract description 16
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title abstract description 11
- 239000013078 crystal Substances 0.000 claims abstract description 20
- 239000003446 ligand Substances 0.000 abstract description 19
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 abstract description 16
- FVTBHYDEFPOYSG-UHFFFAOYSA-N benzimidazol-1-ylphosphane Chemical compound C1=CC=C2N(P)C=NC2=C1 FVTBHYDEFPOYSG-UHFFFAOYSA-N 0.000 abstract description 9
- 150000002500 ions Chemical class 0.000 abstract description 4
- 125000004437 phosphorous atom Chemical group 0.000 abstract description 4
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 3
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 2
- 239000010949 copper Substances 0.000 abstract description 2
- 229910001431 copper ion Inorganic materials 0.000 abstract description 2
- 238000000034 method Methods 0.000 abstract description 2
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 27
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 18
- 239000000243 solution Substances 0.000 description 7
- 238000001914 filtration Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- 229910021595 Copper(I) iodide Inorganic materials 0.000 description 4
- LSXDOTMGLUJQCM-UHFFFAOYSA-M copper(i) iodide Chemical compound I[Cu] LSXDOTMGLUJQCM-UHFFFAOYSA-M 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 239000013256 coordination polymer Substances 0.000 description 3
- 229920001795 coordination polymer Polymers 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000012467 final product Substances 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 238000004020 luminiscence type Methods 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- ICZZIFSROFGMSE-UHFFFAOYSA-N 1h-benzimidazole;phosphane Chemical compound P.C1=CC=C2NC=NC2=C1 ICZZIFSROFGMSE-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000000695 excitation spectrum Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
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- 239000013110 organic ligand Substances 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 230000027756 respiratory electron transport chain Effects 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 1
- 229940045803 cuprous chloride Drugs 0.000 description 1
- 238000013480 data collection Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002189 fluorescence spectrum Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000001748 luminescence spectrum Methods 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000013558 reference substance Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052594 sapphire Inorganic materials 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000012916 structural analysis Methods 0.000 description 1
- 230000001360 synchronised effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
- 238000012800 visualization Methods 0.000 description 1
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Abstract
Description
技术领域
本发明属于金属有机配合物合成技术领域,具体涉及一种具有荧光性能的金属有机铜配合物及其制备方法。
背景技术
金属有机配合物作为当今材料化学的重要研究主题之一,不仅具有结构美学价值,而且在发光、磁性、吸附、储氢、催化和分离等领域具有良好的应用前景。特别是通过金属离子与有机多功能配体的配位来构筑具有高热稳定性结构和特种物化性能的配位聚合物已经引起了人们的极大兴趣。然而设计和构筑这类具有特殊结构和功能的材料属于创新技术,具有很大的挑战性,特别是兼具较好热稳定性和光学性能的材料。近年来,一些具有高热稳定性,或者具有荧光性能的配位聚合物已被广泛研究,并取得了一定的成果,但在这些配合物中,同时兼具较好热稳定性和荧光性能的材料却鲜有报道。
发明内容
为克服以上问题,本发明提供一种具有荧光性能的金属有机铜配合物及其制备方法,该方法反应条件温和,制备过程简单,成本低廉,所得金属有机铜配合物同时具有较好的荧光性能和热稳定性,可用于光学材料。
本发明的目的及解决其技术问题是采用以下技术方案来实现的。依据本发明提出的种具有荧光性能的金属有机铜配合物,其分子式为C63H51CuIN3O2P2,该配合物的晶体属于单斜晶系,晶胞参数为: α=90°,β=107.474°,γ=90°;在每个配合物分子中包含一个铜离子、一个苯并咪唑膦类配体和一个三苯基膦辅助配体;在晶体中,配合物中心的Cu离子分别与I离子及苯并咪唑膦类配体中的N、P原子以及辅助配体三苯基膦中的P原子进行配位,形成四配位的扭曲四面体构型。
进一步地,所述的苯并咪唑膦类配体的结构式为:
进一步地,所述金属有机铜配合物的结构式为:
前述的具有荧光性能的金属有机铜配合物,在光学材料中的应用。
本发明的目的及解决其技术问题还可采用以下技术方案进一步实现。一种具有荧光性能的金属有机铜配合物的制备方法,包括以下步骤:
(1)将3mmol碘化亚铜、3mmol苯并咪唑膦类配体和3mmol三苯基膦加入到20~25ml二氯甲烷与乙腈的混合溶液中,将混合物加热到40℃并在该温度下不断搅拌保持2~3小时;
所述苯并咪唑膦类配体的结构式为:
(2)将步骤(1)反应完的溶液过滤并转移至30ml小玻璃瓶中,自然挥发72~96小时,得到配合物晶体,过滤出晶体,用乙腈洗涤,真空烘干得到最终产品-有机铜配合物;
所得金属有机铜配合物的结构式为:
进一步地,步骤(1)中二氯甲烷与乙腈的体积比为4:1。
与现有技术相比,本发明具有以下优点:
(1)本发明的有机铜配合物具有较强的荧光性,配合物在制备过程中,直接将配体与碘化亚铜进行反应得到,在激发光谱为λex=400nm和293K条件下出现强的发射峰λem=552nm,它的荧光发射可能主要归因于中心原子-配体间的电子传递(MLCT)作用而引起的荧光;
(2)本发明有机铜配合物的TG曲线显示出有机配体从262.5℃开始失重,导致结构框架坍塌;说明该配合物具有较好的热稳定性;
(3)本发明有机铜配合物的制备工艺简单,且生产效率高,设备投资少,同时整个生产过程污染少,符合可持续发展要求。
上述说明仅是本发明技术方案的概述,为了能够更清楚了解本发明的技术手段,可依照说明书的内容予以实施,并且为了让本发明的上述和其他目的、特征和优点能够更明显易懂,以下特举较佳实施例,详细说明如下。
附图说明
图1为本发明铜配合物C63H51CuIN3O2P2的晶体结构,为清晰可见,图1中未显示结构中的氢原子。
图2为本发明铜配合物C63H51CuIN3O2P2的TG曲线。
图3为本发明铜配合物C63H51CuIN3O2P2的在常温293K下的固体荧光发射光谱图。
图4为本发明铜配合物C63H51CuIN3O2P2的合成路线图。
具体实施方式
为更进一步阐述本发明为达成预定发明目的所采取的技术手段及功效,以下结合附图及较佳实施例,对依据本发明提出的一种具有荧光性能的金属有机铜配合物及其制备方法,其具体实施方式、特征及其功效,详细说明如后。
实施例1
在室温条件下,称取0.572g(3mmol)碘化亚铜、2.045g(3mmol)苯并咪唑膦类配体和0.786g(3mmol)三苯基膦加入到20ml二氯甲烷与乙腈的混合溶液中(二氯甲烷与乙腈的体积比=4:1),加热到40℃并在该温度下不断搅拌保持2小时。将反应完的溶液过滤并转移至30ml小玻璃瓶中,自然挥发72小时,得到得到配合物晶体,过滤出晶体,用少量乙腈洗涤,真空烘干得到最终产品,产率89%。
实施例2
在室温条件下,称取0.572g(3mmol)碘化亚铜、2.045g(3mmol)苯并咪唑膦类配体和0.786g(3mmol)三苯基膦加入到25ml二氯甲烷与乙腈的混合溶液中(二氯甲烷与乙腈的体积比=4:1),加热到40℃并在该温度下不断搅拌保持3小时。将反应完的溶液过滤并转移至30ml小玻璃瓶中,自然挥发96小时,得到得到配合物晶体,过滤出晶体,用少量乙腈洗涤,真空烘干得到最终产品,产率87%。
实施例1和实施例2所用的苯并咪唑膦类配体结构式为:
所述苯并咪唑膦类配体与三苯基膦和氯化亚铜按照图4所示的反应原理反应最终得到的有机铜配合物的结构式如下:
对实施例1和实施例2所制得的配位聚合物进行表征检测:
(1)晶体结构
在显微镜下选取合适大小的单晶,使用Bruker AMART APEX Ⅱ CCD X-射线单晶衍射仪(石墨单色器Mo-Kα辐射,)在150K下使用ω/θ扫描方式收集X-射线单晶数据。通过SHELXS-97进行结构解析,并使用SHELXL-97程序包通过全矩阵最小二乘法进行细化精修,在合适位置理论加氢,对所有非氢原子均用各向异性精修。该配合物的晶体结构见图1,晶体学结构精修的部分参数见下表1:
表1.实施例1和实施例2所得配合物的晶体学衍射点数据收集与结构精修参数
(2)差热热重分析表征
采用德国耐驰TG-DSC STA 449 F1型同步热分析仪,以α-Al2O3为参比物,在200ml/min的氮气气流保护,升温速率为10℃/min的条件下测定配合物的TG曲线。该配合物的TG曲线如图2所示,有机配体从262.5℃开始失重,导致框架结构坍塌,说明所得配合物具有较好的热稳定性。
(3)固体粉末发光性质
固体粉末发光性质采用爱丁堡BCEIA 2015 FS5型一体化荧光光谱仪测定,该配合物的固体粉末发光光谱如图3所示,所得配合物在激发光谱为λex=400nm的条件下,在293K时配合物最大发射波长为552nm,它的荧光发射可能主要归因于中心原子-配体间的电子传递(MLCT)作用而引起的荧光。
以上所述,仅是本发明的较佳实施例而已,并非对本发明作任何形式上的限制,本发明的较佳实施例并非用以限定本发明,任何熟悉本专业的技术人员,在不脱离本发明技术方案的范围内,依据本发明的技术实质对以上实施例所作的任何简单修改、等同变化与修饰,均仍属于本发明技术方案的范围内。
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