CN103044494B - 钌金属有机聚合物发光材料及其合成与应用 - Google Patents

钌金属有机聚合物发光材料及其合成与应用 Download PDF

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CN103044494B
CN103044494B CN201310021235.4A CN201310021235A CN103044494B CN 103044494 B CN103044494 B CN 103044494B CN 201310021235 A CN201310021235 A CN 201310021235A CN 103044494 B CN103044494 B CN 103044494B
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dcbpy
heterometallocenes
luminescent material
polymer
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CN103044494A (zh
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罗军华
韩靓
李丽娜
张书泉
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Fujian Institute of Research on the Structure of Matter of CAS
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Abstract

本发明提供钌金属有机聚合物发光材料及其合成与应用。该发光材料为[InRu(dcbpy)3(CH3)2NH2]·6H2O（H2dcbpy=4,4'‑联吡啶二羧酸），立方晶系，F‑3m空间群，晶胞参数为,α=β=γ=90°，，Z=4。该化合物采用溶剂热反应进行制备。该化合物在300‑600 nm光的激发下表现为红色发光，发射峰最大值位于655 nm。

Description

钌金属有机聚合物发光材料及其合成与应用
技术领域
本发明涉及一种[Ru(H2dcbpy)3]·Cl2与铟形成的金属有机聚合物发光材料（分子式为C38H38InN7O18Ru）的合成、发光性能及应用。
背景技术
在众多发光化合物中，钌金属化合物以其独特的化学稳定性、丰富的氧化还原性和发光性质以及合适的激发态寿命逐渐成为光电化学方面研究的重点。钌金属化合物在催化、医药、生物等众多方面得到了充分的研究，而其中发光的钌多吡啶类配合物由于其特殊的配体结构，在化学传感、探针、光电转换等多个领域发挥了极大的作用。目前对于钌配合物的研究，多为以代表性的联吡啶及菲啰啉配体为基础，在配体的不同位置引入具有吸电子性质的基团，合成一系列新型发光钌化合物。
钌的金属有机化合物在可见光区具有良好的吸收能力，并且金属钌影响其系间窜越的效率通常也较高，其次具有良好的动力学和光化学稳定性，同时只要在钌金属有机化合物的周边留有合适的结合位点就很容易与其它金属离子结合，这就形成一类新颖的基于“钌金属有机基元”的异核金属有机发光聚合物。本发明采用了MLCT 跃迁能量相对较低的[Ru(H2dcbpy)3]·Cl2作为发光基元，周围六个羧基对于金属离子是很好的结合位点，选用In离子构筑三维聚合结构并且加强构筑结构的稳定性，合成出Ru-In异核金属有机聚合物。目前国内外用[Ru(H2dcbpy)3]·Cl2作为荧光发光基元的金属有机聚合物研究极少，因此对此类化合物的合成、结构和发光性质的研究，可以寻找到性能优异的钌金属有机发光化合物，拓展钌金属有机发光化合物的应用范围。
发明内容
本发明的目的在于选择[Ru(H2dcbpy)3]·Cl2作为发光基元合成一种发光Ru-In异核金属有机聚合物，分子式为C38H38InN7O18Ru，具体的实施技术方案：
选择[Ru(H2dcbpy)3]·Cl2和三水合氯化铟（）为原料，其摩尔比为1：3，采用N,N-二甲基甲酰胺作为溶剂，溶剂热反应生成Ru-In异核金属有机聚合物[InRu(dcbpy)3(CH3)2NH2]·8H2O（H2dcbpy = 4,4'-联吡啶二羧酸，脱氢即为dcbpy）。荧光光谱测试表明，Ru-In异核金属配位聚合物 [InRu(dcbpy)3(CH3)2NH2]·8H2O具有很宽的吸光范围（300 — 600 nm），在光的激发下产生很强的红光发射，最在发射波长在655 nm附近。
我们测得了该化合物的晶体和分子结构，总体结构可描述为每个[Ru(H2dcbpy)3]·Cl2基元通过六个羧基与周围六个In3+相连，每个In3+与周围六个通过六个羧基基元相连，形成高度对称的立方结构。
分子式为C38H38InN7O18Ru，空间群为F-3m，晶胞参数为a = b = c =，α= β = γ = 90°，， Z = 4。
本发明提供的Ru-In异核金属有机聚合物[InRu(dcbpy)3(CH3)2NH2]·8H2O是采用溶剂热反应合成得到。
以[Ru(H2dcbpy)3]·Cl2作为荧光基元的所构筑的Ru-In异核金属有机聚合物可成为一类优秀的发光材料，本发明制备的[InRu(dcbpy)3(CH3)2NH2]·6H2O可用于***物检测以及生物成像。
附图说明
图1为本发明技术方案中发光聚合物[InRu(dcbpy)3(CH3)2NH2]·6H2O的配位结构图。
图2为本发明技术方案中发光聚合物[InRu(dcbpy)3(CH3)2NH2]·6H2O的立方结构图
图3为本发明实施例2中发光聚合物[InRu(dcbpy)3(CH3)2NH2]·6H2O的荧光激发光谱。
图4为本发明实施例2中发光聚合物[InRu(dcbpy)3(CH3)2NH2]·6H2O在最大激发波长560 nm激发下的发射光谱。
具体实施方式
实施例1
称取[Ru(H2dcbpy)3]·Cl2和InCl3·3H2O，加入N,N-二甲基甲酰胺作为溶剂，装入反应瓶中，溶剂热恒温反应可制备出该Ru-In异核金属有机聚合物，经X射线单晶衍射分析，确定该晶体为[InRu(dcbpy)3(CH3)2NH2]·6H2O。
实施例2
将制备的化合物在Perkin-Elemer LS55荧光光谱仪上进行发光性能测试，结果显示，该化合物在300 - 600 nm的范围内有两个最大激发峰，峰值分别为378 nm和560 nm，用560 nm的波长激发该化合物，产生红光发光，最大发射波长位于655 nm。

Claims (3)

1.一种Ru-In异核金属有机发光聚合物，其特征在于:所述的Ru-In异核金属有机发光聚合物的分子式是C38H38InN7O18Ru，空间群为F-3m，晶胞参数为 α＝β＝γ＝90°，Z＝4；所述的Ru-In异核金属有机发光聚合物的结构为每个[Ru(H2dcbpy)3]·Cl2基元通过六个羧基与周围六个In3+相连，每个In3+与周围六个通过六个羧基基元相连，形成高度对称的立方结构，其中所述的H2dcbpy为4,4'-联吡啶二羧酸。
2.根据权利要求1所述的Ru-In异核金属有机发光聚合物的制备方法，包括如下步骤：原料荧光基元[Ru(H2dcbpy)3·Cl2]和三价金属铟盐的摩尔比为1：3，采用N,N-二甲基甲酰胺为溶剂，溶剂热恒温反应。
3.根据权利要求1所述的Ru-In异核金属有机发光聚合物的应用，其特征在于：所述的Ru-In异核金属有机发光聚合物用于发光材料和器件。
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WO2012073268A1 (en) * 2010-12-03 2012-06-07 Dyepower Process for the synthesis of precursor complexes of titanium dioxide sensitization dyes based on ruthenium polypyridine complexes

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WO2001032665A2 (en) * 1999-11-01 2001-05-10 Fluorrx, Inc. New ruthenium metal ligand complexes
WO2012073268A1 (en) * 2010-12-03 2012-06-07 Dyepower Process for the synthesis of precursor complexes of titanium dioxide sensitization dyes based on ruthenium polypyridine complexes

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