源自芳香族的铽、铕和钆三（吡唑基）硼酸盐配合物中π-π堆积相互作用在发光性质和能量转移方面的表现。

Manifestation of π-π stacking interactions in luminescence properties and energy transfer in aromatically-derived Tb, Eu and Gd tris(pyrazolyl)borate complexes.

作者信息

Mikhalyova Elena A, Yakovenko Anastasiya V, Zeller Matthias, Kiskin Mikhail A, Kolomzarov Yuriy V, Eremenko Igor L, Addison Anthony W, Pavlishchuk Vitaly V

机构信息

†L. V. Pisarzhevskii Institute of Physical Chemistry of the National Academy of Sciences of Ukraine, Prospekt Nauki 31, Kiev, 03028, Ukraine.

‡STARBURSTT CyberInstrumentation Consortium and Department of Chemistry, Youngstown State University, One University Plaza, Youngstown, Ohio 44555-3663, United States.

出版信息

Inorg Chem. 2015 Apr 6;54(7):3125-33. doi: 10.1021/ic502120g. Epub 2015 Mar 23.

DOI:10.1021/ic502120g

PMID:25797500

Abstract

The three new complexes Tp(Py)Ln(CH3CO2)2(H2O) (Ln = Eu (1), Gd(2), or Tb (3)) were prepared and characterized crystallographically. In the crystal lattices of these complexes, separate molecules are connected in infinite chains by π-stacking interactions. Complexes 1 and 3 display intense photoluminescence and triboluminescence (red and green respectively), while compound 3 exhibits electroluminescence commencing at 9 V in an ITO/PVK/3/Al device (ITO = indium-tin oxide, PVK = poly(N-vinylcarbazole)). A series of Eu/Tb-doped Gd compounds was prepared by cocrystallization from mixtures of 1 and 2 or 2 and 3, respectively. It was shown that π-stacking interactions are involved in increasing the efficiency of energy transfer from the gadolinium complex to emitting Tp(Py)Eu or Tp(Py)Tb centers, and this energy transfer occurs through hundreds of molecules, resembling the process of energy harvesting in chloroplast stacks.

摘要

制备了三种新型配合物Tp(Py)Ln(CH3CO2)2(H2O)（Ln = Eu (1)、Gd(2) 或Tb (3)），并通过晶体学对其进行了表征。在这些配合物的晶格中，单个分子通过π堆积相互作用连接成无限长链。配合物1和3分别显示出强烈的光致发光和摩擦发光（分别为红色和绿色），而化合物3在ITO/PVK/3/Al器件（ITO = 铟锡氧化物，PVK = 聚（N-乙烯基咔唑））中在9 V时开始表现出电致发光。通过分别从1和2或2和3的混合物中共结晶制备了一系列Eu/Tb掺杂的Gd化合物。结果表明，π堆积相互作用参与提高从钆配合物到发光的Tp(Py)Eu或Tp(Py)Tb中心的能量转移效率，并且这种能量转移通过数百个分子发生，类似于叶绿体堆叠中的能量收集过程。