March[Article]
物理化学学报（WuliHuaxueXuebao）
Acta Phys. -Chim. Sin. 2012, 28 (3), 733738
doi:10.3866/PKU.WHXB201201131
许邹明
王玉霞戴鹏
孔维权
733
www.whxb.pku.edu.cn
(中国科学院能量转换材料重点实验室，中国科学技术大学材料科学与工程系，合肥230026)
摘要：详细研究了N-(3-三甲氧基硅基乙基)乙二胺(TMSEEDA)的电子结构、光物理性质以及热稳定性.通过密度泛函理论计算获得了基态和第一激发态的结构参数.计算结果还表明在Si一O骨架内存在离域电子，这导致了长波长的吸收.在270nm紫外光的激发下，溶液和固态均能观察到一个宽且强的蓝色发射，其峰位于430 nm，固态的强度高出纯物质5倍左右.在乙醇溶液中，发光强度随着TMSEEDA浓度的增大而增加，并在纯物质时达到最大值.这些结果说明TMSEEDA不存在浓度率灭效应，我们提出了在Si一O骨架内电子离域和d-p T键模型来解释长波长吸收和蓝色发射
关键词：光致发光；：密度泛函理论；d-p键模型：淬灭；机制中图分类号：O641
EfficientBlueEmissionfromSmall-MoleculeOrganosiliconMonomer
N-(3-Trimethoxysilylethyl)ethylenediamine
XU Zou-Ming
WANG Yu-Xia'
DAIPeng
KONGWei-Quan
(CAS Key Laboratory of Materials for Energy Conversion, Department of Materials Science and Engineering,
University of Science and Technology of China, Hefei 230026, P R. China)
Abstract:We investigated the electronic structure, photophysical properties, and thermal stability of N-(3-trimethoxysilylethyl)ethylenediamine (TMSEEDA). The optimized structural parameters in the ground state and first excited state were obtained from density functional theory calculations. The results showed that there was probably r electron delocalization within the Si O skeleton, which induced the long wavelength absorption, A broad and intense blue emission with a maximum at 430 nm was observed for both the solution and the solid state with 270 nm excitation at room temperature. The absorption intensity for the solid state was five-times that of the pure TMSEEDA. For the ethanol solution, the photoluminescence intensityincreased
with increasing concentration of TMSEEDA and reached a
maximum at a
concentration of 100%. These results suggest there is no concentration quenching for TMSEEDA. An accepted model of electron delocalization and d-p r-bonding within the SiO skeleton was applied to explain the long wavelength absorption and blue emission.
KeyWords:
1Introduction
Density functional theory:d-p rr-bonding model;
Photoluminescence; Mechanism
Quenching:
ic light-emitting diodes (OLEDs)," organic solid-state lasers,
r-Conjugated organic materials, especially those containing heavier main group-14 elements,'' play a key role in photonics because of their exceptional luminescencefeatures and thermal stability, attractively with respect to their applications in organ-
organic fluorescent sensor, and organic photovoltaic cells(OPVs)." In addition to the extensive applications as well as lu-minescence features, it is also considerably attractive for desir-able intrinsic properties of solution-processable small mole-
Received: October 26, 2011; Revised: January 5, 2012; Published on Web: January 13, 2012.*Corresponding author. Email: wyxm@ustc.edu.cn; Tel: +86-551-3601695.
The project was supported by the National Natural Science Foundation of China (5067095) 国家自然科学基金(5067095)资助项目
Editorial office of Acta Physico-Chimica Sinica