Gao Yingning, Ma Pan, Chen Yanli, Zhang Ying, Bian Yongzhong, Li Xiyou, Jiang Jianzhuang, Ma Changqin
Department of Chemistry, Shandong University, Jinan 250100, China.
Inorg Chem. 2009 Jan 5;48(1):45-54. doi: 10.1021/ic801040z.
Two amphiphilic heteroleptic tris(phthalocyaninato) europium complexes with hydrophilic crown ether heads and hydrophobic octyloxy tails [Pc(mCn)(4)]Eu[Pc(mCn)(4)]Eu[Pc(OC(8)H(17))(8)] [m = 12, n = 4, H(2)Pc(12C4)(4) = 2,3,9,10,16,17,23,24-tetrakis(12-crown-4)phthalocyanine; m = 18, n = 6, H(2)Pc(18C6)(4) = 2,3,9,10,16,17,23,24-tetrakis(18-crown-6)phthalocyanine; H(2)Pc(OC(8)H(17))(8) = 2,3,9,10,16,17,23,24-octakis(octyloxy)phthalocyanine] (1, 2) were designed and prepared from the reaction between homoleptic bis(phthalocyaninato) europium compound [Pc(mCn)(4)]Eu[Pc(mCn)(4)] (m = 12, n = 4; m = 18, n = 6) and metal-free H(2)Pc(OC(8)H(17))(8) in the presence of Eu(acac)(3).H(2)O (Hacac = acetylacetone) in boiling 1,2,4-trichlorobenzene. These novel sandwich triple-decker complexes were characterized by a wide range of spectroscopic methods and electrochemically studied. With the help of the Langmuir-Blodgett technique, these typical amphiphilic triple-decker complexes were fabricated into organic field effect transistors (OFET) with top contact configuration on bare SiO(2)/Si substrate, hexamethyldisilazane-treated SiO(2)/Si substrate, and octadecyltrichlorosilane (OTS)-treated SiO(2)/Si substrate, respectively. The device performance is revealed to be dependent on the species of crown ether substituents and substrate surface treatment. OFETs fabricated from the triple decker with 12-crown-4 hydrophilic substituents, 1, allow the hole transfer in the direction parallel to the aromatic phthalocyanine rings. In contrast, the devices of a triple-decker compound containing 18-crown-6 as hydrophilic heads, 2, transfer holes in a direction along the long axis of the assembly composed of face-to-face aggregated triple-decker molecules, revealing the effect of molecular structure, specifically the crown ether substituents on the film structure and OFET functional properties. The carrier mobility for hole as high as 0.33 cm(2) V(-1) s(-1) and current modulation of 7.91 x 10(5) were reached for the devices of triple-decker compound 1 deposited on the OTS-treated SiO(2)/Si substrates, indicating the effect of substrate surface treatment on the OFET performance due to the improvement on the film quality as demonstrated by the atomic force microscope investigation results.
设计并制备了两种具有亲水头冠醚和疏水尾辛氧基的两亲性杂配三（酞菁基）铕配合物[Pc(mCn)(4)]Eu[Pc(mCn)(4)]Eu[Pc(OC(8)H(17))(8)] [m = 12，n = 4，H(2)Pc(12C4)(4) = 2,3,9,10,16,17,23,24 - 四（12 - 冠 - 4）酞菁；m = 18，n = 6，H(2)Pc(18C6)(4) = 2,3,9,10,16,17,23,24 - 四（18 -冠 - 6）酞菁；H(2)Pc(OC(8)H(17))(8) = 2,3,9,10,16,17,23,24 - 八（辛氧基）酞菁]（1, 2），它们是由同配双（酞菁基）铕化合物[Pc(mCn)(4)]Eu[Pc(mCn)(4)]（m = 12，n = 4；m = 18，n = 6）与无金属的H(2)Pc(OC(8)H())(8)在Eu(acac)(3).H(2)O（Hacac = 乙酰丙酮）存在下于沸腾的1,2,4 - 三氯苯中反应制得。这些新型夹心三层配合物通过多种光谱方法进行了表征，并进行了电化学研究。借助朗缪尔 - 布洛杰特技术，将这些典型的两亲性三层配合物分别制备成顶接触构型的有机场效应晶体管（OFET），沉积在裸露的SiO(2)/Si衬底、六甲基二硅氮烷处理的SiO(2)/Si衬底和十八烷基三氯硅烷（OTS）处理的SiO(2)/Si衬底上。器件性能显示取决于冠醚取代基的种类和衬底表面处理。由具有12 - 冠 - 4亲水性取代基的三层配合物1制备的OFET，允许空穴在平行于芳香酞菁环的方向上转移。相反，以含有18 - 冠 - 6作为亲水头基的三层配合物2制备的器件，空穴在由面对面聚集的三层分子组成的组装体的长轴方向上转移，揭示了分子结构的影响，特别是冠醚取代基对薄膜结构和OFET功能性质的影响。对于沉积在OTS处理的SiO(2)/Si衬底上的三层配合物1的器件，空穴载流子迁移率高达0.33 cm(2) V(-1) s(-1)，电流调制为7.91 x 10(5)，这表明衬底表面处理对OFET性能的影响，原子力显微镜研究结果证明这是由于薄膜质量的改善。
