Platinum(II)-Based Metallo-Supramolecular Polymer with Controlled Unidirectional Dipoles for Tunable Rectification
Platinum(II)-Based Metallo-Supramolecular Polymer with Controlled Unidirectional Dipoles for Tunable Rectification
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DOI：
10.1021/acsami.5b03434
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发表时间：
2015-09-02
影响因子：
9.5
通讯作者：
Higuchi, Masayoshi
中科院分区：
文献类型：
--
作者：
Chakraborty, Chanchal;Pandey, Rakesh K.;Higuchi, Masayoshi
一种基于铂（II），发光，金属超分子聚合物（聚PtL 1）具有固有的偶极矩通过络合的Pt（II）离子与不对称配体含有三联吡啶和吡啶部分合成。合成的配体和聚合物，以及其特征在于通过各种NMR技术，光谱，和循环伏安法的研究。用原子力显微镜对聚合物链的形态进行了研究，发现聚合物链的高度为1-4个边。将聚合物特异性地附着在Au电极上以产生两种类型的膜（膜1和2），其中聚合物链与它们的偶极子在相反方向上对齐。利用紫外-可见光谱、拉曼光谱、循环伏安法和原子力显微镜对Au表面结合膜进行了表征。量子力学计算确定了PolyPtL 1中每个单体单元的平均偶极矩为约5.8 D。精确的表面衍生化允许有效地调整方向偶极矩，以及所得到的聚合物连接的分子二极管的整流方向。膜1在正偏压区域中更导电，平均整流比（RR = I（+4V）/I（-4V））接近20，而膜2在负偏压区域中更导电，平均整流比（RR = I（-4V）/I（+4 -V））接近18。
A platinum(II)-based, luminescent, metallo-supramolecular polymer (PolyPtL1) having an inherent dipole moment was synthesized via complexation of Pt(II) ions with an asymmetric ligand containing terpyridyl and pyridyl moieties. The synthesized ligand and polymer were well characterized by various NMR techniques, optical spectroscopy, and cyclic voltammetry studies. The morphological study by atomic force microscopy revealed the individual and assembled polymer chains of 1-4 rim height. The polymer was specifically attached on Au-electrodes to produce two types of film (films 1 and 2) in which the polymer chains were aligned with their dipoles in opposite directions. The Au-surface bounded films were characterized by UV-vis, Raman spectroscopy, cyclic voltammetry, and atomic force microscopy study. The quantum mechanical calculation determined the average dipole moment for each monomer unit in PolyPtL1 to be about 5.8 D. The precise surface derivatization permitted effective tuning of the direction dipole moment, as well as the direction of rectification of the resulting polymer-attached molecular diodes. Film 1 was more conductive in positive bias region with an average rectification ratio (RR = I(+4 V)/I(-4 V)) approximate to 20, whereas film 2 was more conducting in negative bias with an average rectification ratio (RR = I(-4 V)/I(+4 -V)) approximate to 18.