Matsuoka Ryota, Toyoda Ryojun, Sakamoto Ryota, Tsuchiya Mizuho, Hoshiko Ken, Nagayama Tatsuhiro, Nonoguchi Yoshiyuki, Sugimoto Kunihisa, Nishibori Eiji, Kawai Tsuyoshi, Nishihara Hiroshi
Department of Chemistry , Graduate School of Science , The University of Tokyo , 7-3-1, Hongo , Bunkyo-ku , Tokyo 113-0033 , Japan . Email:
Graduate School of Materials Science , Nara Institute of Science and Technology (NAIST) , 8916-5 Takayama, Ikoma , Nara 630-0192 , Japan.
Chem Sci. 2015 May 1;6(5):2853-2858. doi: 10.1039/c5sc00273g. Epub 2015 Feb 26.
One-dimensional coordination polymers (1D-CPs) tend either to dissociate into constitutive ligands and metals readily in solution, or to aggregate randomly and amorphously, which prevents them from widespread application. In the present research, 1D-CPs comprising bridging dipyrrin ligands and divalent metal ions (Zn, Ni, and Cu) are synthesized. A liquid/liquid interfacial reaction gives rise to single crystals suitable for X-ray diffraction analysis: A dichloromethane solution of the ligand is layered with aqueous metal(ii) acetate, such that the coordination reaction proceeds at the liquid/liquid interface. Isolated single fibers of the zinc coordination polymer may be exfoliated from the single crystal or bulk solid upon ultrasonication. Atomic force microscopy (AFM) detects the isolated fibers with lengths of more than several μm. The exfoliated 1D-CP wires feature good processability, realizing a conjugate with single-wall carbon nanotubes (SWCNTs), and a thin film on a transparent SnO electrode. The processed materials show electric conversion ability: For example, the modified SnO electrode serves as a photoanode for a photoelectric conversion system. The designability and tunability of the present 1D-CPs is demonstrated by a ligand modification, affording a luminescent property and an extension of the photoelectric conversion response to longer wavelengths.
一维配位聚合物(1D-CPs)在溶液中往往容易解离成组成配体和金属,或者随机无定形聚集,这阻碍了它们的广泛应用。在本研究中,合成了包含桥连二吡咯配体和二价金属离子(锌、镍和铜)的一维配位聚合物。液/液界面反应产生适合X射线衍射分析的单晶:配体的二氯甲烷溶液与金属(II)乙酸盐水溶液分层,使得配位反应在液/液界面进行。超声处理后,锌配位聚合物的孤立单纤维可从单晶或块状固体上剥落。原子力显微镜(AFM)检测到长度超过几微米的孤立纤维。剥落的一维配位聚合物线具有良好的加工性能,实现了与单壁碳纳米管(SWCNTs)的共轭以及在透明SnO电极上形成薄膜。加工后的材料具有电转换能力:例如,改性的SnO电极用作光电转换系统的光阳极。通过配体修饰证明了本一维配位聚合物的可设计性和可调性,赋予了发光特性并将光电转换响应扩展到更长波长。