De Soumen, Pramanik Susnata, Schmittel Michael
Center of Micro and Nanochemistry and Engineering, Organische Chemie I, Universität Siegen, Adolf-Reichwein-Str. 2, D-57068 Siegen, Germany.
Dalton Trans. 2014 Jul 28;43(28):10977-82. doi: 10.1039/c4dt01508h.
A triangular framework with a terpyridine and shielded phenanthroline at its termini constitutes an open/close nanoswitch that is toggled by chemical inputs. In the presence of copper(I) ions, the open triangular framework (OPEN-I) firmly closes to a catalytically inactive heteroleptic Cu(phen)(terpy) complex (CLOSE). Reversible switching between CLOSE and OPEN-I states was demonstrated by successive addition and removal of Cu(+). In contrast, after addition of iron(II) ions to the CLOSE state a bishomoleptic dimeric Fe(terpy)2 complex is formed with the copper(I) ions placed in the phenanthroline cavities (OPEN-II). Due to its coordinatively unsaturated Cu(Phen) sites the dimeric iron complex is able to serve as a catalyst in the cyclopropanation of Z-cyclooctene using ethyl diazoacetate.
一种在其末端带有三联吡啶和屏蔽菲咯啉的三角形框架构成了一个可通过化学输入进行切换的开/关纳米开关。在存在铜（I）离子的情况下，开放的三角形框架（OPEN-I）会牢固地关闭形成催化无活性的杂配体[Cu(phen)(terpy)]⁺配合物（CLOSE）。通过连续添加和去除Cu⁺证明了CLOSE和OPEN-I状态之间的可逆切换。相比之下，在向CLOSE状态添加铁（II）离子后，会形成一种双同配体二聚体[Fe(terpy)₂]²⁺配合物，其中铜（I）离子位于菲咯啉腔内（OPEN-II）。由于其二聚体铁配合物具有配位不饱和的[Cu(Phen)]⁺位点，它能够在使用重氮乙酸乙酯的Z-环辛烯环丙烷化反应中作为催化剂。
