A Lifetime Walk in the Realm of Cyclam
A Lifetime Walk in the Realm of Cyclam
复制标题
在仙客来的王国里度过一生
DOI：
10.1002/9781119053859.ch8
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发表时间：
2016
期刊：
影响因子：
--
通讯作者：
L. Fabbrizzi
中科院分区：
文献类型：
--
作者：
L. Fabbrizzi
14元大环环体是为喜欢四方配位的过渡金属离子（如NiII， CuII）量身定制的配体。特别是，cyclam能够将其四个胺氮原子定位在正方形的角上，从而提供非常强的配位相互作用。环环酮的预组织和封闭排列使其配合物具有很高的热力学和动力学稳定性，既不能在强酸性溶液中脱金属，也不能在高度竞争的配体存在下脱金属，并且可以达到不稳定的氧化态（NiIII, NiI, CuIII, AgII, AgIII, HgIII）。所有这些特征对于不同原子度的四胺大环的金属配合物（12 - 16），包括其他14元的大环异环，形成一个5,5,6,6序列的螯合环（而环环则形成5,6,5,6序列），如果不排除的话，则不那么明显。NiIIand cuiii对cyclam的配位非常满意，他们倾向于配位配体与不同片段的反应，通过模板途径获得类似cyclam的大环配合物。cyclam与各种亚基的功能化产生了各种各样的器件，其中包括用于在液体有机膜上交叉传输电子和阴离子的载体和荧光开关，两者都由NiII/NiIIIredox偶对操作。
The 14‐membered macrocycle cyclam is the tailor made ligand for transition metal ions loving tetragonal coordination, e. g. NiII, CuII. In particular, cyclam is able to position its four amine nitrogen atoms at the corners of a square, thus providing very strong coordinative interactions. Preorganization and closed arrangement of cyclam impart high thermodynamic and kinetic stability to its complexes, which cannot be demetallated neither in a strongly acidic solution nor in the presence of highly competitive ligands, and which can achieve otherwise unstable oxidation states (NiIII, NiI, CuIII, AgII, AgIII, HgIII). All these features are much less pronounced, if not precluded, to metal complexes of tetra‐amine macrocyles of different atomicity, 12 to 16, including the other 14‐membered macrocycle isocyclam, which forms a 5,5,6,6 sequence of chelate rings (whereas cyclam gives a 5,6,5,6 sequence). NiIIand CuIIare so happy with coordination by cyclam that they favour the reaction of a coordinate ligand with different fragments to give cyclam‐like macrocyclic complexes through a template route. Functionalisation of cyclam with a variety of subunits gives rise to a variety of devices, which include a carrier for the cross transport of electrons and anions across a liquid organic membrane and a fluorescence switch, both operated by the NiII/NiIIIredox couple.
影响因子：
18.3
作者：
Shokeen M;Anderson CJ
通讯作者：
Anderson CJ
影响因子：
64.8
作者：
Cho, Jaeheung;Jeon, Sujin;Wilson, Samuel A.;Liu, Lei V.;Kang, Eun A.;Braymer, Joseph J.;Lim, Mi Hee;Hedman, Britt;Hodgson, Keith O.;Valentine, Joan Selverstone;Solomon, Edward I.;Nam, Wonwoo
通讯作者：
Nam, Wonwoo
影响因子：
20.3
作者：
Liles, WC;Broxmeyer, HE;Dale, DC
通讯作者：
Dale, DC