Allosteric Cofacial Porphyrin Complexes超分子变构cofacial卟啉配合物课件.ppt

Supramolecular Allosteric Cofacial Porphyrin Complexes Christopher G. Oliveri, Nathan C. Gianneschi, SonBinh T. Nguyen,*, Chad A. Mirkin,*, Charlotte L. Stern, Zdzislaw Wawrzak,and Maren Pink Allosteric Recognition Introduction-Porphyrin Supramolecular Coordination Chemistry The Directional-Bonding Approach The Symmetry-Interaction Approach The Weak-Link Approach Catalytic Acyl Transfer by a Cyclic Porphyrin Trimer Design of Allosteric Porphyrin-Based Supramolecules NMR Data of 14a and 14b Catalytic efficiency of 4-PC 15a：14a = 2：1 15a：monomer = 14：1 14a is probably dynamic when in solution and the observed catalytic activity may originate from the conformational flexibility around the S atoms. Catalytic efficiency of 3-PC Drop slightly with respect to 4-PC = the cavities of 14a and 15a are still flexible enough to accommodate the change in transition state distance for acyl transfer from acetylimidazole upon binding. Catalytic efficiency of 2-PC Drop significantly with respect to 3-PC and 4-PC Similar to those observed for the monomer = Unfavorable transition state (in comparison to those for 3-PC and 4-PC) for productive acyl transfer. Conclusion They have developed a coordination chemistrybased synthetic approach for the quantitative preparation of flexible cofacial porphyrin assemblies in which the porphyrins act as functional sites within an allosteric framework that istunable via modulation of peripheral structure control domains. This capability enables the cofacial porphyrin structuresto act as allosteric catalysts capable of discriminatingdifferent substrate combinations and selectively transformingthem into the desired products. Homework 1. paper中所合成出來的的15a及14b其催化機制是？ Ans： 2. Weak-link approach (WLA)其transition metal的選擇為？ Ans：Transition metal通常使用晚期過渡金屬，如Rh(Ι)及Pd(ΙΙ)，其可以和磷產生強建結而和醚基及硫醚基產生弱建結1。通常依照欲合成出的macrocycle來選定transition metal，這些性質有空氣和水的敏感性、電荷、孔洞的形狀小分子的反應性等等。常用的有d8的Rh(Ι)的平面四方結構，d10的Cu(Ι)四方角錐結構，d6的八面角錐結構。 Table 1. X-ray Crystallographic Data for