Coordination number incommensurate cluster formation, part 21 -: Design, formation and properties of tetrahedral M4L4 and M4L6 supramolecular clusters
Coordination number incommensurate cluster formation, part 21 -: Design, formation and properties of tetrahedral M4L4 and M4L6 supramolecular clusters
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DOI：
10.1021/ja0104507
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发表时间：
2001-09-19
影响因子：
15
通讯作者：
Raymond, KN
中科院分区：
文献类型：
--
作者：
Caulder, DL;Brückner, C;Raymond, KN
刚性的三-和二（儿茶酚酰胺）配体H（6）A、H4 B和H4 C通过与三价和四价金属离子如Ga-III、Fe-III、Ti-IV和Sn-IV的自组装反应形成M4 L4和M4 L 6类型的四面体簇。一般的设计原则，这种集群的合成与几何要求和动力学和热力学考虑的重点。这些配合物的溶液和固态表征，并描述其动态溶液行为。三-邻苯二酚酰胺H（6）A与Ga-III、Ti-IV和Sn-IV形成M4 L4四面体;（Et 3 N）（8）[Ti（4）A（4）]在柱c（编号167）上以R（3）结晶，a = 22.6143（5）埃，c = 106.038（2）埃。该簇是同构型的外消旋混合物。四面体（在给定簇内的金属中心处的所有Delta或所有A）。虽然簇合物的合成过程明显依赖于金属，但广泛的电喷雾质谱研究表明，M（4）A（4）（M = Ga-III，Ti-IV和Sn-IV）簇合物一旦形成就非常稳定。本文提出了形成M_4L_6四面体团簇的两种途径。在双（儿茶酚酰胺）配体中，H4 B基于“边上”设计形成M4 L 6四面体（M = Ga-III），而H4 C基于“面上”策略形成M4 L 6四面体（M = Ga-III，Fe-III）。K-5[Et 4 N]（7）[Fe 4C 6]在I（4）中在棒3d（No.220）上结晶，a = 43.706（8）埃。该M4 L 6四面体簇也是同构型四面体的外消旋混合物，并且具有足够大的空腔以封装Et 4 N+的分子。这种主客体相互作用保持在溶液中所揭示的Ga-III复合物的NMR研究。
The rigid tris- and bis(catecholamide) ligands H(6)A, H4B and H4C form tetrahedral clusters of the type M4L4 and M4L6 through self-assembly reactions with tri- and tetravalent metal ions such as Ga-III, Fe-III, Ti-IV and Sn-IV. General design principles for the synthesis of such clusters are presented with an emphasis on geometric requirements and kinetic and thermodynamic considerations. The solution and solid-state characterization of these complexes is presented, and their dynamic solution behavior is described. The tris-catecholamide H(6)A forms M4L4 tetrahedra with Ga-III, Ti-IV, and Sn-IV; (Et3N)(8)[Ti(4)A(4)] crystallizes in R(3) over bar c (No. 167), with a = 22.6143(5) Angstrom, c = 106.038(2) Angstrom. The cluster is a racemic mixture of homoconfigurational. tetrahedra (all Delta or all A at the metal centers within a given cluster). Though the synthetic procedure for synthesis of the cluster is markedly metal-dependent, extensive electrospray mass spectrometry investigations show that the M(4)A(4) (M = Ga-III, Ti-IV, and Sn-IV) clusters are remarkably stable once formed. Two approaches are presented for the formation Of M4L6 tetrahedral clusters. Of the bis(catecholamide) ligands, H4B forms an M4L6 tetrahedron (M = Ga-III) based on an "edge-on" design, while H4C forms an M4L6 tetrahedron (M = Ga-III, Fe-III) based on a "face-on" strategy. K-5[Et4N](7)[Fe4C6] crystallizes in I (4) over bar 3d (No. 220) with a = 43.706(8) Angstrom. This M4L6 tetrahedral cluster is also a racemic mixture of homoconfigurational tetrahedra and has a cavity large enough to encapsulate a molecule of Et4N+. This host-guest interaction is maintained in solution as revealed by NMR investigations of the Ga-III complex.