Phosphorescent Decanuclear Bimetallic Pt6M4 (M = Zn, Fe) Tetrahedral Cages
Phosphorescent Decanuclear Bimetallic Pt6M4 (M = Zn, Fe) Tetrahedral Cages
复制标题
磷光十核双金属 Pt6M4（M = Zn、Fe）四面体笼
DOI：
10.1021/acs.inorgchem.7b00501
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发表时间：
2017
影响因子：
4.6
通讯作者：
Cook Timothy R.
中科院分区：
文献类型：
--
作者：
Zhang Yuzhen;Crawley Matthew R.;Hauke Cory E.;Friedman Alan E.;Cook Timothy R.
协调驱动的自组装提供了离散的纳米级结构，可以保留或增强其母体构件的物理化学性质。在此，我们报道了两种四面体笼的合成、表征和光物理性质，[ZnII4L6](PF6)8(C1)和[FeII4L6](OTf)8(C2)，其中L= PtII(PEt3)2(CC-bpy)2(PEt3=三乙基膦；CC-bpy = 5-乙炔基-2,2'-联吡啶）和OTf = 三氟甲磺酸盐。通过用3当量的L处理2当量的Zn(NO3)2·6H2O或Fe(OTf)2，分别以72%和81%的分离产率组装C1和C2。两种笼均通过核磁共振、电喷雾电离质谱和单晶 X 射线衍射 (SCXRD) 进行了全面表征。每个聚吡啶金属节点的局部D3对称性增加了存在多个异构笼的可能性；然而，基于 1 H NMR 和 SCXRD，仅形成纯手性对映体（ΔΔΔΔ 和 ΛΛΛΛ）。C1 在 25 °C 的 N2 脱气乙腈中表现出中心位于 545 nm 的磷光，量子产率为 10%。由于 FeII 节点引入的 5MC（MC = 金属中心）态的非辐射弛豫，C2 的量子产率显着降低。
Coordination-driven self-assembly delivers discrete, nanoscopic architectures that may preserve or enhance the physicochemical properties of their parent building blocks. Herein, we report the syntheses, characterization, and photophysical properties of two tetrahedral cages, [ZnII4L6](PF6)8(C1) and [FeII4L6](OTf)8(C2), whereL= PtII(PEt3)2(CC-bpy)2(PEt3= triethylphosphine; CC-bpy = 5-ethynyl-2,2′-bipyridine) and OTf = trifluoromethanesulfonate.C1andC2were assembled in isolated yields of 72% and 81% by treating 2 equiv of Zn(NO3)2·6H2O or Fe(OTf)2with 3 equiv ofL, respectively. Both cages were fully characterized by NMR, electrospray ionization mass spectrometry, and single-crystal X-ray diffraction (SCXRD). The localD3symmetry at each polypyridyl metal node raises the possibility of a number of isomeric cages; however, only the homochiral enantiomers (ΔΔΔΔ and ΛΛΛΛ) are formed based on1H NMR and SCXRD.C1exhibits phosphorescence centered at 545 nm with a quantum yield of 10% in N2-degassed acetonitrile at 25 °C. The quantum yield ofC2is significantly lower due to a nonradiative relaxation from5MC (MC = metal-centered) states introduced by the FeIInodes.