A rock-salt-like lattice structure consisting of monocationic and monoanionic AuIAgICuII supramolecular cages of D-penicillaminate.
A rock-salt-like lattice structure consisting of monocationic and monoanionic AuIAgICuII supramolecular cages of D-penicillaminate.
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DOI：
10.1002/anie.200462205
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发表时间：
2005-02
影响因子：
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通讯作者：
Atsushi Toyota;Tadashi Yamaguchi;A. Igashira-Kamiyama;Tatsuya Kawamoto;T. Konno
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文献类型：
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作者：
Atsushi Toyota;Tadashi Yamaguchi;A. Igashira-Kamiyama;Tatsuya Kawamoto;T. Konno
6AgI 9S12核心结构。簇3b的结构似乎与簇3a的结构几乎相同(图2)，该簇还在笼子的中心包裹了一个氯原子(av Ag∑∑∑Cl 3.140(5)ä)。然而，在3b中，由三个[Au2Ag2(d-PEN-S)4]4个单元(Av Au？S 2.298(5)，Ag？S 2.472(5)ä，S-Au-S 173.5(2)，S-Ag-S 157.2(2)8)和六个CuII离子组成的笼子被两个[Ag(H2O)]+部分(av Ag？S 2.534(6)，Ag？O2.34(2)ä)结合，它们在三个位置中的两个无序，而不是3a中的三个[AgCl]0部分。因此，3b由6个AuI、8个AgI和6个CuII离子与12个d-Pen 2？配体、1个C l？原子和2个H_2O分子组成，构成一个20核的单阳离子笼状结构。在3b中，6个反式CuN2O2平面中只有3个被顶端水分子(CuO2.30(1)ä)配位，每个分子都与相邻的3a(O∑∑∑O2.85(2)ä)单阴离子团簇的羧基O原子形成氢键。[8]其余三个反式CuN2O2平面的顶端位置被来自三个不同单阴离子团簇的三个CoO_2基团所束缚，它们的铜氧距离为2.38(1)ä。因此，单阴离子和单阳离子笼状簇合物相互连接，使得每个阴离子/阳离子笼状物被六个阳离子/阴离子笼状物八面体包围，形成一种岩盐式晶格结构，其体积约为氯化钠的200倍(图3)。此外，还观察到了一个很弱的半场跃迁带，这表明相邻的两个CuII中心之间存在弱的磁交换相互作用。[10]在2-300K的温度范围内，3的磁测量揭示了CuII中心之间相互作用的弱反铁磁性特征。CMT-T图几乎不变
6AgI 9S12 core structure. The structure of cluster 3b, which also encapsulates a Cl¿ atom at the center of the cage (av Ag∑∑∑ Cl 3.140 (5) ä), appears to be virtually the same as that of cluster 3a (Figure 2). However, in 3b the cage consisting of three [Au2Ag2 (d-pen-S) 4] 4¿ units (av Au¿ S 2.298 (5), Ag¿ S 2.472 (5) ä, S-Au-S 173.5 (2), S-Ag-S 157.2 (2) 8) and six CuII ions is bound by two [Ag (H2O)]+ moieties (av Ag¿ S 2.534 (6), Ag¿ O 2.34 (2) ä), which are disordered in two of three positions, in place of three [AgCl] 0 moieties in 3a. Thus, 3b is composed of 6 AuI, 8 AgI, and 6 CuII ions in combination with 12 d-pen2¿ ligands, one Cl¿ atom, and two H2O molecules, which construct a 20-nuclear monocationic cage structure. In 3b only three of six trans-CuN2O2 planes are coordinated by apical water molecules (Cu¿ O 2.30 (1) ä), each of which forms a hydrogen bond to the carboxylato O atom of the adjacent monoanionic cluster of 3a (O∑∑∑ O 2.85 (2) ä).[8] The apical positions of the remaining three trans-CuN2O2 planes are bound by three COO¿ groups from three different monoanionic clusters with a Cu¿ O distance of 2.38 (1) ä. As a result, the monoanionic and monocationic cage clusters are connected to each other such that each anionic/cationic cage is octahedrally surrounded by six cationic/anionic cages to form a rock-salt-like lattice structure with a volume that is about 200 times larger than that of NaCl (Figure 3).[8, 9] The EPR spectrum of a solid sample of 3 at 77 K displays a simple isotropic signal with g= 2.12, consistent with the presence of CuII ions. Furthermore, a very weak half-field transition band is observed, which is indicative of the presence of a weak magnetic exchange interaction between two adjacent CuII centers.[10] The weak antiferromagnetic character of the interaction between CuII centers was revealed by the magnetic measurements for 3 in the temperature range of 2 to 300 K. The plot of cmT versus T is almost constant in