Octalanthanide wheels supported by p-tert-butylsulfonylcalix[4]arene
Octalanthanide wheels supported by p-tert-butylsulfonylcalix[4]arene
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DOI：
10.1002/anie.200353449
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发表时间：
2004-01-01
影响因子：
16.6
通讯作者：
Miyano, S
中科院分区：
文献类型：
--
作者：
Kajiwara, T;Wu, HS;Miyano, S
GdIII 离子由四个 L4À 和八个 AcOÀ 基团支持。 Gd8簇核的直径(Gd1…Gd1*)为％9.8。 L4À 基团桥接三个 GdIII 离子，从而通过四个 Ophenoxo 原子充当 Gd1 和 Gd3 的四齿配体，并且还通过 Ophenoxo 和一个 Osulfonyl 原子充当 Gd2 和 Gd4 的双齿螯合配体（图 2）。该轮包含两种 AcOÀ 离子，它们都与 Gd2 螯合；一个 AcOÀ 离子通过 μ2-k1O 中的 O15 桥接 Gd1/Gd2； k2O、O®方式，其他桥Gd1/Gd2/Gd3通过μ3-k1O中的O13和O14； k2O，O®； k1O®方式。 Gd4 站点的情况类似。因此，Gd1/Gd2 和 Gd3/Gd4 组中的 GdIII 离子是三重连接的，而 Gd2/Gd3 和 Gd4/Gd1* 是双重连接的。 GdIII 八边形稍微弯曲（图 1 b），与理想平面 À0 存在偏差。 Gd2 为 97，Gd4 为 0.98。 Gd1 和 Gd3 是八配位的，Gd2 和 Gd4 是非配位的，每个配位球由末端配体（例如 EtOH 和 H2O）完成。使用 Sm (AcO) 3· 4 H2O 代替 Gd (Ac-O) 3· 4 H2O，也获得了 Sm8 轮 1о（产率 95%），其与 1 同构（SmÀOphenoxo= 2.255 (3)–2.509 (3)）。[8]Nd (AcO) 3· 4 H2O 和 H4L 的类似反应在EtOH/CHCl 3 中以2:1的比例，然后从MeOH/CHCl 3 重结晶，得到[Nd8(L) 4 (AcO) 8-(MeOH) 4 (H 2 O) 8](2)晶体。 2的结构与1类似（图3），不同之处在于2以四方晶系结晶，并且分子中只有1/8是晶体学独立的。 L4À 离子通过四个 Ophenoxo 连接充当 Nd1 的四齿配体，并且还通过 Ophenoxo 原子和 Osulfonyl 原子充当 Nd2 和 Nd2* 的双齿配体（图 2）。 Nd8 簇核由 μ2-k1O 中的八个乙酸基团完成； k1O® 或 μ3-k1O； k2O，O®； k1O®方式。 Nd8磁芯的直径为%10.5。 2 中的 Nd8 磁芯比 1 中的 Gd8 磁芯更平坦（图 3），与 Nd1 的理想平面的偏差为 0.2296 (2)。 Pr8 轮 2® 也通过使用 Pr (AcO) 3· 42O (32%
GdIII ions supported by four L4À and eight AcOÀ groups. The diameter of the Gd8 cluster core (Gd1··· Gd1*) is% 9.8. The L4À groups bridge three GdIII ions, thus acting as a tetradentate ligand for Gd1 and Gd3 via four Ophenoxo atoms, and also acting as a bisbidentate chelating ligand for Gd2 and Gd4 via an Ophenoxo and an Osulfonyl atom (Figure 2). The wheel involves two kinds of AcOÀ ions, which both chelate to Gd2; one AcOÀ ion bridges Gd1/Gd2 via O15 in a μ2-k1O; k2O, Oо manner, and the other bridges Gd1/Gd2/Gd3 via O13 and O14 in a μ3-k1O; k2O, Oо; k1Oо manner. The situation is similar at the Gd4 site. As a result, GdIII ions in sets of Gd1/Gd2 and Gd3/Gd4 are triply connected, whereas Gd2/Gd3 and Gd4/Gd1* are doubly connected. The GdIII octagon is slightly bent (Figure 1 b) giving deviations from the ideal plane of À0. 97 for Gd2 and 0.98 for Gd4. Gd1 and Gd3 are octacoordinated and Gd2 and Gd4 are nonacoordinated, with each coordination sphere completed by terminal ligands such as EtOH and H2O. Using Sm (AcO) 3· 4 H2O instead of Gd (Ac-O) 3· 4 H2O, a Sm8 wheel 1о was also obtained (95% yield) which is isostructural to 1 (SmÀOphenoxo= 2.255 (3)–2.509 (3)).[8]A similar reaction of Nd (AcO) 3· 4 H2O and H4L in 2: 1 ratio in EtOH/CHCl3 followed by recrystallization from MeOH/CHCl3 gave crystals of[Nd8 (L) 4 (AcO) 8-(MeOH) 4 (H2O) 8](2). The structure of 2 is similar to 1 (Figure 3) except that 2 crystallized in a tetragonal crystal system and only 1/8 of the molecule is crystallographically independent. The L4À ion acts as a tetradentate ligand for Nd1 via four Ophenoxo linkages, and also acts as a bisbidentate ligand for Nd2 and Nd2* via an Ophenoxo atom and an Osulfonyl atom (Figure 2). The Nd8 cluster core is completed by eight acetate groups in either a μ2-k1O; k1Oо or a μ3-k1O; k2O, Oо; k1Oо manner. The diameter of the Nd8 core is% 10.5. In 2, the Nd8 core is flatter than the Gd8 core in 1 (Figure 3), with a deviation from the ideal plane of 0.2296 (2) for Nd1. A Pr8 wheel 2о was also obtained by the use of Pr (AcO) 3· 42O (32%