Toward heteronuclear supramolecular architectures of pyridine-4-thiolate
Toward heteronuclear supramolecular architectures of pyridine-4-thiolate
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DOI：
10.1039/c2ce26367j
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发表时间：
2012-10
期刊：
影响因子：
3.1
通讯作者：
Biing‐Chiau Tzeng;Chau-Shiung Ding;Tsung-Yi Chang;C. Hu;Gene-Hsiang Lee
中科院分区：
文献类型：
--
作者：
Biing‐Chiau Tzeng;Chau-Shiung Ding;Tsung-Yi Chang;C. Hu;Gene-Hsiang Lee
Pt（d-t-bpy）（S-4-py）2（1; d-t-bpy = 4，4 ′-二叔丁基-2，2 ′-联吡啶，S-4-py =吡啶-4-硫醇盐）与ZnX 2（X = Cl，Br，I）反应生成相应的杂双环[Pt（d-t-bpy）（S-4-py）2（ZnX 2）]2（X = Cl 2，Br 3，I4）.特别是，存在弱的分子间Pt（II）-Pt（II）（2为3.374和3.453 A; 3为3.364和3.452 A）和π <$π（2）3.279和3.490 A; 3.574和3.793 A对于3）相互作用使杂环协同堆叠形成单螺旋链，并且四个单螺旋通过非经典氢键进一步堆叠以得到一种新的四重单螺旋结构。然而，可能由于I的原子尺寸较大，仅具有π <$π相互作用的4不能形成与2和3类似的结构框架。因此，弱Pt（II）-Pt（II）相互作用的存在似乎对这种新结构基序的形成起着至关重要的作用。对于NO3配合物[Pt 2（d-t-bpy）2（S-4-py）4（Zn（NO3））2（μ-O）]n（5），形成一维梯形结构，而不是杂原子结构.因此，一个微妙的阴离子诱导组装已被证明。此外，2-5的发射与Pt（d-t-bpy）（S-4-py）2的发射非常相似，其已被归属为配体到配体电荷转移（LLCT）跃迁，表明Pt（d-t-bpy）（S-4-py）2通过吡啶基-4-硫醇盐配体与Zn（II）离子的配位不会对其LLCT发射造成显著影响。
The reaction of Pt(d-t-bpy)(S-4-py)2 (1; d-t-bpy = 4,4′-di-tert-butyl-2,2′-bipyridine, S-4-py = pyridine-4-thiolate) with ZnX2 (X = Cl, Br, I) gave the respective heteronuclear metallocycles, [Pt(d-t-bpy)(S-4-py)2(ZnX2)]2 (X = Cl 2, Br 3, and I 4). In particular, the presence of weak intermolecular Pt(II)⋯Pt(II) (3.374 and 3.453 A for 2; 3.364 and 3.452 A for 3) and π⋯π (3.279 and 3.490 A for 2; 3.574 and 3.793 A for 3) interactions makes the heteronuclear metallocycles cooperatively stack to form a monohelical chain, and four monohelices are further stacked to give a novel bundle-of-quadruple-monohelix through nonclassical hydrogen bonding. However, 4 having only π⋯π interactions, possibly due to the larger atom size for I, cannot form a similar structural framework as those of 2 and 3. Hence, the presence of weak Pt(II)⋯Pt(II) interactions seems to play a vital role for the formation of such a novel structural motif. For the NO3 complex, [Pt2(d-t-bpy)2(S-4-py)4(Zn(NO3))2(μ-O)]n (5), a one-dimensional ladder structure is formed instead of a heteronuclear metallocycle. Therefore, a delicate anion-induced assembly has been demonstrated. In addition, the emissions of 2–5 are quite similar to that of Pt(d-t-bpy)(S-4-py)2, which has been assigned to a ligand-to-ligand charge-transfer (LLCT) transition, indicating that the coordination to Zn(II) ions through pyridyl-4-thiolate ligands of Pt(d-t-bpy)(S-4-py)2 cannot cause a significant effect on their LLCT emissions.