Molecular Networks Based on CN Coordination Bonds
Molecular Networks Based on CN Coordination Bonds
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DOI：
10.1002/ejic.201200427
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发表时间：
2012-11-01
影响因子：
2.3
通讯作者：
Voss, Karsten
中科院分区：
文献类型：
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作者：
Karsch, Markus;Lund, Henrik;Voss, Karsten
本研究探讨了利用四面体[E(O-C6X4-CN)(4)]（-）阴离子（E = B, Al; X = H， F）作为阴离子连接剂，由四面体NaBH4/LiAlH4和HO-C6X4-CN反应合成，用于生成二维和三维晶体配位聚合物网络。这种聚合物网络是通过四面体对氰苯氧铝酸盐或硼酸盐连接剂与单离子金属中心（Li+, Na+， Ag+和Cu+）连接而得到的。这些研究特别集中在这些聚合物的合成、结构和稳定性上。此外，使用全氟化O-C6F4-CN连接剂研究了电子影响。含全氟[E(O-C6F4-CN)(4)]（-）阴离子的盐在加入路易斯酸(B(C6F5)(3)时也会分解成E(O-C6F4-CN)(3)和[O-C6F4-CN]（-）。此外，B(C6F5)(3)的加成导致分子离子对的形成，因为氰基现在完全或部分被阻断。讨论了M[Al(O-C6H4-CN)(4)] （M = Li, Ag, Cu）、Na[B(O-C6H4-CN)(4)]和Li[Al(O-C6H4-CN)(4)]的结构以及分解产物Na（O-C6F4-CN）、（THF）Al[O-C6H4-CN中心点B(C6F5)(3)]（THF =四氢呋喃）、Na[(F5C6)(3)B中心点O-C6H4-CN中心点B(C6F5)(3)]和Li[NC-C6F4-O-Al{O-C6F4-CN中心点B(C6F5)(3)}(3)]的结构。
This study examines the use of tetrahedral [E(O-C6X4-CN)(4)](-) anions (E = B, Al; X = H, F), which can be synthesized from the reaction of tetrahedral NaBH4/LiAlH4 and HO-C6X4-CN, as anionic linkers for the generation of 2D and 3D crystalline coordination polymer networks. Such polymer networks were obtained by the connection of tetrahedral p-cyanophenoxy aluminate or borate linkers with monocationic metal centers such as Li+, Na+, Ag+, and Cu+. These studies are specifically focused on the synthesis, structure, and stability of such polymers. Additionally, the perfluorinated O-C6F4-CN linker was used to study electronic influences. Salts bearing the perfluorinated [E(O-C6F4-CN)(4)](-) anion decompose into E(O-C6F4-CN)(3) and [O-C6F4-CN](-), which is also observed when a Lewis acid such as B(C6F5)(3) is added. Moreover, addition of B(C6F5)(3) leads to the formation of molecular-ion pairs because the cyano groups are now either completely or partly blocked. The structures of M[Al(O-C6H4-CN)(4)] (M = Li, Ag, Cu), Na[B(O-C6H4-CN)(4)], and Li[Al(O-C6F4-CN)(4)] as well as of the decomposition products Na(O-C6F4-CN), (THF)Al[O-C6H4-CN center dot B(C6F5)(3)](3) (THF = tetrahydrofuran), Na[(F5C6)(3)B center dot O-C6H4-CN center dot B(C6F5)(3)], and Li[NC-C6F4-O-Al{O-C6F4-CN center dot B(C6F5)(3)}(3)] are discussed.