Framework engineering by anions and porous functionalities of Cu(II)/4,4′-bpy coordination polymers
Framework engineering by anions and porous functionalities of Cu(II)/4,4′-bpy coordination polymers
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DOI：
10.1021/ja0113192
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发表时间：
2002-03-20
影响因子：
15
通讯作者：
Yamashita, M
中科院分区：
文献类型：
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作者：
Noro, S;Kitaura, R;Yamashita, M
框架构建体（铜（II）离子和4,4'-联吡啶（4,4'-bpy）配体）与框架调节剂（AF(6)型阴离子；A = Si、Ge和P）的组合提供了一系列新型多孔配位聚合物。高度多孔的配位聚合物{[Cu(AF(6))(4,4'-bpy)(2)]·8H(2)O}(n)（A = Si（1a·8H(2)O），Ge（2a·8H(2)O））通过使用AF(6)²⁻阴离子形成坚固的三维（3 - D）微孔网络（3 - D规则网格）。这些配合物沿c轴的通道尺寸约为8×8埃²，沿a轴或b轴为6×2埃²。当化合物1a·8H(2)O或2a·8H(2)O浸入水中时，三维网络（1a·8H(2)O或2a·8H(2)O）转变为互穿网络{[Cu(4,4'-bpy)₂(H₂O)₂]·AF(6)}(n)（A = Si（1b）和Ge（2b））（二维互穿）。这种二维互穿网络1b显示出独特的动态阴离子交换特性，并伴随着剧烈的结构转变。当使用PF₆⁻单阴离子而非AF(6)²⁻二阴离子作为框架调节剂以及另一种共存阴离子时，得到了具有各种框架类型的多孔配位聚合物，{[Cu₂(4,4'-bpy)₅(H₂O)₄]·阴离子·2H(2)O·4EtOH}(n)（阴离子 = 4PF₆⁻（3·2H(2)O·4EtOH），2PF₆⁻ + 2ClO₄⁻（4·2H(2)O·4EtOH））（二维双层），{[Cu₂(PF₆)(NO₃)(4,4'-bpy)₄]·2PF₆·2H(2)O}(n)（5·2PF₆·2H(2)O）（三维起伏网格），{[Cu(PF₆)(4,4'-bpy)₂(MeCN)]·PF₆·2MeCN}(n)（6·2MeCN）（二维网格）和{[Cu(4,4'-bpy)₂(H₂O)₂]·PF₆·BF₄}(n)（7）（二维网格），其中观察到了PF₆⁻阴离子的三种模式。5·2PF₆·2H(2)O具有罕见的PF₆⁻桥。PF₆⁻和NO₃⁻单阴离子交替连接到[Cu(4,4'-bpy)₂](n)的起伏二维片层中的铜（II）中心，形成三维多孔网络。游离的PF₆⁻阴离子包含在通道中。6·2MeCN同时具有游离的和末端桥连的PF₆⁻阴离子。3·2H(2)O·4EtOH、4·2H(2)O·4EtOH和7含有游离的PF₆⁻阴离子。3 - 2H(2)O·4EtOH和4·2H(2)O·4EtOH中的所有阴离子都自由地位于由主体网络构建的通道中。有趣的是，这些铜（II）框架可通过抗衡阴离子合理控制，并选择性地转变为其他框架。
A combination of framework-builder (Cu(II) ion and 4,4'-bipyridine (4,4'-bpy) ligand) and framework-regulator (AF(6) type anions; A = Si, Ge, and P) provides a series of novel porous coordination polymers. The highly porous coordination polymers {[Cu(AF(6))(4,4'-bpY)(2)].8H(2)O}(n) (A = Si (1a-8H(2)O), Ge (2a.8H(2)O)) afford robust 3-dimensional (3-D), microporous networks (3-D Regular Grid) by using AF(6)(2)-anions. The channel size of these complexes is ca. 8 x 8 Angstrom(2) along the c-axis and 6 x 2 Angstrom(2) along the a-or b-axes. When compounds 1a.8H(2)O or 2a.8H(2)O were immersed in water, a conversion of 3-D networks (1a.8H(2)O or 2a.8H(2)O) to interpenetrated networks {[Cu(4,4'-bpy)2(H2O)(2)].AF(6)}(n) (A = Si (1b) and Ge (2b)) (2-D Interpenetration) took place. This 2-D interpenetrated network 1b shows unique dynamic anion-exchange properties, which accompany drastic structural conversions. When a PF6- monoanion instead of AF(6)(2-) dianions was used as the framework-regulator with another co-counteranion (coexistent anions), porous coordination polymers with various types of frameworks, {[Cu-2(4,4'-bpy)(5)(H2O)(4)].anions-2H(2)O.4EtOH}(n) (anions= 4PF(6)(-) (3.2H(2)O-4EtOH), 2PF(6) +2ClO(4)(-)(4.2H(2)O-4EtOH))(2-DDouble-Layet),{[CU2-(PF6)(NO3)(4,4'-bPY)(4)].2PF(6).2H(2)O}(n) (5.2PF(6).2H(2)O) (3-D Undulated Grid), {[Cu(PF6)(4,4'-bPY)(2)(MeCN)].PF6.2MeCN}(n) (6.2MeCN) (2-D Grid), and {[Cu(4,4'-bpy)(2)(H2O)(2)].PF6.BF4}(n) (7) (2-D Grid), were obtained, where the three modes of PF6- anions are observed. 5.2PF(6).2H(2)O has rare PF6- bridges. The PF6- and NO3- monoanions alternately link to the Cu(II) centers in the undulated 2-D sheets of [Cu(4,4'-bPY)(2)](n) to form a 3-D porous network. The free PF6- anions are included in the channels. 6.2MeCN affords both free and terminal-bridged PF6- anions. 3.2H(2)O.4EtOH, 4.2H(2)O.4EtOH, and 7 bear free PF6- anions. All of the anions in 3-2H(2)O.4EtOH and 4.2H(2)O.4EtOH are freely located in the channels constructed from a host network. Interestingly, these Cu(II) frameworks are rationally controlled by counteranions and selectively converted to other frameworks.