Triphenylene-Bridged Trinuclear Complexes of Cu: Models for Spin Interactions in Two-Dimensional Electrically Conductive MOFs.
Triphenylene-Bridged Trinuclear Complexes of Cu: Models for Spin Interactions in Two-Dimensional Electrically Conductive MOFs.
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DOI：
10.1021/jacs.9b04822
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发表时间：
2019-06
影响因子：
15
通讯作者：
Luming Yang;Xin He;M. Dincǎ
中科院分区：
文献类型：
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作者：
Luming Yang;Xin He;M. Dincǎ
2，3，6，7，10，11-六羟基苯并菲和2，3，6，7，10，11-六氨基苯并菲与[Cu（Me 3 tacn）]2+的反应（Me 3 tacn = 1，4，7-三甲基-1，4，7-三氮杂环壬烷）生成三角形三铜络合物[（Me 3 tacnCu）3（HOTP）]3+（1）和[（Me 3 tacnCu）3（HITP）]4+（2）（HOTP，HITP分别=六氧基和六亚氨基苯并菲）。这些三核配合物是二维导电金属有机框架（MOFs）铜六氧苯并菲（Cu 3 HOTP 2）和铜六亚氨基苯并菲（Cu 3 HITP 2）中自旋交换相互作用的分子模型。而络合物1与HOTP 3 β分离，HOTP 3 β具有与在氧桥连的MOF中发现的相同的氧化态，在Cu 3 HITP 2中发现的三重氧化的HITP 3 β相对于分子模型中的反硝化是不稳定的。事实上，磁性测量揭示配体为中心的自由基字符1和2的闭壳结构，与配体的氧化还原状态。所有相邻的自旋在1和2中反铁磁耦合。这些结果有助于探测导电MOFs中的金属-配体-金属相互作用，并为其他具有离域电子的二维材料的合成提供潜在的灵感。
Reaction of 2,3,6,7,10,11-hexahydroxytriphenylene (HHTP) and 2,3,6,7,10,11-hexaaminotriphenylene (HATP) with [Cu(Me3tacn)]2+ (Me3tacn = 1,4,7-trimethyl-1,4,7-triazacyclononane) produces trigonal tricopper complexes [(Me3tacnCu)3(HOTP)]3+ (1) and [(Me3tacnCu)3(HITP)]4+ (2) (HOTP, HITP = hexaoxy- and hexaimino-triphenylene, respectively). These trinuclear complexes are molecular models for spin exchange interactions in the two-dimensional conductive metal-organic frameworks (MOFs) copper hexaoxytriphenylene (Cu3HOTP2) and copper hexaiminotriphenylene (Cu3HITP2). Whereas complex 1 is isolated with HOTP3‒ bearing the same oxidation state as found in the oxy-bridged MOF, the triply oxidized HITP3‒ found in Cu3HITP2 is unstable with respect to disproportionation in the molecular model. Indeed, magnetic measurements reveal ligand-centered radical character for 1 and a closed-shell structure for 2, in agreement with the redox state of the ligands. All neighboring spins are antiferromagnetically coupled in 1 and 2. These results help probe metal-ligand-metal interactions in conductive MOFs and provide potential inspiration for the synthesis of other two-dimensional materials with delocalized electrons.