Triphenylene-Bridged Trinuclear Complexes of Cu: Models for Spin Interactions in Two-Dimensional Electrically Conductive MOFs,Journal of the American Chemical Society

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Triphenylene-Bridged Trinuclear Complexes of Cu: Models for Spin Interactions in Two-Dimensional Electrically Conductive MOFs
Journal of the American Chemical Society ( IF 14.4 ) Pub Date : 2019-06-10 , DOI: 10.1021/jacs.9b04822
Luming Yang ₁ , Xin He ₁ , Mircea Dincă ₁

Affiliation

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.

中文翻译：

铜的三亚苯桥联三核配合物：二维导电 MOF 中的自旋相互作用模型

2,3,6,7,10,11-六羟基苯并苯 (HHTP) 和 2,3,6,7,10,11-六氨基苯 (HATP) 与 [Cu(Me3tacn)]2+ 的反应 (Me3tacn = 1,4 ,7-trimethyl-1,4,7-triazacyclononane) 产生三方三铜配合物 [(Me3tacnCu)3(HOTP)]3+ (1) 和 [(Me3tacnCu)3(HITP)]4+ (2) (HOTP, HITP = 六氧基-和六亚氨基-三亚苯基，分别）。这些三核配合物是二维导电金属有机骨架 (MOF) 六氧化三亚苯基铜 (Cu3HOTP2) 和六亚氨基三亚苯基铜 (Cu3HITP2) 中自旋交换相互作用的分子模型。复合物 1 与 HOTP3 分离，其氧化态与氧桥接 MOF 中的氧化态相同，而在 Cu3HITP2 中发现的三重氧化 HITP3 就分子模型中的歧化而言是不稳定的。确实，磁性测量揭示了 1 的以配体为中心的自由基特征和 2 的封闭壳结构，与配体的氧化还原状态一致。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 MOF 中的金属-配体-金属相互作用，并为合成其他具有离域电子的二维材料提供潜在的灵感。

更新日期：2019-06-10

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