1,1'-Bis(pyrazol-3-yl)ferrocene: A Clip Ligand That Forms Supramolecular Aggregates and Prismatic Hexanuclear Coinage Metal Complexes.
1,1'-Bis(pyrazol-3-yl)ferrocene: A Clip Ligand That Forms Supramolecular Aggregates and Prismatic Hexanuclear Coinage Metal Complexes.
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DOI：
10.1021/acs.inorgchem.5b00898
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发表时间：
2015-06
影响因子：
4.6
通讯作者：
Mattia Veronelli;S. Dechert;S. Demeshko;F. Meyer
中科院分区：
文献类型：
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作者：
Mattia Veronelli;S. Dechert;S. Demeshko;F. Meyer
合成了两个含吡唑取代基的二茂铁衍生物：1，1‘-双(5-甲基-1H-吡唑-3-基)二茂铁(H_2LH)和1，1’-bis(5-trifluoromethyl-1H-pyrazol-3-yl)ferrocene(H_2LF)。在固体状态下，它们形成不同的氢键二聚体，两个二茂铁/吡唑杂化分子具有正向排列(H_2LF，C_2对称)或反平行排列(H_2LF，C_2H对称)。虽然扩散有序谱和变温核磁共振谱揭示了几个动力学过程，但在低温溶液中也检测到了超分子二聚现象。二茂铁衍生物的氧化还原电位受吡唑取代基(Me，CF3)性质的影响。在去质子化形式的[LR]2-中，两种二茂铁/吡唑杂化化合物都作为配体形成了寡核CuI、AgI和AUI络合物，并用基质辅助激光解吸电离质谱仪对其进行了鉴定。X-射线单晶分析揭示了Cu6L3H和Ag6L3F的结构，它们都含有两个平行的和遮蔽的[M(μ-PZ)]3个金属大环(M=铜，银)，由三个二茂铁单元相连。在Ag6L3F中，两个三角形M3N6甲板之间的MI距离较小(Cu6L3H为3.28-3.30比3.44-3.51ä)，这表明分子内有大量的闭壳Ag(D10)-Ag(D10)相互作用。然而，Cu6L3H具有分子间紧密的铜···铜接触，最短可达3.37？收集了配体和配合物的穆斯堡尔数据，并测量了电化学性质；报道了初步的发光数据。
Two ferrocene derivatives with appended pyrazole substituents, namely, 1,1'-bis(5-methyl-1H-pyrazol-3-yl)ferrocene (H2LH) and 1,1'-bis(5-trifluoromethyl-1H-pyrazol-3-yl)ferrocene (H2LF), were synthesized. In solid state they form distinct H-bonded dimers with orthogonal (H2LH, C2 symmetry) or antiparallel (H2LF, C2h symmetry) arrangement of the two ferrocene/pyrazole hybrid molecules. Supramolecular dimerization was also detected in solution at low temperatures, though diffusion-ordered spectroscopy and variable-temperature NMR spectroscopy revealed several dynamic processes. Redox potentials of the ferrocene derivatives are affected by the nature of the pyrazole substituent (Me, CF3). In their deprotonated form [LR]2-, both ferrocene/pyrazole hybrids serve as ligands and form oligonuclear CuI, AgI, and AuI complexes that were identified by matrix-assisted laser desorption ionization mass spectrometry. X-ray crystallography revealed the structures of Cu6L3H and Ag6L3F, which both contain two parallel and eclipsed [M(μ-pz)]3 metallamacrocycles (M = Cu, Ag) linked by three ferrocene units. MI···MI distances between the two triangular M3N6 decks are shorter in Ag6L3F (3.28-3.30 vs 3.44-3.51 Å in the case of Cu6L3H), indicating substantial intramolecular closed-shell Ag(d10)-Ag(d10) interactions. However, Cu6L3H features close intermolecular Cu···Cu contacts as short as 3.37 Å. Mössbauer data for both the ligands and complexes were collected, and electrochemical properties were measured; preliminary luminescence data are reported.