Nine Cu(I)-cyanide metal–organic frameworks (MOFs), namely, [Cu₄(CN)₂(4-bpt)₂]_n (1), {[Cu₃(CN)₂(4-bpt)]·H₂O}_n (2), [Cu₂(CN)(3-bpt)]_n (3), [Cu₂(CN)₂(3-Hptz)]_n (4), [Cu₃(CN)₂(3-ptz)]_n (5), [Cu₇(CN)₇(3-tpt)₂]_n (6), {[Cu₉(CN)₉(btb)₂]·btb}_n (7), [Cu₂(CN)₂(4-azpy)]_n (8), and [Cu₃(CN)₃(bpp)]_n (9) (4/3-Hbpt = 3,5-bis(4/3-pyridyl)-1,2,4-triazole; 3-Hptz = 3-pyridyl-tetrazole; 3-tpt = 2,4,6-tris(3-pyridyl)-1,3,5-triazine; btb = 1,4-bis(1,2,4-triazol-4-yl)benzene; 4-azpy = 4,4′-azobispyridine; bpp = 1,3-bis(4-pyridyl)propane), were synthesized under hydrothermal conditions and structurally characterized. The 4-bpt, 3-bpt, and 3-Hptz ligands in 1–4 were in situ generated by cycloaddition reactions. Their structural features vary from two-dimensional (2D) (3), three-dimensional (3D) (4, 5, 6), 3D 2-fold interpenetration (1, 2, 8), to 3D 3-fold interpenetration (7, 9). Complex 1 is an intriguing 3D metal–organic framework (MOF) with a nanosized rectangular channel. Complex 3 exhibits a chiral 2D double-layered network prepared by achiral component. Complex 6 is a 3D MOF constructed from six μ₂-cyanides, a μ₃-cyanide, and a μ₃-tpt ligand. Complex 7 shows an interesting 3D MOF with (3.4)-connected 5-nodal net, containing a btb guest molecule in the rectangular channel. Complex 8 is a 3D MOF assembled by a 2D [Cu₂(CN)₂]_n network pillared by a 4-azpy spacer. Complex 9 is a 3D MOF with ths topology. Their structural diversity originates from the variation of Cu(I) coordination numbers and three types of cyanide-bridging modes, tuned via various bidentate (4-azpy, bpp), tridentate (3-Hptz, 3-tpt), and tetradentate (4-bpt, 3-bpt, 3-ptz, btb) N-heterocyclic ligands. Infrared spectra and cyanide coordination modes are discussed in detail. The characteristic ν(C≡N) stretching frequencies in μ₂-CN complexes show linear correlation with the Cu–CN bond distances. A decrease of about 6.7 cm^–1 in ν(C≡N) corresponds to a 0.01 Å elongation of the Cu–CN bond. These Cu(I) complexes exhibit good thermally stability and emit strong luminescence at 386–593 nm.

中文翻译：

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具有原位生成的N-杂环配体的九种Cu（I）-氰化物金属-有机骨架的结构多样性和振动光谱

九种Cu（I）-氰化物金属-有机骨架（MOF），即[Cu ₄（CN）₂（4-bpt）₂ ] _n（1），{[Cu ₃（CN）₂（4-bpt）] ·H ₂ O} _n（2），[Cu ₂（CN）（3-bpt）] _n（3），[Cu ₂（CN）₂（3-Hptz）] _n（4），[Cu ₃（CN） ）₂（3-ptz）] _n（5），[Cu ₇（CN）₇（3-tpt）₂ ] _n（6），{[Cu ₉（CN）₉（btb）₂ ]·btb} _n（7），[Cu ₂（CN）₂（4-azpy）] _n（8）和[Cu ₃（CN）₃（bpp）] _n（9）（4 / 3-Hbpt = 3,5-双（4 / 3-吡啶基）-1,2,4-三唑; 3-Hptz = 3-吡啶基-四唑; 3-tpt = 2,4,6-三（3-吡啶基）-1,3,5-三嗪; btb = 1,4-双（1,2,4-三唑-4-基）苯; 4-azpy = 4，在水热条件下合成了4'-偶氮二吡啶； bpp = 1,3-双（4-吡啶基）丙烷），并对其结构进行了表征。4 BPT，3- BPT和3- Hptz配体在1 - 4是通过环加成反应原位生成的。它们的结构特征由两维（2D）（变化3），三维（3D）（4，5，6），3D 2倍穿插（1，2，8），到3D 3倍穿插（7，9）。复杂1是一个有趣的3D金属-有机框架（MOF），具有纳米尺寸的矩形通道。配合物3显示出由非手性组分制备的手性2D双层网络。复杂6是3D MOF从六个μ构造₂ -cyanides，一个μ ₃-氰化物，和μ ₃ -tpt配体。配合物7显示了一个有趣的3D MOF，其具有（3.4）连接的5节点网，在矩形通道中包含btb来宾分子。配合物8是一个3D MOF，它是由一个由4-azpy间隔基柱撑的2D [Cu ₂（CN）₂ ] _n网络组装而成。复杂9是一个三维MOF与部份拓扑。它们的结构多样性源自Cu（I）配位数和三种氰化物桥联模式的变化，可通过各种双齿（4-azpy，bpp），三齿（3-Hptz，3-tpt）和四齿（4 -bpt，3-bpt，3-ptz，btb）N-杂环配体。详细讨论了红外光谱和氰化物配位模式。特征ν（C≡N）中μ的拉伸频率_2个-CN配合物表现出与所述Cu-CN键长的线性相关性。ν（C≡N）减少约6.7 cm ^–1对应于Cu-CN键的0.01Å伸长。这些Cu（I）配合物表现出良好的热稳定性，并在386–593 nm处发出强烈的发光。