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首页> 外文期刊>Crystal growth & design >Ag(I) and Cu(I) [2 × 2] chiral grids containing pyrimidine ligands with camphor moieties. Arene encapsulation
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Ag(I) and Cu(I) [2 × 2] chiral grids containing pyrimidine ligands with camphor moieties. Arene encapsulation

机译：Ag（I）和Cu（I）[2×2]手性网格，其中含有带有樟脑部分的嘧啶配体。芳烃封装

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摘要

The C_2 symmetric chiral ligand 4,6-bis[(4S,7R)-7,8,8′- trimethyl-4,5,6,7-tetrahydro-4,7-methaneindazol-2-yl]pyrimidine (bpz ~(Cam) pm) was synthesized and reacted with Cu(I) and Ag(I) salts to give four chiral [2 × 2] grid-type structures: [M_4(bpz ~(Cam)pm)_4]X_4,M=Cu(I),Ag(I);X =BF_4~-,PF_6~-. The structures of the two BF _4~- derivatives were determined by X-ray diffraction. The grids contain facing ligands that are not parallel and, in contrast to the situation found in previous examples, the anions are not hosted within the cavities but toluene molecules are. In the case of the copper derivative, π-stacking interactions are established between the pyrimidine rings and these toluene molecules and others situated in the intercationic regions, giving rise to the formation of π-stacked columns with alternating pyrimidine and toluene molecules. Due to the chirality of bpz~(Cam) pm, chiral cavities are generated in the crystalline structure. From NMR studies, it was concluded that the copper grids are maintained in solution but this is not the case for the silver derivatives. The UV-vis spectra of the copper complexes show an MLCT band, higher for the PF_6~- derivative. Some derivatives exhibit fluorescence with a high influence of the solvent and counteranion in the intensity of the emission.
机译：C_2对称手性配体4,6-双[（4S，7R）-7,8,8'-三甲基-4,5,6,7-四氢-4,7-甲烷吲唑-2-基]嘧啶（bpz〜合成（Cam）pm）并与Cu（I）和Ag（I）盐反应，得到四个手性[2×2]网格型结构：[M_4（bpz〜（Cam）pm）_4] X_4，M = Cu（I），Ag（I）; X = BF_4〜-，PF_6〜-。通过X射线衍射确定了两个BF _4〜-衍生物的结构。网格包含不平行的面对配体，与先前示例中发现的情况相反，阴离子不在空穴内，而是甲苯分子。在铜衍生物的情况下，在嘧啶环与这些甲苯分子以及位于阳离子间区域的其他甲苯分子之间建立了π堆积相互作用，从而形成了具有交替的嘧啶和甲苯分子的π堆积柱。由于bpz〜（Cam）pm的手性，在晶体结构中会产生手性空洞。从NMR研究可以得出结论，铜网格保持在溶液中，但是对于银衍生物而言并非如此。铜配合物的紫外-可见光谱显示出MLCT谱带，对于PF_6〜-衍生物更高。一些衍生物在发射强度方面显示出对溶剂和抗衡阴离子具有高度影响的荧光。

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