Tuning Dimensions of Complexes through Selective In Situ Reaction, Mechanistic Insights into Ni(II)-Catalyzed Br–OH Exchange, Magnetic Properties, and Density Functional Theory Studies
Tuning Dimensions of Complexes through Selective In Situ Reaction, Mechanistic Insights into Ni(II)-Catalyzed Br–OH Exchange, Magnetic Properties, and Density Functional Theory Studies
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通过选择性原位反应调节配合物的尺寸、Ni(II) 催化的 Br-OH 交换的机理见解、磁性和密度泛函理论研究
DOI：
10.1021/acs.inorgchem.2c03643
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发表时间：
2022
影响因子：
4.6
通讯作者：
Kun Yuan
中科院分区：
文献类型：
--
作者：
Chang-Dai Si;Jian-Bin Zhang;Feng-Feng Pan;Xu Yan;Peng Wang;Dong-Qian Xue;Xiu-Juan Li;Jia-Cheng Liu;Kun Yuan
在水热条件下合成了[Mn3(L)2(4,4′-bipy)2(H2O)2]n(1)和[Ni(L1)(1,4-bib)(H2O)]n（2) （H3L = 5-（3-羟基苯氧基）间苯二甲酸，H2L1= 5-（3-羟基苯氧基）间苯二甲酸，4,4′-bpy = 4,4′-联吡啶，1,4-bib = 1,4-双（1h -咪唑-1-基）苯））。最值得注意的是，在溴原子诱导效应的帮助下，在配合物2的结构中观察到配体转化，并通过单晶x射线晶体学和x射线光电子能谱（XPS）对其进行了彻底的研究。引人注目的是，在此过程中，Ni（II）离子既被用作配位原子，又被用作H3L原位Br-OH交换的催化剂，因此产物倾向于形成一维链。同样的反应不能在1中发生，从而形成二维结构。此外，利用密度泛函理论（DFT）计算很好地解释了Ni（II）催化和磁交换机制。最后，配合物1 - 2由于分子间弱相互作用（C-Br··π、C-H··π、C-H··O和π··π堆积）而表现出三维（3D）超分子结构，并表现出完全不同的反铁磁耦合相互作用。
Two coordination polymers (CPs), namely, [Mn3(L)2(4,4′-bipy)2(H2O)2]n(1) and [Ni(L1)(1,4-bib)(H2O)]n(2) (H3L = 5-(3-bromo-4-carboxyphenoxy)isophthalic acid, H2L1= 5-(3-hydroxyphenoxy)isophthalic acid, 4,4′-bpy = 4,4′-bipyridine, and 1,4-bib = 1,4-bis(1H-imidazol-1-yl)benzene), were synthesized under hydrothermal conditions. Most notably, with the help of the bromine atom-inducing effect, ligand transformation was observed in the structure of complex2, which was scrutinized thoroughly by single crystal X-ray crystallography and X-ray photoelectron spectroscopy (XPS). Strikingly, Ni(II) ions were utilized as both coordinated atoms and as a catalyst for in situ Br–OH exchange of H3L in the process, as a result of which the product would have preferred to form a one-dimensional chain. The same reaction cannot happen in1, leading to form a two-dimensional structure. Moreover, Ni(II)-catalyzed and magnetic exchange mechanisms were well interpreted using density functional theory (DFT) calculations. Finally, complexes1–2show three-dimensional (3D) supramolecular structures because of intermolecular weak interactions (C–Br···π, C–H···π, C–H···O, and π···π stacking) and exhibit utterly different antiferrimagnetic coupling interactions.