Can Solventless Reactions Sometimes Succeed When Solvent-Mediated Reactions Fail? A Second Case Study for Cu(I) and Ag(I) Complexes of Divergently Bridging Diimines without or with Fluorinated Azolates
Can Solventless Reactions Sometimes Succeed When Solvent-Mediated Reactions Fail? A Second Case Study for Cu(I) and Ag(I) Complexes of Divergently Bridging Diimines without or with Fluorinated Azolates
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DOI：
10.1080/02603594.2020.1770738
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发表时间：
2020-09
影响因子：
5.4
通讯作者：
Ruaa M. Almotawa;Christopher Hu;A. Cimino;V. Nesterov;M. Omary;Manal A. Rawashdeh-Omary
中科院分区：
文献类型：
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作者：
Ruaa M. Almotawa;Christopher Hu;A. Cimino;V. Nesterov;M. Omary;Manal A. Rawashdeh-Omary
摘要本文提供了一个新传统的第五个表现形式，通过这个新传统，《无机化学评论》的编辑们希望以身作则，我们开始发表原创的研究内容，尽管如此，我们仍然保留了杂志作为当代无机化学文献批判性讨论的利基的身份（关于之前的表现，请参见：评论Inorg. Chem. 2018，38，1-35; 2019，39，1-26; 2019，39，188-215; 2020，40，1-24。）本文描述了一组银（I）和铜（I）配合物的合成细节、固态结构和电子物理性质。已经获得了两种基于银的配位聚合物：{[3，5-（CF 3）2 Pz]2（bpp）Ag 2}∞（1）和{[3，5-（CF 3）2 Pz][5-（C6 F5）Ttz]（bpp）Ag}∞（2）-由弯曲的1，3-双3，5-双（4-吡啶基）丙烷（bpp）（三氟甲基）吡唑（[3，5-（CF 3）2 Pz]H）和5-五氟苯基-四唑（[5-（C6 F5）Ttz]H）的混合配体，以考察混合配体对所得银基配合物的影响。化合物1的结构为畸变三角平面构型，bpp和[3，5-（CF 3）2 Pz]配体均与银原子结合. 2中的银与三种不同的配体表现出不寻常的相互作用。另外，对于两种不同的银原子，还得到了畸变四面体和畸变三角体两种不同的几何构型。在无溶剂反应中成功合成了Cu（I）配位聚合物{[Cu（bpp）2][BF 4]}∞（3），而不是溶剂介导的反应，从而显示了一条“绿色”化学路线。3的结构显示出与先前公开的银类似物{[Ag（bpp）2][BF 4]}∞（3a）类似的理想四面体几何形状，而在本文中，我们通过更容易的常规合成路线获得具有相同晶体结构的相同产物。所有四个配合物显示bpp配体为中心的绿色排放在环境温度和低温。最后，本文对无溶剂与溶剂介导的反应进行了对比，并对同一作者小组的一个先例进行了评述（Inorg.Chem.2018，57，9962-9976），由此反应仅通过无溶剂途径成功地进行，在此通过机械研磨和通过蒸气扩散从固体中自发升华，一种反应物的状态转化为另一种非挥发性反应物，分别在文献先例中。图形摘要
ABSTRACT This paper provides the fifth manifestation of a new tradition by which the editors of Comments on Inorganic Chemistry wish to lead by example, whereby we start publishing original research content that, nonetheless, preserves the Journal’s identity as a niche for critical discussion of contemporary literature in inorganic chemistry (For the previous manifestations, see: Comments Inorg. Chem. 2018, 38, 1–35; 2019, 39, 1–26; 2019, 39, 188–215; 2020, 40, 1–24.) Herein, synthetic details, solid-state structures, and photophysical properties of a group of silver(I) and copper(I) complexes are described. Two silver-based coordination polymers have been obtained: {[3,5-(CF3)2Pz]2(bpp)Ag2}∞ (1) and {[3,5-(CF3)2Pz][5-(C6F5)Ttz](bpp)Ag}∞ (2) – constructed from bent 1,3-bis(4-pyridyl)propane (bpp), 3,5-bis(trifluoromethyl)pyrazole ([3,5-(CF3)2Pz]H) and 5-pentafluorophenyl-tetrazole ([5-(C6F5)Ttz]H) in order to inspect the influence of mixed ligands on the resulting silver-based coordination complexes. The structure of 1 shows a distorted trigonal planar geometry with both the bpp and [3,5-(CF3)2Pz] ligands binding to the silver atom. The silver in 2 shows an uncommon interaction with the three different ligands. Also, two different geometries including distorted tetrahedral and distorted trigonal were presented for two different silver atoms. An interesting result was obtained for the Cu(I) coordination polymer {[Cu(bpp)2][BF4]}∞ (3) which was successfully synthesized in a solventless reaction but not a solvent-mediated reaction, hence manifesting a “green” chemistry route. The structure of 3 shows an ideal tetrahedral geometry similar to that for the silver analogue, {[Ag(bpp)2][BF4]}∞ (3a), published previously, whereas herein we obtained the same product with the same crystal structure via a more facile conventional synthetic route. All four complexes show bpp ligand-centered green emissions at ambient and cryogenic temperatures. Finally, a commentary is added to contrast the solventless vs solvent-mediated reactions in both this investigation and a precedent thereof by the same corresponding author’s group (Inorg. Chem. 2018, 57, 9962–9976), whereby reactions proceeded successfully only via the solventless route through mechanical grinding herein and spontaneous sublimation by vapor diffusion from the solid-state of one reactant to another yet nonvolatile reactant in the literature precedent, respectively. Graphical Abstract