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New Coordination Polymers of Copper(I) and Silver(I) with Pyrazine and Piperazine: A Step Toward “Green” Chemistry and Optoelectronic Applications
Inorganic Chemistry ( IF 4.3 ) Pub Date : 2018-08-06 00:00:00 , DOI: 10.1021/acs.inorgchem.8b01131 Ruaa M. Almotawa 1, 2 , Ghadah Aljomaih 1 , Daniela Vargas Trujillo 1 , Vladimir N. Nesterov 2 , Manal A. Rawashdeh-Omary 1
Inorganic Chemistry ( IF 4.3 ) Pub Date : 2018-08-06 00:00:00 , DOI: 10.1021/acs.inorgchem.8b01131 Ruaa M. Almotawa 1, 2 , Ghadah Aljomaih 1 , Daniela Vargas Trujillo 1 , Vladimir N. Nesterov 2 , Manal A. Rawashdeh-Omary 1
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Five coordination polymers and one hexanuclear cluster have been obtained, and their crystal structures were determined upon reaction of Cu(I) or Ag(I) precursors with pyrazine (Pyz) or piperazine (Ppz). Five complexes are mixed-imine-ligand with anionic-fluorinated pyrazolate [3,5-(CF3)2Pz]− ([PzF]−) besides Pyz or Ppz, whereas the sixth had the neutral diimine as a single chromophore. Complexes 1–3 are isomers of the same Cu/PzF/Pyz composition with the same or different unit cell stoichiometry, namely, {Cu6[3,5-(CF3)2Pz]6(Pyz)3(CH2Cl2)}∞ (1·CH2Cl2), {Cu2[3,5-(CF3)2Pz]}2(Pyz)2·toluene}∞ (2·toluene), and {Cu3[3,5-(CF3)2Pz]3(Pyz)1.5·1.5benzene}∞ (3·1.5benzene), respectively. Altering only the metal attains {Ag6[3,5-(CF3)2Pz]6(Pyz)2·2benzene} (4·2benzene), while also changing the neutral diimine attains {Ag2[3,5-(CF3)2Pz]2(Ppz)}∞ (5). Using Pyz without an anionic imine yields {[Cu(Pyz)(MeCN)2][BF4]}∞ (6). The crystal structure of 1 shows two trimers linked together with two pyrazine ligands. Crystals of 2 represent a metal–organic framework (MOF-TW1) with significant surface area (1278 m2/g) and porosity (23.7% void volume) without considering toluene adsorbates in channels. MOF-TW1 was obtained serendipitously upon a reaction attempt to attain a mixed-metal product, instead attaining a Cu(I)-only product with interconnected four-coordinate dinuclear units. Likewise, 3 was obtained through a transmetalation of all Ag atoms in 4 to replace them by Cu atoms. Three reactions (to obtain 1, 4, and 5) were successfully carried out by both solvent-mediated and solventless transformations, whereas 2 and 3 were obtained only by solvent-mediated reactions, while 6 was attainable only by solventless transformations. The solventless transformations occurred either by sublimation and vapor diffusion or by mechanical grinding at ambient laboratory conditions—without the aid of heating, high pressure, vacuum, or any automated equipment. All transformations could be monitored by the human eye as the reaction progresses, as evidenced by progressive discoloration and/or luminescence changes. All crystal structures were obtained with the aid of conventional crystal growth methods from organic solvents for bulk products obtained from both solvelntless and solvent-mediated reactions. Powder X-ray diffraction was used to compare bulk products with one another and the crystallographic products. All Cu(I) products are colored and nonluminescent; the progress of their vapor diffusion-based solventless reactions can be followed by gradual discoloration of white solid reactants and/or quenching precursor’s phosphorescence. Both Ag(I) products were colorless with 4 being luminescent but not 5.
中文翻译：
铜（I）和银（I）与吡嗪和哌嗪的新型配位聚合物：迈向“绿色”化学和光电应用的一步
获得了五种配位聚合物和一个六核簇，并根据Cu（I）或Ag（I）前驱体与吡嗪（Pyz）或哌嗪（Ppz）的反应确定了其晶体结构。除Pyz或Ppz以外，还有5种配合物与亚胺基配体与阴离子氟化吡唑酸酯[3,5-（CF 3）2 Pz] -（[Pz F ] -）混合，而第六种具有中性二亚胺作为单个发色团。配合物1 - 3是相同的Cu /的Pz的异构体˚F具有相同或不同的单元电池化学计量/ PYZ组合物，即，{的Cu 6 [3,5-（CF 3）2的Pz] 6（PYZ）3（CH 2 Cl 2）} ∞（1 ·CH 2 Cl 2），{Cu 2 [3,5-（CF 3）2 Pz]} 2（Pyz）2 ·甲苯} ∞（2 ·甲苯），和{Cu 3 [3,5-（CF 3）2 Pz] 3（Pyz）1.5 · 1.5苯} ∞（3 ·1.5苯）。仅改变金属即可达到{Ag 6 [3,5-（CF 3）2 Pz] 6（Pyz）2 · 2苯}（4 ·2苯），同时改变中性二亚胺也达到{Ag 2 [3,5-（CF 3）2 Pz] 2（Ppz）} ∞（5）。使用不含阴离子亚胺的Pyz会产生{[Cu（Pyz）（MeCN）2 ] [BF 4 ]} ∞（6）。的晶体结构1只显示了两个三聚体具有两个配位体吡嗪连接在一起。2的晶体代表具有明显表面积（1278 m 2）的金属-有机骨架（MOF-TW1）/ g）和孔隙率（23.7％的空隙体积），而不考虑通道中的甲苯吸附物。MOF-TW1是在尝试获得混合金属产物的过程中偶然获得的，而不是获得具有相互连接的四坐标双核单元的仅Cu（I）产物。同样，3是通过所有的Ag原子的转移金属化中获得的4通过Cu原子来取代它们。三种反应（以获得1，4，和5）由两个溶剂介导的和无溶剂的转化都成功地进行了，而2和3只通过溶剂介导的反应，获得，而6只有通过无溶剂转化才能达到。无溶剂转化是通过升华和蒸汽扩散或在环境实验室条件下通过机械研磨而发生的，无需加热，高压，真空或任何自动化设备。随着反应的进行，人眼可以监控所有的转化，如逐渐变色和/或发光变化所证明的。借助于常规晶体生长方法，从无溶剂和溶剂介导的反应获得的本体产物的有机溶剂中获得所有晶体结构。粉末X射线衍射用于比较散装产物和晶体产物。所有的Cu（I）产品都是有色且不发光的。它们的基于蒸汽扩散的无溶剂反应的进展可以跟随白色固体反应物的逐渐变色和/或淬灭前体的磷光。两种Ag（I）产品均无色4是发光的，而不是5。
更新日期：2018-08-06
中文翻译：
铜（I）和银（I）与吡嗪和哌嗪的新型配位聚合物：迈向“绿色”化学和光电应用的一步
获得了五种配位聚合物和一个六核簇，并根据Cu（I）或Ag（I）前驱体与吡嗪（Pyz）或哌嗪（Ppz）的反应确定了其晶体结构。除Pyz或Ppz以外，还有5种配合物与亚胺基配体与阴离子氟化吡唑酸酯[3,5-（CF 3）2 Pz] -（[Pz F ] -）混合，而第六种具有中性二亚胺作为单个发色团。配合物1 - 3是相同的Cu /的Pz的异构体˚F具有相同或不同的单元电池化学计量/ PYZ组合物，即，{的Cu 6 [3,5-（CF 3）2的Pz] 6（PYZ）3（CH 2 Cl 2）} ∞（1 ·CH 2 Cl 2），{Cu 2 [3,5-（CF 3）2 Pz]} 2（Pyz）2 ·甲苯} ∞（2 ·甲苯），和{Cu 3 [3,5-（CF 3）2 Pz] 3（Pyz）1.5 · 1.5苯} ∞（3 ·1.5苯）。仅改变金属即可达到{Ag 6 [3,5-（CF 3）2 Pz] 6（Pyz）2 · 2苯}（4 ·2苯），同时改变中性二亚胺也达到{Ag 2 [3,5-（CF 3）2 Pz] 2（Ppz）} ∞（5）。使用不含阴离子亚胺的Pyz会产生{[Cu（Pyz）（MeCN）2 ] [BF 4 ]} ∞（6）。的晶体结构1只显示了两个三聚体具有两个配位体吡嗪连接在一起。2的晶体代表具有明显表面积（1278 m 2）的金属-有机骨架（MOF-TW1）/ g）和孔隙率（23.7％的空隙体积），而不考虑通道中的甲苯吸附物。MOF-TW1是在尝试获得混合金属产物的过程中偶然获得的，而不是获得具有相互连接的四坐标双核单元的仅Cu（I）产物。同样，3是通过所有的Ag原子的转移金属化中获得的4通过Cu原子来取代它们。三种反应（以获得1，4，和5）由两个溶剂介导的和无溶剂的转化都成功地进行了，而2和3只通过溶剂介导的反应，获得，而6只有通过无溶剂转化才能达到。无溶剂转化是通过升华和蒸汽扩散或在环境实验室条件下通过机械研磨而发生的，无需加热，高压，真空或任何自动化设备。随着反应的进行，人眼可以监控所有的转化，如逐渐变色和/或发光变化所证明的。借助于常规晶体生长方法，从无溶剂和溶剂介导的反应获得的本体产物的有机溶剂中获得所有晶体结构。粉末X射线衍射用于比较散装产物和晶体产物。所有的Cu（I）产品都是有色且不发光的。它们的基于蒸汽扩散的无溶剂反应的进展可以跟随白色固体反应物的逐渐变色和/或淬灭前体的磷光。两种Ag（I）产品均无色4是发光的，而不是5。
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