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Five- and Six-Coordinated Silver(I) Complexes Formed by a Metallomacrocyclic Ligand with a "Au2N2" Donor Group: Observation of Pendulum and Linear Motions and Dual Phosphorescence.
Inorganic Chemistry ( IF 4.3 ) Pub Date : 2020-03-31 , DOI: 10.1021/acs.inorgchem.0c00482 Sara Nayeri 1 , Sirous Jamali 1 , Ali Jamjah 1 , Julia R Shakirova 2 , Sergey P Tunik 2 , Vladislav Gurzhiy 3 , Hamidreza Samouei 4 , Hamid R Shahsavari 5
Inorganic Chemistry ( IF 4.3 ) Pub Date : 2020-03-31 , DOI: 10.1021/acs.inorgchem.0c00482 Sara Nayeri 1 , Sirous Jamali 1 , Ali Jamjah 1 , Julia R Shakirova 2 , Sergey P Tunik 2 , Vladislav Gurzhiy 3 , Hamidreza Samouei 4 , Hamid R Shahsavari 5
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The six-coordinated silver(I) complex [Au2Ag(μ-(PPh2)2py)2(OTf)2](OTf), 4 (py = pyridine, OTf = CF3SO3), and the five-coordinated silver(I) complex [Au2Ag(acetone)(μ-(PPh2)2py)2](PF6)3, 6, were prepared by the reaction of the precursor complexes 1(OTf)2 and 1(PF6)2, in which 1 = [Au2(μ-(PPh2)2py)2]2+, with 1 equiv of Ag(OTf) in dichloromethane and excess of Ag(PF6) in a mixture of dichloromethane/acetone, respectively. Also, the five-coordinated silver(I) complex [Au2Ag(μ-(PPh2)2py)2(py)(OTf)](OTf)2, 5, was obtained by the reaction of 4 with pyridine. The clusters 4-6 were characterized using multinuclear NMR spectroscopy and elemental microanalysis. The single-crystal X-ray diffraction analysis revealed the octahedral and distorted square pyramidal geometries around the silver(I) centers in the crystal structures of 4 and 6, respectively; a dynamic structure was observed for cluster 5 due to pendulum motion of the Ag(pyridine) moiety, which was anchored in the metallomacrocyclic unit [Au2(μ-(PPh2)2py)2]2+. Although the crystal structure of 6 did not display disorders for the silver atom and the acetone ligand similar to that observed for 5, the low-temperature NMR spectroscopies and calculations show a dynamic structure for cluster 6 due to linear motion of the Ag(acetone) moiety. The reaction of the precursor complex 1(PO2F2)2 with 2 equiv of Ag(PO2F2) yielded the tetranuclear Au2Ag2 cluster [Au2Ag2(PO2F2)2(μ-(PPh2)2py)2](PO2F2)2, 7, with a planar-shaped {Au2Ag2} metal core in which alternating Au and Ag atoms occupy the tetragon vertices and showed a strong argentophillic interaction between the silver(I) centers. All clusters 4-7 are emissive in the solid state, and the origins of their emissive excited states were determined using time-dependent density functional theory calculations. Cluster 7 showed a dual phosphorescence emission, which displays strong dependence of the contributions of each emissive component onto the excitation wavelength.
中文翻译：
由具有“ Au2N2”供体基团的金属大环配体形成的五配位和六配位的银（I）配合物：摆和线性运动以及双重磷光的观察。
六配位银（I）络合物[Au2Ag（μ-（PPh2）2py）2（OTf）2]（OTf），4（py =吡啶，OTf = CF3SO3）和五配位银（I）络合物[Au2Ag（丙酮）（μ-（PPh2）2py）2]（PF6）3，6通过前体配合物1（OTf）2和1（PF6）2的反应制备，其中1 = [Au2（ μ-（PPh2）2py）2] 2+，分别在二氯甲烷中有1当量的Ag（OTf）和在二氯甲烷/丙酮的混合物中有过量的Ag（PF6）。而且，通过4与吡啶的反应获得了五配位的银（I）络合物[Au2Ag（μ-（PPh2）2py）2（py）（OTf）]（OTf）2、5。使用多核NMR光谱和元素微分析对簇4-6进行表征。X射线单晶衍射分析表明，在4和6晶体结构中，银（I）中心周围的八面体和扭曲的方形锥体形状；观察到簇5的动态结构，这归因于锚定在金属大环单元[Au2（μ-（PPh2）2py）2] 2+中的Ag（吡啶）部分的摆运动。尽管6的晶体结构没有显示出与5相似的银原子和丙酮配体紊乱，但低温NMR光谱和计算结果显示，由于Ag（丙酮）的线性运动，簇6具有动态结构。部分。前体络合物1（PO2F2）2与2当量的Ag（PO2F2）的反应产生了四核Au2Ag2簇[Au2Ag2（PO2F2）2（μ-（PPh2）2py）2]（PO2F2）2、7，形状的{Au2Ag2}金属核，其中交替排列的Au和Ag原子占据了四边形顶点，并且在银（I）中心之间显示出很强的亲银相互作用。所有星团4-7都处于固态发射状态，并使用随时间变化的密度泛函理论计算确定了它们的发射激发态的起源。团簇7显示出双重磷光发射，其显示每种发射组分的贡献对激发波长的强烈依赖性。
更新日期：2020-04-24
中文翻译：
由具有“ Au2N2”供体基团的金属大环配体形成的五配位和六配位的银（I）配合物：摆和线性运动以及双重磷光的观察。
六配位银（I）络合物[Au2Ag（μ-（PPh2）2py）2（OTf）2]（OTf），4（py =吡啶，OTf = CF3SO3）和五配位银（I）络合物[Au2Ag（丙酮）（μ-（PPh2）2py）2]（PF6）3，6通过前体配合物1（OTf）2和1（PF6）2的反应制备，其中1 = [Au2（ μ-（PPh2）2py）2] 2+，分别在二氯甲烷中有1当量的Ag（OTf）和在二氯甲烷/丙酮的混合物中有过量的Ag（PF6）。而且，通过4与吡啶的反应获得了五配位的银（I）络合物[Au2Ag（μ-（PPh2）2py）2（py）（OTf）]（OTf）2、5。使用多核NMR光谱和元素微分析对簇4-6进行表征。X射线单晶衍射分析表明，在4和6晶体结构中，银（I）中心周围的八面体和扭曲的方形锥体形状；观察到簇5的动态结构，这归因于锚定在金属大环单元[Au2（μ-（PPh2）2py）2] 2+中的Ag（吡啶）部分的摆运动。尽管6的晶体结构没有显示出与5相似的银原子和丙酮配体紊乱，但低温NMR光谱和计算结果显示，由于Ag（丙酮）的线性运动，簇6具有动态结构。部分。前体络合物1（PO2F2）2与2当量的Ag（PO2F2）的反应产生了四核Au2Ag2簇[Au2Ag2（PO2F2）2（μ-（PPh2）2py）2]（PO2F2）2、7，形状的{Au2Ag2}金属核，其中交替排列的Au和Ag原子占据了四边形顶点，并且在银（I）中心之间显示出很强的亲银相互作用。所有星团4-7都处于固态发射状态，并使用随时间变化的密度泛函理论计算确定了它们的发射激发态的起源。团簇7显示出双重磷光发射，其显示每种发射组分的贡献对激发波长的强烈依赖性。
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