Self-assembly reactions between AgNO3, L (PPh3, PPh2Py, AsPh3, SbPh3) and [β-Mo8O26]4- in DMF led to the formation of [β-{AgL}2Mo8O26]2- anions, which were isolated as Bu4N+ salts (1-4) and characterized by XRD, IR and elemental analysis. In the crystal structures Ag+ can switch the coordination number from 5 (P, As) to 6 (Sb) by uptake of a DMF molecule. High-level QAIM analysis of the coordination sphere around Ag shows critical points even in the case of longer Ag-O distances. Changing the ligand type to a family of substituted pyridines results in novel Ag-L-POM complexes with different environments around Ag+. For 3-X-pyridine ligands (X = Cl, Br, I), complexes with additional DMF molecules [β-{AgL(DMF)}2Mo8O26]2- (5-7) have been isolated. Halogen bonding of the XO type was detected in the crystal structures of 5-7 and studied by DFT calculations, providing estimated energies from 0.9 to 3.4 kcal mol-1. Variation of substituents at the pyridine ring results in the formation of [β-{AgL}2Mo8O26]2- in the case of 2-NH2-py (8), 2-CH3-Py (9), 2,4,6-collidine (10) and 2,6-NH2-py (11). Solution behavior of 1-4 in CH3CN was studied by a hyphenated HPLC-ICP-AES technique. According to the results, the [β-{AgL}2Mo8O26]2- anions are largely dissociated in this medium. An attempt to change the [Mo8O26]4- precursor to [Mo6O19]2- (in the case of AgNO3 and PyPPh2) resulted in the crystallization of [Ag2(PyPPh2)2(DMF)4][Mo6O19] (12).

中文翻译：

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[{AgL} 2Mo8O26] n-配合物：结合实验和理论研究。

AgNO3，L（PPh3，PPh2Py，AsPh3，SbPh3）和[β-Mo8O26] 4-在DMF中的自组装反应导致形成[β-{AgL} 2Mo8O26] 2-阴离子，将其分离为Bu4N +盐（1-4）并通过XRD，IR和元素分析进行​​表征。在晶体结构中，Ag +可以通过吸收DMF分子将配位数从5（P，As）切换为6（Sb）。对Ag周围的协调域的高级QAIM分析显示出关键点，即使在Ag-O距离较长的情况下也是如此。将配体类型更改为取代的吡啶家族，将导致新型Ag-L-POM复合物在Ag +周围具有不同的环境。对于3-X-吡啶配体（X ＝ Cl，Br，I），已经分离了具有另外的DMF分子[β-{AgL（DMF）} 2Mo8O26] 2-（5-7）的配合物。在5-7的晶体结构中检测到XO型的卤素键，并通过DFT计算进行了研究，从而提供了从0.9到3.4 kcal mol-1的估计能量。在2-NH2-py（8），2-CH3-Py（9），2,4,6-的情况下，吡啶环上取代基的变化导致[β-{AgL} 2Mo8O26] 2-的形成可力丁（10）和2，6-NH 2 -py（11）。通过联用HPLC-ICP-AES技术研究了1-4在CH3CN中的溶液行为。根据结果​​，[β-{AgL} 2Mo8O26] 2-阴离子在该介质中大量解离。尝试将[Mo8O26] 4-前体更改为[Mo6O19] 2-（在AgNO3和PyPPh2的情况下）导致[Ag2（PyPPh2）2（DMF）4] [Mo6O19]结晶。在2-NH2-py（8），2-CH3-Py（9），2,4,6-的情况下，吡啶环上取代基的变化导致[β-{AgL} 2Mo8O26] 2-的形成可力丁（10）和2，6-NH 2 -py（11）。通过联用HPLC-ICP-AES技术研究了1-4在CH3CN中的溶液行为。根据结果​​，[β-{AgL} 2Mo8O26] 2-阴离子在该介质中大量解离。尝试将[Mo8O26] 4-前体更改为[Mo6O19] 2-（在AgNO3和PyPPh2的情况下）导致[Ag2（PyPPh2）2（DMF）4] [Mo6O19]结晶。在2-NH2-py（8），2-CH3-Py（9），2,4,6-的情况下，吡啶环上取代基的变化导致[β-{AgL} 2Mo8O26] 2-的形成可力丁（10）和2，6-NH 2 -py（11）。通过联用HPLC-ICP-AES技术研究了1-4在CH3CN中的溶液行为。根据结果​​，[β-{AgL} 2Mo8O26] 2-阴离子在该介质中大量解离。尝试将[Mo8O26] 4-前体更改为[Mo6O19] 2-（在AgNO3和PyPPh2的情况下）导致[Ag2（PyPPh2）2（DMF）4] [Mo6O19]结晶。