Molecular Motion and Ligand Stacking Influence Thermal Expansion Behavior and Argentophilic Forces in Silver Coordination Complexes
Molecular Motion and Ligand Stacking Influence Thermal Expansion Behavior and Argentophilic Forces in Silver Coordination Complexes
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DOI：
10.1021/acs.cgd.2c00446
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发表时间：
2022-06
期刊：
影响因子：
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通讯作者：
Gary C. George;D. Unruh;R. Groeneman;Kristin M. Hutchins
中科院分区：
文献类型：
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作者：
Gary C. George;D. Unruh;R. Groeneman;Kristin M. Hutchins
我们使用具有相似分子结构的配体设计了一系列金属有机固体，预计可以提供具有相似固态结构的配位络合物。金属成分是对甲苯磺酸银(I)，配体的动态分子运动能力不同。尽管配体的分子结构相似，但由于π堆积排列的差异以及Ag·Ag相互作用的存在或缺乏，金属配合物表现出不同的固态结构。每个复合物中的配位单元（配体-银-配体）对温度变化的响应不同，这导致该系列内的热膨胀行为范围从负到零再到正。用含偶氮配体获得了两种独特的配合物，并且通过合成条件控制每种配合物的批量制备。用含烯烃配体获得了两种多晶型物，尽管超分子结构差异很大，但两种配合物都经历动态分子运动。总的来说，我们表明对配体结构的简单修改可以显着影响固态结构、晶型和随后的热膨胀行为。
We designed a series of metal–organic solids using ligands with similar molecular structures that were expected to afford coordination complexes with similar solid-state structures. The metal component is silver(I)p-toluenesulfonate, and the ligands differ in their ability to undergo dynamic molecular motion. Although the ligands are similar in their molecular structure, the metal complexes exhibit different solid-state structures because of differences in π-stacking arrangements and the presence or lack of Ag···Ag interactions. The coordination units (ligand-Ag-ligand) in each complex respond differently to temperature changes, which results in thermal expansion behaviors ranging from negative to zero to positive within the series. Two unique complexes were obtained with the azo-containing ligand, and preparation of each complex in bulk was controlled by synthetic conditions. Two polymorphs were obtained with the olefin-containing ligand, and both complexes undergo dynamic molecular motion, although the supramolecular structures differed dramatically. Overall, we show that simple modifications to the ligand structure can significantly affect solid-state structure, crystal form, and subsequent thermal expansion behavior.