Silver(I) Arylsulfonates: A Systematic Study of “Softer” Hybrid Inorganic−Organic Solids

The present study represents the first systematic examination of the effects on the layered structure of simple
silver aryl−monosulfonates as the breadth of the pendant aryl group is increased beyond that where a simple
“phosphonate-like” motif is sustainable. Five new silver arenesulfonates are reported. On the basis of comparison
with Ag benzenesulfonate, a threshold of ∼6.4 Å is proposed and confirmed as the critical breadth of an aryl group
for a simple layered motif to be observed in silver sulfonates. Ag 1,1‘-biphenyl-4-sulfonate (1) and Ag
2-naphthalenesulfonate (2) are below this threshold and so form simple layered networks, termed type 1 solids.
When the pendant group is broadened to a 1-naphthyl group, the layer incorporates coordinated water to maintain
a layered structure giving Ag 1-naphthalenesulfonate hemihydrate (3a). This more diffuse structure is termed a
type 2 solid. For anhydrous Ag 1-naphthalenesulfonate (3) and Ag 1-pyrenesulfonate (4), the additional breadth is
compensated for by the formation of Ag−π interactions and the formation of type 3 solids. Interactions between the
pendant groups are observed to play a significant role in the packing of the solid. All frameworks are characterized
by single crystal and powder X-ray diffraction, IR, DSC-TGA, and elemental analysis. The significance of this
adaptable framework is discussed along with implications for design of stacked arene arrays.

本研究首次系统考察了当取代芳基侧链宽度超出简单“类膦酸酯”基序的稳定承载范围时，对简单芳基单磺酸银层状结构的影响。本文报道了五种新型芳磺酸银化合物。通过与苯磺酸银（Ag benzenesulfonate）的对比分析，本文提出并验证了芳基侧链的临界宽度约为6.4埃（Å），此为磺酸银体系中形成简单层状基序的阈值条件。1,1'-联苯-4-磺酸银（Ag 1,1'-biphenyl-4-sulfonate，化合物1）与2-萘磺酸银（Ag 2-naphthalenesulfonate，化合物2）的芳基侧链宽度低于该阈值，因此形成了被称为1型固体的简单层状网络结构。当取代侧基拓展为1-萘基时，层状结构会引入配位水以维持层状骨架，由此得到半水合1-萘磺酸银（Ag 1-naphthalenesulfonate hemihydrate，化合物3a），这种更为弥散疏松的结构被归类为2型固体。对于无水1-萘磺酸银（Ag 1-naphthalenesulfonate，化合物3）与1-芘磺酸银（Ag 1-pyrenesulfonate，化合物4），其额外的侧链宽度可通过Ag-π相互作用得到补偿，从而形成3型固体。研究发现，芳基侧链之间的相互作用对晶体堆积具有显著影响。所有骨架结构均通过单晶X射线衍射、粉末X射线衍射、红外光谱（IR）、差示扫描量热-热重联用分析（DSC-TGA）以及元素分析完成表征。本文还探讨了这种柔性骨架的重要意义，及其在堆叠芳环阵列设计中的潜在应用价值。