Bis-argentivorous molecules (L^a and L^b), which have phenyl and 4,4′-biphenyl groups as linkers, have been prepared. The structures of Ag⁺ complexes with the new ligands (L^a and L^b) were investigated in solution and the solid state. The CSI-MS and ¹H NMR titration of L^a and L^b with Ag⁺ show 1:1 and 1:2 complexes depending on the [Ag⁺]:[L] ratios. In the solid-state structures, single crystals of L^a and L^b with 2 equiv of Ag⁺ were prepared. X-ray crystallography of the silver(I) complexes with L^a and L^b showed that an intramolecular racemic structure (Δ(δδδδ)Λ(λλλλ) form) and a racemic mixture of Δ(δδδδ)Δ(δδδδ) and Λ(λλλλ)Λ(λλλλ) forms were formed, respectively. The dynamic ¹H NMR studies suggest the following: (i) the activation entropies (ΔS^⧧) of the side arm rotations in the Ag⁺ complex with L^a were all negative, indicating restricted rotation of the side arms due to their shortness, and (ii) the ΔS^⧧ values of the Ag⁺ complexes with L^b were negative only when the side arms of both cyclens rotated simultaneously, and the ΔS^⧧ values for the 1:1 and 1:2 complexes were positive when one cyclen side arm was rotated. These values of ΔS^⧧ indicate that the biphenyl side arms between the two cyclens are not long enough to rotate the ring freely.

中文翻译：

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由苯基和 4,4'-联苯基桥接的双银分子：银配合物的结构和动态行为

已经制备了具有苯基和 4,4'-联苯基作为连接基团的双食原子分子（L ^a和L ^b）。在溶液和固态中研究了 Ag ⁺与新配体（L ^a和L ^b）配合物的结构。L ^a和L ^b与 Ag ⁺的 CSI-MS 和¹ H NMR 滴定显示 1:1 和 1:2 复合物，具体取决于 [Ag ⁺ ]:[ L ] 比率。在固态结构中，L ^a和L ^{b 的}单晶用 2 当量的 Ag ⁺制备。银 (I) 与L ^a和L ^b配合物的 X 射线晶体学显示分子内外消旋结构（Δ( δδδδ )Λ( λλλλ ) 形式）和 Δ( δδδδ )Δ( δδδδ ) 和 Λ(分别形成了λλλλ )Λ( λλλλ ) 形式。动态¹ H NMR 研究表明：(i)与L ^a的 Ag ⁺复合物中侧臂旋转的激活熵 (Δ S ^⧧ )都是负的，表明侧臂的旋转受限，因为它们很短，并且（ii）只有当两个循环的侧臂同时旋转时，Ag ⁺与L ^b复合物的 Δ S ^⧧值为负，并且 Δ S当一个循环侧臂旋转时，1:1 和 1:2 复合物的^⧧值为正。这些 Δ S ^⧧值表明两个循环单元之间的联苯侧臂不够长，无法自由旋转环。