1D coordination polymers of 1,3,5-triaza-7-phosphaadamantane and N-methyl-1,3,5-triaza-7-phosphaadamante with silver(I) perchlorate: structural elucidation

Two novel 1D silver(I) coordination polymers, [Ag(H2O)(PTA)]n·(ClO4)n (1) and [Ag(PTAMe)(CH3OH)(ClO4)]n·(ClO4)n (2), have been isolated as air- and light-stable products from the reactions of silver(I) perchlorate with 1,3,5-triaza-7-phosphaadamantane (PTA) and N-methyl-1,3,5-triaza-7-phosphaadamantane (PTAMe), respectively, at ambient temperature. The synthesized silver(I) coordination polymers were characterized by NMR, IR spectroscopy, and single-crystal X-ray diffraction. Compound 1 exhibits a zigzag 1D polymeric structure with Ag+ centers coordinated in a distorted trigonal planar geometry to phosphorus and nitrogen atoms from PTA ligands and an oxygen atom, while compound 2 forms a linear 1D chain featuring Ag+ centers in a distorted tetrahedral environment coordinated by PTAMe ligands, methanol, and perchlorate oxygen atoms. Both coordination polymers utilize classical P,N-coordination modes of the phosphine ligands but differ in topology and dimensional propagation along distinct crystallographic axes. These findings highlight the influence of ligand substituents and coordination environments on the structural diversity and supramolecular assembly of silver(I) coordination polymers.本研究成功制备了两种新型一维银(I)配位聚合物：[Ag(H₂O)(PTA)]ₙ·(ClO₄)ₙ (1) 与 [Ag(PTAMe)(CH₃OH)(ClO₄)]ₙ·(ClO₄)ₙ (2)。二者分别由高氯酸银(I)与1,3,5-三氮杂-7-磷杂金刚烷(1,3,5-triaza-7-phosphaadamantane, PTA)、N-甲基-1,3,5-三氮杂-7-磷杂金刚烷(N-methyl-1,3,5-triaza-7-phosphaadamantane, PTAMe)在室温下反应得到，且产物在空气与光照条件下均具备良好稳定性。所合成的银(I)配位聚合物通过核磁共振(NMR)、红外(IR)光谱以及单晶X射线衍射完成了结构表征。化合物1呈现锯齿形一维聚合物链结构，Ag⁺中心处于畸变三角平面配位几何环境中，分别与PTA配体的磷、氮原子以及一个配位氧原子结合；化合物2则形成线性一维链结构，Ag⁺中心处于畸变四面体配位环境中，由PTAMe配体、甲醇分子以及高氯酸根氧原子共同配位。两种配位聚合物均采用膦配体经典的P、N双齿配位模式，但在拓扑结构以及沿不同晶轴的延伸方向上存在显著差异。本研究结果揭示了配体取代基与配位环境对银(I)配位聚合物结构多样性及超分子组装行为的调控作用。