Combined Single-Crystal XRD, solution ¹³C and ¹⁹⁵Pt NMR, solid-state ¹⁹⁵Pt NMR and UV-vis measurements, together with comprehensive (TD)DFT calculations, are used to describe the supramolecular interactions and sequential concerted structural transformation occurring in a {PPh₄⁺;[Pt(CN)₄]²⁻;TCP;CH₂Cl₂} supramolecular system (TCP – tetracyanopyrazine). In the solid-state, a mixture of needle-like co-crystals first appears, (PPh₄)₂{[TCP][Pt(CN)₄]} (1) and (PPh₄)₂{[TCP][Pt(CN)₄]}·2CH₂Cl₂ (2), and subsequent recrystallization leads to block-shaped co-crystals of (PPh₄)₂{[TCP]₂[Pt(CN)₄]}·2CH₂Cl₂ (3), wherein double {[Pt(CN)₄]²⁻;TCP} and triple {[Pt(CN)₄]²⁻;TCP;CH₂Cl₂} and {PPh₄⁺;[Pt(CN)₄]²⁻;TCP} synthons present either in 1 or 2 are reproduced in 3. The structural pathway (1,2→3) is accompanied by a 1D-to-2D modular evolution of anion-π interactions between [Pt(CN)₄]²⁻ and π-acidic TCP that seems to be driven, as indicated by calculations, not by maximizing their strength but rather by optimizing other crystal interactions, e.g. between PPh₄⁺ cations. Formation of the corresponding {[Pt(CN)₄]²⁻;π-acid} anion-π contacts in solution is evidenced by ¹³C NMR shifts and by new low-energy electronic absorption in the visible region (UV-vis). Finally, a combined solution/solid-state ¹⁹⁵Pt NMR approach is used for the first time to shed light on the geometry and interactions involving such aggregates; it shows that the degree of trapping of [Pt(CN)₄]²⁻ near a π-acidic surface can be monitored by ¹⁹⁵Pt NMR chemical shifts. The results give fresh insight into block arrangement tactics and characterization of hybrid organic-inorganic co-crystal salts, and into aggregation controlled properties.

中文翻译：

---

阳离子中超分子相互作用的协同进化 金属络合物 π-酸; 溶剂}阴离子-π体系

结合使用单晶XRD，溶液¹³ C和¹⁹⁵ Pt NMR，固态¹⁹⁵ Pt NMR和UV-vis测量以及全面的（TD）DFT计算，可描述超分子相互作用和相继发生的一致结构转变。 {PPh ₄ ⁺ ; [Pt（CN）₄ ] ²⁻ ; TCP; CH ₂ Cl ₂ }超分子体系（TCP –四氰基吡嗪）。在固态下，首先出现针状共晶体的混合物，（PPh ₄）₂ {[TCP] [Pt（CN）₄ ]}（1）和（PPh ₄）₂{[TCP] [Pt（CN）₄ ]}·2CH ₂ Cl ₂（2），然后进行重结晶，得到（PPh ₄）₂ {[TCP] ₂ [Pt（CN）₄ ]的块状共晶体。}·2CH ₂ Cl ₂（3），其中双{[Pt（CN）₄ ] ^2- ; TCP}和三重{[Pt（CN）₄ ] ^2- -TCP; CH ₂ Cl ₂ }和{PPh ₄ ⁺ ; [Pt（CN）₄ ] ^2- ;; TCP}合成子以1或2形式存在复制于3。结构途径（1，2 → 3）伴随之间阴离子-π相互作用的1D到2D模块化进化[PT（CN）₄ ] ^2-和π酸性TCP似乎被驱动，由所指示的通过计算，不是通过最大化其强度，而是通过优化其他晶体相互作用，例如PPh ₄ ⁺阳离子之间的相互作用。溶液中相应的{[Pt（CN）₄ ] ² ;;π-酸}阴离子-π接触的形成由¹³证明。在可见光区域（紫外可见光），C NMR发生位移并通过新的低能电子吸收而移动。最后，首次使用溶液/固态¹⁹⁵ Pt NMR组合方法首次阐明了涉及此类聚集体的几何形状和相互作用。结果表明，通过¹⁹⁵ Pt NMR化学位移可以监测π-酸性表面附近[Pt（CN）₄ ] ^2-的俘获程度。结果提供了新的见解，以块排列策略和有机有机-无机共晶体杂化盐的表征，以及聚集控制的性质。