Assembly of a family of 12 supramolecular compounds containing [AnO₂Cl₄]^2– (An = U, Np, Pu), via hydrogen and halogen bonds donated by substituted 4-X-pyridinium cations (X = H, Cl, Br, I), is reported. These materials were prepared from a room-temperature synthesis wherein crystallization of unhydrolyzed and valence-pure [An(VI)O₂Cl₄]^2– (An = U, Np, Pu) tectons is the norm. We present a hierarchy of assembly criteria based on crystallographic observations and subsequently quantify the strengths of the non-covalent interactions using Kohn–Sham density functional calculations. We provide, for the first time, a detailed description of the electrostatic potentials of the actinyl tetrahalide dianions and reconcile crystallographically observed structural motifs and non-covalent interaction acceptor–donor pairings. Our findings indicate that the average electrostatic potential across the halogen ligands (the acceptors) changes by only ∼2 kJ mol^–1 across the AnO₂²⁺ series, indicating that the magnitude of the potential is independent of the metal center. The role of the cation is therefore critical in directing structural motifs and dictating the resulting hydrogen and halogen bond strengths, the former being stronger due to the positive charge centralized on the pyridyl nitrogen, N–H⁺. Subsequent analyses using the quantum theory of atoms in molecules and natural bond orbital approaches support this conclusion and highlight the structure-directing role of the cations. Whereas one can infer that Columbic attraction is the driver for assembly, the contribution of the non-covalent interaction is to direct the molecular-level arrangement (or disposition) of the tectons.

中文翻译：

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超铀混合材料：超分子组装的晶体学和计算度量

组件的家庭的含有[12种ANO超分子化合物的₂氯₄ ] ^{2- （}安= U，NP，PU），通过由取代的4-X-吡啶鎓阳离子捐赠（X = H，氯，溴氢和卤素键我），被报道。这些材料是由室温合成制备的，其中未水解和化合价的[An（VI）O ₂ Cl ₄ ] ^2–（An = U，Np，Pu）构造是常态。我们根据晶体学观察结果提出了组装标准的层次结构，随后使用Kohn-Sham密度泛函计算定量了非共价相互作用的强度。我们首次提供了对in基四卤化物二价阴离子的静电势的详细描述，以及晶体学上观察到的结构基序和非共价相互作用的受体-供体对的调和。我们的发现表明，在整个卤素配体（受体）上的平均静电势在整个AnO ₂ ²⁺系列中仅变化了约2 kJ mol ^–1，表明该电位的大小与金属中心无关。阳离子的作用因此，在引导结构基序和决定氢和卤素键的强度方面起着至关重要的作用，前者由于集中在吡啶氮N–H ⁺上的正电荷而更强。随后使用分子中的原子量子理论和自然键轨道方法进行的分析支持了这一结论，并强调了阳离子的结构指导作用。尽管可以推断出哥伦布吸引力是组装的驱动力，但非共价相互作用的作用是指导构造子的分子水平排列（或布置）。