Fluoride, chloride, and bromide affinities of 1,3,5‐triazacyclohexane (TACH) and 1,4,7,10‐tetraazacyclododecane (Cyclen) were studied theoretically using ωB97XD and B3LYP functionals and 6‐311++G(d,p) basis set. To enhance and modify the anion affinities of TACH and Cyclen, several anion receptors with –(CH₂)_nOH and –(CH₂)_nNH₂ (n = 1–3) substituents were designed and investigated. These anion receptors are attached to the halides (X⁻) via formation of NH … X and OH … X hydrogen bonds. The anion affinities calculated by ωB97XD were larger than those obtained by B3LYP indicating the dispersion contribution to the anion affinities. It was found that the anion affinities of these compounds depend on both the alkyl chain length and nature of the interaction, NH … X or OH … X. The ωB97XD‐calculated fluoride affinities of TACH and Cyclen were 149.5 and 207.2 kJ mol⁻¹, respectively. By substitution of –(CH₂)_nOH groups, anion receptors with F⁻ affinities of 277 and 326 kJ mol⁻¹ were obtained, which can be classified among the strongest organic anion receptors. The affinity of all TACH and Cyclen toward the halides was as F⁻ > Cl⁻ > Br⁻, while substitution of –(CH₂)₃OH and –(CH₂)₃NH₂ into Cyclen changed the trend to F⁻ > Br⁻ > Cl⁻.

中文翻译：

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具有1,3,5-三氮杂环己烷和1,4,7,10-四氮杂环十二烷骨架的阴离子受体

理论上使用ωB97XD和B3LYP官能团和6-311 ++ G（d，p）对1,3,5-三氮杂环己烷（TACH）和1,4,7,10-四氮杂十二烷（Cyclen）的氟化物，氯化物和溴化物亲和力）基础集。为了增强和修饰TACH和Cyclen的阴离子亲和力，设计并研究了几种带有–（CH ₂）_n OH和–（CH ₂）_n NH ₂（n = 1-3）取代基的阴离子受体。这些阴离子受体附着于卤化物（X ^-）形成NH…X和OH…X氢键。通过ωB97XD计算得出的阴离子亲和力大于通过B3LYP获得的阴离子亲和力，表明分散度对阴离子亲和力的贡献。发现这些化合物的阴离子亲和力取决于烷基链长度和相互作用的性质，即NH…X或OH…X。ωB97XD计算得出的TACH和Cyclen的氟化物亲和力分别为149.5和207.2 kJ mol ^-1，分别。通过取代- （CH ₂）_Ñ OH基团，阴离子受体有F ^- 277亲和力和千焦摩尔326 ^-1获得，其可以最强有机阴离子受体中被分类。所有TACH并朝向卤化物的亲和力环烯是为F ^->氯^- >溴^- ，而替代- （CH ₂）₃ OH和- （CH ₂）₃ NH ₂到CYCLEN改变的趋势到F ^- >溴^- >氯^- 。