Fluxional halogen bonds in linear complexes of tetrafluorodiiodobenzene with dinitrobenzene

IF 3.4 3区 化学 Q2 CHEMISTRY, MULTIDISCIPLINARY Journal of Computational Chemistry Pub Date : 2024-10-01 DOI:10.1002/jcc.27483
Cai-Yue Gao, Bin-Bin Pei, Si-Dian Li
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Abstract

The fluxional nature of halogen bonds (XBs) in small molecular clusters, supramolecules, and molecular crystals has received considerable attention in recent years. In this work, based on extensive density-functional theory calculations and detailed electrostatic potential (ESP), natural bonding orbital (NBO), non-covalent interactions-reduced density gradient (NCI-RDG), and quantum theory of atoms in molecules (QTAIM) analyses, we unveil the existence of fluxional halogen bonds (FXBs) in a series of linear (IC6F4I)m(OONC6H4NOO)n (m + n = 2–5) complexes of tetrafluorodiiodobenzene with dinitrobenzene which appear to be similar to the previously reported fluxional hydrogen bonds (FHBs) in small water clusters (H2O)n (n = 2–6). The obtained GS TS GS ' fluxional mechanisms involve one FXB in the systems which fluctuates reversibly between two linear CI···O XBs in the ground states (GS and GS') via a bifurcated CI  O2N van der Waals interaction in the transition state (TS). The cohesive energies (Ecoh) of these complexes with up to four XBs exhibit an almost perfect linear relationship with the numbers of XBs in the systems, with the average calculated halogen bond energy of Ecoh/XB = 3.48 kcal·mol−1 in the ground states which appears to be about 55% of the average calculated hydrogen bond energy (Ecoh/HB = 6.28 kcal·mol−1) in small water clusters.

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四氟二碘苯与二硝基苯线性络合物中的通性卤素键。
近年来,小分子团簇、超分子和分子晶体中卤素键(XBs)的通性受到了广泛关注。在这项研究中,我们基于广泛的密度泛函理论计算和详细的静电位(ESP)、天然成键轨道(NBO)、非共价相互作用-还原密度梯度(NCI-RDG)以及分子中原子量子理论(QTAIM)分析,揭示了卤素键(XBs)的通性、我们揭示了四氟二碘苯与二硝基苯的一系列线性 (IC6F4I)m(OONC6H4NOO)n (m + n = 2-5) 复合物中存在的通性卤素键 (FXB),这似乎与之前报道的小型水簇 (H2O)n (n = 2-6) 中的通性氢键 (FHB) 相似。得到的 GS ⇌ TS ⇌ GS ' $$ \mathrm{GS}\rightleftharpoons \mathrm{TS}\rightleftharpoons {\mathrm{GS}}^{\hbox{'}} $$ 通量机制涉及系统中的一个 FXB,该 FXB 在基态(GS 和 GS')中通过过渡态(TS)中分叉的 CI O2N 范德瓦耳斯相互作用在两个线性 CI---O XB 之间可逆地波动。这些具有多达四个 XB 的复合物的内聚能(Ecoh)与体系中的 XB 数量呈现出几乎完美的线性关系,在基态中计算出的平均卤键能为 Ecoh/XB = 3.48 kcal-mol-1,这似乎是计算出的小型水簇中平均氢键能(Ecoh/HB = 6.28 kcal-mol-1)的 55%。
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来源期刊
CiteScore
6.60
自引率
3.30%
发文量
247
审稿时长
1.7 months
期刊介绍: This distinguished journal publishes articles concerned with all aspects of computational chemistry: analytical, biological, inorganic, organic, physical, and materials. The Journal of Computational Chemistry presents original research, contemporary developments in theory and methodology, and state-of-the-art applications. Computational areas that are featured in the journal include ab initio and semiempirical quantum mechanics, density functional theory, molecular mechanics, molecular dynamics, statistical mechanics, cheminformatics, biomolecular structure prediction, molecular design, and bioinformatics.
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