Thermodynamics and kinetics of O₂ adsorption and its impacts on structural features and conductive behavior of 2D π-stacked layered metal–organic frameworks (MOFs) are studied using periodic PBE-D3 quantum mechanical calculations. Our computed O₂ adsorption energies of Co₃(HTTP)₂ (HTTP = hexathiotriphenylene), as a representative of the 2D MOFs family, show that not only open-Co(II) sites but also redox-active HTTP linkers take part in chemisorption of O₂ by forming strong S=O bonds. This is in contrast to conventional 3D Co₂(OH)₂(BBTA) and Fe₂(dobdc) MOFs with similar hexagonal 1D channels where O₂ adsorption occurs solely via coordination to the open-metal sites. Due to the adsorptive capability of its redox-active linkers, Co₃(HTTP)₂ is superior to the analogues 3D MOFs where the change in the oxidation state of the transition metal centers is suggested to result in hindering both the kinetics and thermodynamics of the adsorption process. Our calculated band structures and density of states show that the conductive behavior of the studied Co₃(HTTP)₂ 2D MOF changes dramatically from metallic in the parent system to semiconducting under oxygen rich conditions, with direct bandgap openings that range from 123 to 251 meV. The results presented in this work are helpful in understanding the effects of different electroactive guest molecules on the structure and conductive behavior of 2D layered MOFs and related nonporous materials.

中文翻译：

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通过主客体相互作用调节导电二维层状金属有机框架的电子特性：双氧作为电活性化学刺激

使用周期性 PBE-D3 量子力学计算研究O ₂吸附的热力学和动力学及其对 2D π堆叠层状金属有机框架 (MOF) 的结构特征和导电行为的影响。我们计算的 Co ₃ (HTTP) ₂ (HTTP = hexathiotriphenylene) 的O ₂吸附能，作为 2D MOFs 家族的代表，表明不仅开放 Co(II) 位点而且氧化还原活性 HTTP 链接器都参与化学吸附O ₂通过形成强 S=O 键。这与具有类似六角形一维通道的常规3D Co ₂（OH）₂（BBTA）和Fe ₂（dobdc）MOF形成对比，其中O₂吸附仅通过与开放金属位点的配位发生。由于其氧化还原活性接头的吸附能力，Co ₃ (HTTP) ₂优于类似物 3D MOF，其中过渡金属中心氧化态的变化被认为会阻碍材料的动力学和热力学。吸附过程。我们计算的能带结构和态密度表明所研究的 Co ₃ (HTTP) ₂的导电行为2D MOF 在富氧条件下从母体系统中的金属转变为半导体，直接带隙开口范围为 123 至 251 meV。这项工作中提出的结果有助于理解不同电活性客体分子对二维层状 MOF 和相关无孔材料的结构和导电行为的影响。