Tuning the spin-crossover properties of [Fe2] metal–organic cages,Dalton Transactions

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Tuning the spin-crossover properties of [Fe2] metal–organic cages
Dalton Transactions ( IF 3.5 ) Pub Date : 2024-07-23 , DOI: 10.1039/d4dt01213e
Laia Navarro ₁ , Arnau Garcia-Duran ₁ , Jordi Cirera ₁

Affiliation

A computational study on the interplay between ligand functionalization and guest effects on the transition temperature (T_1/2) in the [Fe₂(L₁^R)₃]@X (L₁ = 1,3-bis-(3-(pyridin-2-yl)-1H-pyrazol-5-yl)benzene, X = H⁻, F⁻, Cl⁻, Br⁻, I⁻ and [BF₄]⁻, R = H, F, or CH₃) family of metal–organic cages (MOCs) is presented. Our results indicate that ligand functionalization with electron-donating or electron-withdrawing groups can significantly impact the T_1/2 as expected, while the guest effect in lowering the T_1/2 has a linear correlation with the increasing guest size. More importantly, small guests can move away from the center of the cavity, thus enhancing the two-step characteristic of the transition. All the data can be understood by analyzing the underlying electronic structure of the studied systems in terms of the relevant d-based molecular orbitals. These results can help in the rational design of new MOCs that can operate as sensors at specific temperatures, thus accelerating the discovery of new SCO devices with tailored properties.

中文翻译：

调整 [Fe2] 金属-有机笼的自旋交越特性

关于配体功能化与客体效应对 [Fe 2（L ₁^R）₃]@X （L₁ = 1,3-bis-（3-（吡啶-2-基）-1H-吡唑-5-基）苯、X = H^-、F^-、Cl^-、Br^-、I^-中键体功能化与客体效应之间相互作用的计算研究和 [BF₄] ⁻， R = H， F 或 CH₃）金属-有机笼（MOC）家族。我们的结果表明，具有供电子或吸电子基团的配体功能化可以按预期显着影响 T_1/2，而降低 T_1/2 的客体效应与客体大小的增加呈线性相关。更重要的是，小客体可以远离型腔的中心，从而增强过渡的两步特性。所有数据都可以通过根据相关的基于 d 的分子轨道分析所研究系统的底层电子结构来理解。这些结果有助于合理设计可以在特定温度下用作传感器的新型 MOC，从而加速发现具有定制特性的新型 SCO 器件。

更新日期：2024-07-23

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