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：

调节[Fe2]金属有机笼的自旋交叉特性

配_体功能化与客体效应对[Fe ₂ (L ₁ ^R ) ₃ ]@X (L ₁ = 1,3-bis-(3-(吡啶-2-基)-1 H-吡唑-5-基)苯，X = H ^- 、F ^- 、Cl ^- 、Br ^- 、I ^-和 [BF ₄ ] ^- ，R = H、F 或 CH ₃ ）提出了金属有机保持架（MOC）系列。我们的结果表明，具有给电子或吸电子基团的配体官能化可以显着影响T _1/2 ，如预期的那样，而降低T _1/2的客体效应与增加的客体尺寸呈线性相关。更重要的是，小客人可以远离腔体的中心，从而增强了过渡的两步特性。通过根据相关 d 基分子轨道分析所研究系统的基础电子结构，可以理解所有数据。这些结果有助于合理设计可在特定温度下作为传感器运行的新型 MOC，从而加速具有定制特性的新型 SCO 器件的发现。

更新日期：2024-07-23

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