Samawi Khalida Abaid, Imad Ali Shaimaa, Salman Taghried A, Alshekhly Belal A
Department of Chemistry, College of sciences, Al-Nahrain University, Jadriya, Baghdad, Iraq.
Department of Chemistry, College of sciences, Al-Nahrain University, Jadriya, Baghdad, Iraq.
J Mol Graph Model. 2025 Nov;140:109088. doi: 10.1016/j.jmgm.2025.109088. Epub 2025 May 26.
Phthalocyanine-based covalent organic frameworks (PC-COFs) are a novel subclass of COFs that integrate phthalocyanine units to enhance electronic, optical, and catalytic properties. These frameworks are particularly effective in CO adsorption due to their high surface area, tunable porosity, and exceptional stability. In this study, we have employed density functional theory (DFT) calculations to explore the electronic properties of phthalocyanine doped with various metal centers (Co, Cu, Fe, Ni, Zn) and their impact on CO adsorption. The geometries of metal-doped phthalocyanines and their CO complexes were optimized using the B3PW91 functional with the LANL2DZ basis set. Adsorption energies, electronic structures, and reactivity indices such as HOMO-LUMO gaps, ionization potentials, and electron affinities were analyzed. The findings revealed that Fe-doped phthalocyanines exhibited the highest reactivity and strongest CO adsorption due to favorable charge transfer interactions. Additionally, aromaticity indices (HOMA and Bird) indicated enhanced aromatic character upon CO adsorption. These insights provide a foundation for designing more efficient PC-COF materials for CO capture, emphasizing the crucial role of electronic properties and metal center selection in optimizing adsorption performance.
基于酞菁的共价有机框架（PC-COFs）是共价有机框架的一个新型子类，它整合了酞菁单元以增强电子、光学和催化性能。由于其高比表面积、可调节的孔隙率和出色的稳定性，这些框架在CO吸附方面特别有效。在本研究中，我们采用密度泛函理论（DFT）计算来探索掺杂各种金属中心（Co、Cu、Fe、Ni、Zn）的酞菁的电子性质及其对CO吸附的影响。使用带有LANL2DZ基组的B3PW91泛函对金属掺杂酞菁及其CO配合物的几何结构进行了优化。分析了吸附能、电子结构和诸如HOMO-LUMO能隙、电离势和电子亲和势等反应性指数。研究结果表明，由于有利的电荷转移相互作用，Fe掺杂的酞菁表现出最高的反应性和最强的CO吸附。此外，芳香性指数（HOMA和Bird）表明CO吸附后芳香性增强。这些见解为设计更高效的用于CO捕获的PC-COF材料提供了基础，强调了电子性质和金属中心选择在优化吸附性能中的关键作用。
