Computational design of the novel building blocks for the metal-organic frameworks based on the organic ligand protected Cu4 cluster
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Francisca Claveria-Cádiz
and
Aleksey E. Kuznetsov
Abstract
Metal-organic frameworks (MOFs) are tunable porous network compounds composed of inorganic nodes bound by various organic linkers. Here we report the density functional theory (DFT) study of the MOF novel building blocks made of the Cu4 clusters protected by four organic ligands having two phenyl rings and terminated either with Cl or Br atom (precursors 1 and 2, respectively). The research was performed both in the gas phase and with the implicit effects of acetonitrile included, with two functionals, B3LYP and PBE, both with and without the second-order dispersion correction. We analyzed the structural features of the precursors 1 and 2, their electronic structures, molecular electrostatic potential (MEP) distribution, and global reactivity parameters (GRPs). Both functionals resulted in the singlets of the precursors 1 and 2 as the most stable species. The precursor structures optimized with the hybrid functional were found to be quite similar for both halogens, both containing somewhat distorted from planarity Cu4 cluster, with the outer phenyls of the ligands rotated relative to the inner phenyls. With both halogens and both DFT approaches, the frontier molecular orbitals (FMOs) of the precursors 1 and 2 were shown to have quite similar compositions. The change of the substituent from Br to Cl was found to cause slight stabilizations or destabilizations of the HOMOs and LUMOs. The central parts and especially the inner phenyl ring parts of the precursors 1 and 2 were suggested to play a role of nucleophile in various chemical reactions due to the significant accumulation of negative electrostatic potential. Also, weak intermolecular interactions might exist between the ligands of neighboring precursor molecules. Finally, with both substituents the precursors 1 and 2 should be relatively unreactive and demonstrate thermodynamic stability. Further, the precursors 1 and 2 should be quite stable in oxidation reactions and more active in reduction processes. Generally, the substituent nature was shown not to affect significantly the reactivity of the precursors 1 and 2, as well as their other properties.
Funding source: Agencia Nacional de Investigación y Desarrollo
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Author contributions: All the authors have accepted responsibility for the entire content of this submitted manuscript and approved submission.
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Research funding: F.C. is thankful for the financial support of USM and ANID (Agencia Nacional de Investigación y Desarrollo), Chile. Powered@NLHPC: This research was partially supported by the supercomputing infrastructure of the NLHPC (ECM-02). This research was also partially supported by the high-performance computing system of PIDi-UTEM (SCC-PIDi-UTEM CONICYT–FONDEQUIP - EQM180180).
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Conflict of interest statement: The authors declare no conflicts of interest regarding this article.
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- Triterpenoids of antibacterial extracts from the leaves of Bersama abyssinica Fresen (Francoaceae)
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- Xanthoangelol, geranilated chalcone compound, isolation from pudau leaves (Artocarpus kemando Miq.) as antibacterial and anticancer
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