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<p>The thermally induced, solvent-based synthesis of [Cu(Ina)<sub>2</sub>·(H<sub>2</sub>O)]ISB (CuMOF) and [Ba(Ina)<sub>2</sub>·(H<sub>2</sub>O)]ISB (BaMOF) was achieved by refluxing at 200&#xa0;°C for 30&#xa0;min while stirring at 1000 revolutions per minute. The resulting complexes were characterized using elemental analysis, melting point determination, IR spectroscopy, UV–Visible spectroscopy, and mass spectroscopy. Yields of 79% and 96% were obtained for BaMOF and CuMOF, respectively. The IR spectra of the MOFs showed distinct differences from those of the ligand, indicating successful coordination between the ligand and the metal ion. Elemental analyses for C, H, and N were consistent with the proposed product formula units, demonstrating a strong correlation between the theoretically calculated values and the experimentally determined results. Characterization results revealed that copper and barium ions coordinate with isonicotinic acid through the carbonyl oxygen and the nitrogen of the pyridine ring. Additionally, a water molecule coordinates with the metal ions, contributing to an octahedral geometry with the ligand. Furthermore, isobutanol (C<sub>4</sub>H<sub>7</sub>O) is likely to act as a guest molecule within the complex's pore, forming an intermolecular hydrogen bond with the metal-isonicotinate. Quantum chemical calculations were performed on the molecular geometry, electronic, and optical properties of CuMOF and BaMOF using the DFT/B3LYP/LANL2DZ/6-311++G(d,p) level of theory. The reactivity parameters (such as energy gap) computed using hybrid B3LYP were standardized against highly parameterized M06-2x/LANL2DZ/6-311++G(d,p) method. The static (ħω = 0) and dynamic (ħω = 0.042823&#xa0;au) optical properties of these materials were compared to those of potassium dihydrogen phosphate as a standard. The analysis of kinetic stability and selectivity indices including energy gap, electronegativity, global softness, electrophilicity, and electroaccepting power indicated that CuMOF is more chemically reactive, polarizable, and strongly electrophilic than BaMOF, while exhibiting lower electron-donating power. The molecular electrostatic potential analysis revealed that the nitrogen atom of isonicotinic acid and the oxygen atom of the carboxyl group serve as strong local nucleophilic sites. The nonlinear optical (NLO) response of the materials was significantly enhanced, showing an increase of 2 to 16 times compared to the standard. Additionally, CuMOF exhibited superior NLO properties compared to BaMOF. Notably, both materials demonstrated laser-enhanced NLO properties, as their dynamic optical characteristics exceeded those of their static counterparts suggesting their potentials in optical communication, optical data storage, optical limiters and optical switches.</p>

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Thermally Induced Solvent-Based Synthesis of Copper and Barium Metal–Organic Frameworks of Isonicotinic Acid: Characterization and Quantum Chemical Analysis of Electronic, Static, and Dynamic Optical Properties

  • 期刊论文

  • 发表日期：

    2025年1月7日

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  • Margaret D. Olawale,
  • Nathanael D. Ojo,
  • Oluwatoba E. Oyeneyin,
  • Adedibu C. Tella

摘要

The thermally induced, solvent-based synthesis of [Cu(Ina)2·(H2O)]ISB (CuMOF) and [Ba(Ina)2·(H2O)]ISB (BaMOF) was achieved by refluxing at 200 °C for 30 min while stirring at 1000 revolutions per minute. The resulting complexes were characterized using elemental analysis, melting point determination, IR spectroscopy, UV–Visible spectroscopy, and mass spectroscopy. Yields of 79% and 96% were obtained for BaMOF and CuMOF, respectively. The IR spectra of the MOFs showed distinct differences from those of the ligand, indicating successful coordination between the ligand and the metal ion. Elemental analyses for C, H, and N were consistent with the proposed product formula units, demonstrating a strong correlation between the theoretically calculated values and the experimentally determined results. Characterization results revealed that copper and barium ions coordinate with isonicotinic acid through the carbonyl oxygen and the nitrogen of the pyridine ring. Additionally, a water molecule coordinates with the metal ions, contributing to an octahedral geometry with the ligand. Furthermore, isobutanol (C4H7O) is likely to act as a guest molecule within the complex's pore, forming an intermolecular hydrogen bond with the metal-isonicotinate. Quantum chemical calculations were performed on the molecular geometry, electronic, and optical properties of CuMOF and BaMOF using the DFT/B3LYP/LANL2DZ/6-311++G(d,p) level of theory. The reactivity parameters (such as energy gap) computed using hybrid B3LYP were standardized against highly parameterized M06-2x/LANL2DZ/6-311++G(d,p) method. The static (ħω = 0) and dynamic (ħω = 0.042823 au) optical properties of these materials were compared to those of potassium dihydrogen phosphate as a standard. The analysis of kinetic stability and selectivity indices including energy gap, electronegativity, global softness, electrophilicity, and electroaccepting power indicated that CuMOF is more chemically reactive, polarizable, and strongly electrophilic than BaMOF, while exhibiting lower electron-donating power. The molecular electrostatic potential analysis revealed that the nitrogen atom of isonicotinic acid and the oxygen atom of the carboxyl group serve as strong local nucleophilic sites. The nonlinear optical (NLO) response of the materials was significantly enhanced, showing an increase of 2 to 16 times compared to the standard. Additionally, CuMOF exhibited superior NLO properties compared to BaMOF. Notably, both materials demonstrated laser-enhanced NLO properties, as their dynamic optical characteristics exceeded those of their static counterparts suggesting their potentials in optical communication, optical data storage, optical limiters and optical switches.