Synthesis of Crystalline Fluoro-Functionalized Imines, Single Crystal Investigation, Hirshfeld Surface Analysis, and Theoretical Exploration

Ashfaq, Muhammad; Khalid, Muhammad; Tahir, Muhammad Nawaz; Ali, Akbar; Arshad, Muhammad Nadeem; Asiri, Abdullah M.

doi:10.1021/acsomega.2c00288

Cited by 33 publications

(14 citation statements)

References 78 publications

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“…Figure 7 (a–b) represents the crystal voids in the crystal structure of 2AP6NO and 2AP4ETH . The voids are measured by assuming that all the atoms of a molecule are spherically symmetric [53–58] . The percentage of crystal void was calculated by the ratio of void volume to unit cell volume.…”

Section: Resultsmentioning

confidence: 99%

Synthesis, Characterization, Crystal Structure and Computational Study of Third‐Order NLO Properties of Schiff bases

et al. 2022

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The current study involves the synthesis of two azomethine compounds, (E)‐2‐((6‐nitrobenzo[d][1,3]dioxol‐5‐yl)methylene)amino)phenol (2AP6NO) and (E)‐2‐((4‐ethylbenzylidene)amino)phenol (2AP4ETH), as well as their theoretical investigations. The synthesized azomethine compounds were then characterized by combustion analysis (CHN), FT‐IR, NMR (1H and 13C), and single crystal X‐ray diffraction (SC‐XRD) analysis. The SC‐XRD study confirmed the enol tautomeric form of 2AP6NO as well as 2AP4ETH. The strong and comparatively weak intermolecular interactions were elaborated by Hirshfeld surface analysis. For both compounds, intermolecular interaction energies between the pair of molecules, energy framework, and void analysis were calculated to visualize the three‐dimensional topology of the crystal packing. Additionally, quantum chemical computations were also utilized to study the optical and nonlinear optical (NLO) response. The molecular geometries were optimized at the M06‐2X/6‐311G* method and equated to their respective experimental counterparts. The third‐order NLO polarizabilities were also calculated at the same level of theory. The calculated average third‐order NLO polarizabilities were 62.55×10−36 esu and 55.08×10−36 esu, respectively, predicting the modest behavior of the above compounds when displaying NLO properties.

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Section: Resultsmentioning

confidence: 99%

Synthesis, Characterization, Crystal Structure and Computational Study of Third‐Order NLO Properties of Schiff bases

et al. 2022

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“…To study the IHB in more detail, we evaluated the second-order interaction energy through NBO calculations. − The interaction energy is related to stabilizing donor–acceptor interactions due to electron delocalization concerning the zeroth-order natural Lewis structure. , In addition, NBO analysis provides an efficient method for studying the participation of the IHB in the stability of N-harboring compounds …”

Section: Computational Detailsmentioning

confidence: 99%

Intramolecular Hydrogen Bond in Pyridine Schiff Bases as Ancillary Ligands of Re(I) Complexes Is a Switcher between Visible and NIR Emissions: A Relativistic Quantum Chemistry Study

et al. 2022

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Rhenium(I) tricarbonyl complexes have been described as suitable fluorophores, particularly for biological applications. fac-[Re(CO)3(N,N)L](0 or 1+) complexes, where N,N is a substituted dinitrogenated ligand (bipyridine or derivatives with relatively small substituents) and L the ancillary ligand [a pyridine Schiff base (PSB) harboring an intramolecular hydrogen bond (IHB)], have presented promissory results concerning their use as fluorophores, especially for walled cells (i.e., bacteria and fungi). In this work, we present a relativistic theoretical analysis of two series of fac-[Re(CO)3(N,N)PSB]1+ complexes to predict the role of the IHB in the ancillary ligand concerning their photophysical behavior. N,N corresponds to 2,2′-bipyridine (bpy) (series A) or 4,4′-bis(ethoxycarbonyl)-2,2′-bipyridine (deeb) (series B). We found that all the complexes present absorption in the visible light range. In addition, complexes presenting a PSB with an IHB exhibit luminescent emission suitable for biological purposes: large Stokes shift, emission in the range of 600–700 nm, and τ in the order of 10–2 to 10–3 s. By contrast, complexes with PSB lacking the IHB show a predicted emission with the lowest triplet excited-state energy entering the NIR region. These results suggest a role of the IHB as an important switcher between visible and NIR emissions in this kind of complexes. Since the PSB can be substituted to modulate the properties of the whole Re(I) complex, it will be interesting to explore whether other substitutions can also affect the photophysical properties, mainly the emission range.

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“… 8 Therefore, the preparation of new Schiff bases and their metal complexes along with computational exploration is a significant research endeavor. 15 …”

Section: Introductionmentioning

confidence: 99%

“…8 Therefore, the preparation of new Schiff bases and their metal complexes along with computational exploration is a significant research endeavor. 15 We report the synthesis and characterization of a Schiff base, H 2 AD1Me, and its palladium(II) complex, [Pd(AD1Me)] and nickel(II) complex, [Ni(AD1Me)] (Scheme 1). The molecular structures of all compounds were elucidated through elemental analysis, magnetic susceptibility, molar conductivity, FTIR, 1 H NMR, UV−vis analysis, and single crystal X-ray diffraction.…”

Section: Introductionmentioning

confidence: 99%

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Synthesis, Structural Characterization, Hirshfeld Surface Analysis, and Antibacterial Study of Pd(II) and Ni(II) Schiff Base Complexes Derived from Aliphatic Diamine

et al. 2022

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A Schiff base bearing two methyl substituents, namely, 6,6′-((1E,1′E)-((2,2-dimethylpropane-1,3-diyl) bis(azanylylidene)) bis(methanylylidene)) bis(2-methylphenol) [H2AD1Me] was synthesized and characterized through physicochemical and spectroscopic analyses. Then, the Schiff base was complexed with Pd(II) and Ni(II) to form [Pd(AD1Me)] and [Ni(AD1Me)], respectively. Both metal complexes were successfully obtained and characterized through several analyses, viz., melting point, elemental analysis, molar conductivity, magnetic susceptibility, FTIR, 1H NMR, UV–vis, and single crystal X-ray diffraction. A quantitative analysis of the intermolecular interactions in the crystal structures has been performed using Hirshfeld surface analysis. Both metal complexes were crystallized in a monoclinic crystal system with the space group of P21/c. Additionally, the deprotonated phenolic oxygen atom (O1/O2) and azomethine nitrogen atom (N1/N2) of the ligand chelate the Pd(II) and Ni(II) ions, forming a slightly distorted square-planar complex containing three six-membered rings encircling the metal core with dsp2 hybridization. The shift of ν(CN) to a higher frequency in FTIR by 26–28 cm–1 indicated that the complexation to Pd(II) and Ni(II) through the azomethine N was established. It was further supported through the shifting of the azomethine proton signal to higher or lower chemical shifts with Δδ = 0.43–1.15 ppm in 1H NMR. In addition, the shifting of the n−π*(CN) band in UV–vis spectra with Δλ = 24–40 nm indicated the involvement of azomethine nitrogen in the complexation. All the compounds showed no significant antibacterial activity against three bacterial strains, namely, Staphylococcus aureus subsp. aureus Rosenbach (ATCC 6538), Streptococcus mutans Clarke (ATCC 700,610), and Proteus vulgaris (ATCC 6380), as the percent growth inhibition calculated was less than 90%.

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Synthesis of Crystalline Fluoro-Functionalized Imines, Single Crystal Investigation, Hirshfeld Surface Analysis, and Theoretical Exploration

Cited by 33 publications

References 78 publications

Synthesis, Characterization, Crystal Structure and Computational Study of Third‐Order NLO Properties of Schiff bases

Synthesis, Characterization, Crystal Structure and Computational Study of Third‐Order NLO Properties of Schiff bases

Intramolecular Hydrogen Bond in Pyridine Schiff Bases as Ancillary Ligands of Re(I) Complexes Is a Switcher between Visible and NIR Emissions: A Relativistic Quantum Chemistry Study

Synthesis, Structural Characterization, Hirshfeld Surface Analysis, and Antibacterial Study of Pd(II) and Ni(II) Schiff Base Complexes Derived from Aliphatic Diamine

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