Synthesis and single crystal X-ray diffraction studies of coumarin-based Zn(II) and Mn(II) complexes, involving supramolecular interactions

Stefanou, Valentina; Matiadis, Dimitris; Tsironis, Dimitrios; Igglessi‐Markopoulou, Olga; McKee, Vickie; Markopoulos, John

doi:10.1016/j.poly.2017.12.011

Cited by 8 publications

(4 citation statements)

References 42 publications

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“…The continuously evolving and never-ending exploration of this prospect has led to the discovery of numerous innovative materials with sundry applications as well as an advancement of knowledge leading to a better understanding of the structure–property relationship. Crystal engineering plays a pivotal role in the synthesis of such ordered materials as it provides a platform to amalgamate different organic molecules that have requisite topologies with inorganic components (metal ions) to produce ordered materials with predictable structures . This strategy also provides an opportunity to vary the metal ions, which allows the tuning of the properties of materials.…”

Section: Introductionmentioning

confidence: 99%

Amidine/Amidinate Cobalt Complexes: One-Pot Synthesis, Mechanism, and Photocatalytic Application for Hydrogen Production

et al. 2020

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A new synthetic route was carried out via a one-pot reaction to prepare a novel series of amidine/amidinate cobalt complexes 8−10 by mixing ligand 2 (6-pyridin-2-yl-[1,3,5]triazine-2,4-diamine) with Co(II) in acetonitrile or benzonitrile. We observed that a change of solvent from methanol (used in complex 7, previously reported) to nitrile solvents (MeCN and PhCN) led to the in situ incorporation of the amidine group, ultimately forming 8−10. So far, this is a unique method reported to introduce amidine/amidinate groups into a pyridinyl-substituted diaminotriazine complex. Remarkably, the single crystal X-ray diffraction study (SCXRD) of these new compounds reveals associations involving Janus DATamidine and Janus DATamidinate. A mechanism is proposed to explain the formation of amidine/ amidinate groups by investigating the single crystal structures of the possible intermediates 11 and 12 where the cobalt ion acts as a template. These amidine/amidinate cobalt complexes were used as a model to assess the photocatalytic activity for the hydrogen evolution reaction (HER). Complexes 9 and 10 show a 74% and 86% enhancement, respectively, of the catalytic activity towards the HER compared to complex 7. This highlights the structure−property relationship. By examining the novel cobalt complexes described here, we discovered the following: (i) a method to introduce an amidine group into a pyridine DAT-based complex, (ii) the efficiency of amidine complexes to form multiple hydrogen bonds to direct the molecular organization, (iii) the plausible mechanism of formation of amidines based on the SCXRD study, (iv) the modification of the final structure and hence the final properties by varying the reaction conditions, and (v) the utility of amidine complexes towards photocatalytic HER activity.

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Section: Introductionmentioning

confidence: 99%

Amidine/Amidinate Cobalt Complexes: One-Pot Synthesis, Mechanism, and Photocatalytic Application for Hydrogen Production

et al. 2020

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“…These distances were comparable to values reported in the literature. [ 31,32 ] The dihedral angle between two coordination planes (N2–Mn1–N2 and O1–Mn1–O1) was 86.876°.…”

Section: Resultsmentioning

confidence: 99%

Antimicrobial activities of two 1‐D, 2‐D, and 3‐D mononuclear Mn (II) and dinuclear Bi (III) complexes: X‐ray structures, spectroscopic, electrostatic potential, Hirshfeld surface analysis, and time‐dependent/density functional theory studies

Chai

Zhang

et al. 2022

Applied Organom Chemis

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Two mononuclear and dinuclear octahedral complexes, [Mn(L1)2Cl2] (1) and [Bi2(L2)2Cl8] (2) (L1 = 2‐(2‐pyridyl)‐4‐methyl‐1,2‐dihydroquinazoline‐N3‐oxide, L2 = 2‐(3‐pyridyl)‐4‐methyl‐1,2‐dihydroquinazoline‐N3‐oxide) were prepared by natural volatilization method. The ligands and both complexes were compared with spectroscopic methods, as well as characterized by elemental analysis. The photoluminescence behaviors of both complexes in different solvents were also investigated. The coordination possibility of ligands toward Mn (II)/Bi (III) was verified using X‐ray crystallography, and it revealed that the ratio of ligand to metal was 2:1 in 1, whereas 1:1 in 2. The adjacent molecules of six‐coordinated complex 1 constituted an infinite 1‐D chain, 2‐D network, and ladder‐like 3‐D supramolecular frameworks. Most strikingly, hexa‐coordinated complex 2 with dinuclear structure formed an infinite 1‐D chain, 2‐D layered and meter‐shaped 3‐D supramolecular skeleton. Density functional theory (DFT) calculation was used to optimize the geometry of complexes, compute the electrostatic potential diagrams, and evaluate the HOMO‐LUMO energy gap. The electronic transition simulated through time‐dependent (TD)‐DFT level of calculation rationalized the experimental data. The antibacterial properties of all compounds were evaluated against Gram‐positive and Gram‐negative bacterial strains. In addition, the Hirshfeld surface was utilized to quantify some hydrogen bonding interactions and their contributions.

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“…The octahedral high-spin d 5 complexes have no excited states of the same spin multiplicity [48] as the ground state. The bands that are observed as the consequence of spin-forbidden transitions are typically weak [51] . The Mn(II) complex exhibit three absorption bands in the range of 529 nm (ε = 278 M -1 ‧ cm -1 ), 489 (ε = 298 M -1 ‧ cm -1 ) and 454 (ε = 385 M -1 ‧ cm -1 ) assigned to the transitions 6 A1g→ 4 T1g (4G), 6 A1g→ 4 T2g (4G) and 6 A1g→ 4 A1g (4G), 4 Eg (4E) respectively.…”

Section: Mn(ii) Complexmentioning

confidence: 99%

Synthesis, characterization and antimicrobial activity of N-acetyl-3-acetyl-5-benzylidene tetramic acid-metal complexes. X-ray analysis and identification of the Cd(II) complex as a potent antifungal agent

Matiadis

Tsironis

Stefanou

et al. 2019

Journal of Inorganic Biochemistry

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Synthesis and single crystal X-ray diffraction studies of coumarin-based Zn(II) and Mn(II) complexes, involving supramolecular interactions

Cited by 8 publications

References 42 publications

Amidine/Amidinate Cobalt Complexes: One-Pot Synthesis, Mechanism, and Photocatalytic Application for Hydrogen Production

Amidine/Amidinate Cobalt Complexes: One-Pot Synthesis, Mechanism, and Photocatalytic Application for Hydrogen Production

Antimicrobial activities of two 1‐D, 2‐D, and 3‐D mononuclear Mn (II) and dinuclear Bi (III) complexes: X‐ray structures, spectroscopic, electrostatic potential, Hirshfeld surface analysis, and time‐dependent/density functional theory studies

Synthesis, characterization and antimicrobial activity of N-acetyl-3-acetyl-5-benzylidene tetramic acid-metal complexes. X-ray analysis and identification of the Cd(II) complex as a potent antifungal agent

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