Structural diversity and non-covalent interactions in Cd(II) and Zn(II) complexes derived from 3,5-dinitrobenzoic acid and pyridine: Experimental and theoretical aspects

Roy, Subhadip; Bauzá, Antonio; Schaper, Frank; Banik, R.; Purkayastha, Atanu; Reddy, Benjaram M.; Sridhar, Balasubramanian; Drew, Michael G. B.; Das, Subrata; Das, Subrata

doi:10.1016/j.ica.2015.10.025

Cited by 20 publications

(9 citation statements)

References 99 publications

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“…Among different benzene core monocarboxylic acids, 3,5-dinitrobenzoic acid (3,5-Hdnb) represents a particularly interesting multifunctional ligand due to the presence of one carboxylic group capable of binding to metal ions in both anionic and neutral acid forms, two nitro groups for both complexation and noncovalent interactions and an aromatic ring favoring π-stacking interactions. In addition, an ancillary ligand like pyridine (py) is useful to prevent undesired aggregation of metal centers binding through its nitrogen atom as well as to provide supramolecular contacts. − …”

Section: Introductionmentioning

confidence: 99%

Two Polymorphic Forms of a Six-Coordinate Mononuclear Cobalt(II) Complex with Easy-Plane Anisotropy: Structural Features, Theoretical Calculations, and Field-Induced Slow Relaxation of the Magnetization

et al. 2016

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A mononuclear cobalt(II) complex [Co(3,5-dnb)2(py)2(H2O)2] {3,5-Hdnb = 3,5-dinitrobenzoic acid; py = pyridine} was isolated in two polymorphs, in space groups C2/c (1) and P21/c (2). Single-crystal X-ray diffraction analyses reveal that 1 and 2 are not isostructural in spite of having equal formulas and ligand connectivity. In both structures, the Co(II) centers adopt octahedral {CoN2O4} geometries filled by pairs of mutually trans terminal 3,5-dnb, py, and water ligands. However, the structures of 1 and 2 disclose distinct packing patterns driven by strong intermolecular O-H···O hydrogen bonds, leading to their 0D→2D (1) or 0D→1D (2) extension. The resulting two-dimensional layers and one-dimensional chains were topologically classified as the sql and 2C1 underlying nets, respectively. By means of DFT theoretical calculations, the energy variations between the polymorphs were estimated, and the binding energies associated with the noncovalent interactions observed in the crystal structures were also evaluated. The study of the direct-current magnetic properties, as well as ab initio calculations, reveal that both 1 and 2 present a strong easy-plane magnetic anisotropy (D > 0), which is larger for the latter polymorph (D is found to exhibit values between +58 and 117 cm(-1) depending on the method). Alternating current dynamic susceptibility measurements show that these polymorphs exhibit field-induced slow relaxation of the magnetization with Ueff values of 19.5 and 21.1 cm(-1) for 1 and 2, respectively. The analysis of the whole magnetic data allows the conclusion that the magnetization relaxation in these polymorphs mainly takes place through a virtual excited state (Raman process). It is worth noting that despite the notable difference between the supramolecular networks of 1 and 2, they exhibit almost identical magnetization dynamics. This fact suggests that the relaxation process is intramolecular in nature and that the virtual state involved in the two-phonon Raman process lies at a similar energy in polymorphs 1 and 2 (∼20 cm(-1)). Interestingly, this value is recurrent in Co(II) single-ion magnets, even for those displaying different coordination number and geometry.

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Section: Introductionmentioning

confidence: 99%

Two Polymorphic Forms of a Six-Coordinate Mononuclear Cobalt(II) Complex with Easy-Plane Anisotropy: Structural Features, Theoretical Calculations, and Field-Induced Slow Relaxation of the Magnetization

et al. 2016

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“…[ 50 ] Analysis revealed that L emerged emission at 441 nm while Zn (II) complex showed the strongest emission at 489 nm upon excitation at 335 nm and underwent a red‐shift of 48 nm relative to the ligand, which was tentatively attributed to intra‐ligand π → π * electronic transitions, because the closed–shell d 10 configurations was difficult to oxidize/reduce. [ 51 ] Comparatively, it can be seen that fluorescence quenching of Ni (II) complex relative to L can be attributed to the interaction between the ligand L and Ni 2+ . The benzene ring was distorted and the degree of conjugation of the system changed after the ligand was coordinated with the metal, leading to the phenomenon of fluorescence quenching.…”

Section: Resultsmentioning

confidence: 99%

Novel zinc (II) and nickel (II) complexes of a quinazoline‐based ligand with an imidazole ring: Synthesis, spectroscopic property, antibacterial activities, time‐dependent density functional theory calculations and Hirshfeld surface analysis

Chai

et al. 2022

Applied Organom Chemis

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Two complexes [Zn(L) 2 (CH 3 OH) 2 ](NO 3 ) 2 (1) and [Ni(L) 3 ]Á(NO 3 ) 2 (2) (L = 2-[2-imidazolyl]-4-methyl-1,2-dihydroquinazoline-N 3 -oxide) were obtained successfully by means of slow evaporation solution technique (SEST)and characterized using elemental analysis, FT-IR, UV-vis, and fluorescence spectroscopic. X-ray diffraction revealed that the metal in complex 1 is chelated by two L ligands and two lattice methanol molecules, whereas in 2 by three L ligands, counterbalanced by nitrate ions. The crystal structures of both showed infinite 1-D, 2-D, and 3-D supramolecular architecture due to intermolecular interactions. Most strikingly, Zn (II) complex showed different fluorescence properties in diverse solvents. The antimicrobial activities of all compounds were compared and showed perceptible efficiency against Gramnegative and Gram-positive bacteria. Electrostatic potential (ESP) calculation was used to predict the nucleophilic and electrophilic attack sites. Density functional theory (DFT) calculation results showed good agreement with experimental data, as well as the frontier molecular orbital energy gaps were detected by time-dependent (TD)-DFT method with HOMO-LUMO calculations. Additionally, the non-covalent interactions of both complexes were further quantified and explored with the help of Hirshfeld surface analysis.

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“…1622 and 1398 cm −1 are due to asymmetric (ν asy COO -) and symmetric (ν s COO -) stretches of carboxylate, respectively. νCOO -[ν asy (COO -)-ν sym (COO -)] is 224 cm −1 (>200 cm −1 ), typical of monodentate carboxylate [53]. The stretching frequencies observed at ca.…”

Section: Ir Spectroscopymentioning

confidence: 99%

Field Induced Slow Magnetic Relaxation in a Non Kramers Tb(III) Based Single Chain Magnet

Kharwar¹,

Mondal²,

Konar³

2018

Magnetochemistry

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Herein, we report a novel Tb(III) single chain magnet with the chemical formulae [Tb(μ-OH2)(phen)(μ-OH)(nb)2]n by using 4-nitrobenzoic acid (Hnb) and 1,10-phenanthroline (phen) as ligand system. The single-crystal X-ray diffraction reveals that 4-nitrobenzoic acid acts as a monodentate ligand, water and hydroxyl ions are the bridging ligand and the phen serves as a bidentate chelating ligand. The static magnetic susceptibility measurement (from 2 K to 300 K) shows ferromagnetic interaction at very low temperature (below 6 K). The alternating current (AC) susceptibility data of the complex show temperature and frequency dependence under an applied 2000 Oe DC (direct current) field. The phen moiety behaves as an antenna and enables the complex to show the green light fluorescence emission by absorption-energy transfer-emission mechanism. To calculate the exchange interaction, broken symmetry density functional theory (BS-DFT) calculations have been performed on a model compound which also reveals weak ferromagnetic interaction. Ab initio calculations reveals the anisotropic nature (gz = 15.8, gy, gy = 0) of the metal centre and the quasi doublet nature of ground state with small energy gap and that is well separated from the next excited energy state.

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Structural diversity and non-covalent interactions in Cd(II) and Zn(II) complexes derived from 3,5-dinitrobenzoic acid and pyridine: Experimental and theoretical aspects

Cited by 20 publications

References 99 publications

Two Polymorphic Forms of a Six-Coordinate Mononuclear Cobalt(II) Complex with Easy-Plane Anisotropy: Structural Features, Theoretical Calculations, and Field-Induced Slow Relaxation of the Magnetization

Two Polymorphic Forms of a Six-Coordinate Mononuclear Cobalt(II) Complex with Easy-Plane Anisotropy: Structural Features, Theoretical Calculations, and Field-Induced Slow Relaxation of the Magnetization

Novel zinc (II) and nickel (II) complexes of a quinazoline‐based ligand with an imidazole ring: Synthesis, spectroscopic property, antibacterial activities, time‐dependent density functional theory calculations and Hirshfeld surface analysis

Field Induced Slow Magnetic Relaxation in a Non Kramers Tb(III) Based Single Chain Magnet

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