A Themed Issue in Honor of Late Professor Samiran Mitra

A special issue of Magnetochemistry (ISSN 2312-7481).

Deadline for manuscript submissions: closed (31 October 2018) | Viewed by 43568

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Department of Inorganic Chemistry, Faculty of Chemistry, University of Valencia, C/Dr. Moliner 50, 46100 Burjasot, Valencia, Spain
Interests: molecular magnetism; coordination magnetic polymers; magnetic MOFs; magnetic polyoxometalates; conducting magnetic materials; multifunctional magnetic materials
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Department of Chemistry, University of Calcutta, 92, APC Road, Kolkata- 700 009, India
Interests: Coordination Chemistry

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Centre de Recherche Paul Pascal, Research team for “Molecular Magnetic Materials” (M3), 115, Avenue du Dr. A. Schweitzer, 33600 Pessac, France
Interests: coordination chemistry, magnetochemistry, single chain magnets, photomagnetism

Special Issue Information

Dear Colleagues,

Magnetochemistry is pleased to announce a memorial Special Issue, dedicated to Professor Samiran Mitra at Jadavpur University, India, on the occasion of his passing away in December 2017, for his outstanding contribution in the research fields of inorganic, coordination, and solid-state chemistry.

Short biography

Dr. Samiran Mitra was born on 28th of March 1949 in West Bengal, India. He obtained his Ph.D. in inorganic chemistry in 1976 from the Indian Association for the Cultivation of Science. He was a JSPS post-doctoral fellow in the Department of Chemistry, Kanazawa University, Japan (1978-1979) and also worked as a guest scientist in Kernforschungszentrum, Karlsruhe, Germany (1980-1981). He joined Department of Chemistry, Manipur University in India as an assistant professor in 1984 and worked as a guest professor of chemistry at the Univerisity of Kassel, Germany (1990-1991). He moved to Jadavpur University, Kolkata, India as a reader in 1992 and continued his research career there till 2016 as a Professor and Emeritus Professor. In his prolonged research career he received Prof. Priyadaranjan Ray Memorial Award from the Indian Chemical Society in 2006. He supervised the PhD theses of 33 scholars and published 234 scientific articles in peer reviewed journals.

His research interest was focused on the development of the techniques for the synthesis of new multinuclear complexes (homo- or heterometallic) of transition, non-transition, and inner-transition metal ions possessing fascinating architectures. Various Schiff base chelators and bridging co-ligands were used to design such complexes aiming at increasing the molecularity and dimensionality of the complexes utilizing the covalent and weak interactions. The characterizations were performed using various physico-chemical techniques like elemental analyses, UV-Vis, IR, NMR, Mass, EPR spectroscopies, and electrochemical and thermogravimetric analysis. The structures of the synthesized complexes were established by single-crystal X-ray diffraction studies. Variable temperature magnetic susceptibility measurements were performed in relevant cases. Magneto-structural correlations, along with the DFT calculations, were carried out to establish the probable pathways for the exchange magnetic interactions. His research also diversified to the photophysical properties (fluoroscence, as well as photoluminescence), biological activities of the complexes for DNA binding, cleavage studies, and cell inhibitory effect in vitro and in the field of catalysis. The catalase and catecholase mimetic activities of the complexes were investigated with gas volummetry and spectroscopic methods. The transition metal Schiff base complexes were tested as catalysts in various organic transformations such as asymmetric epoxidation of olefins, epoxide ring opening, selective oxygen binding, cycloalkane oxidation, and alkene oxidation in the phase transfer condition, etc.

The main aim of this Special Issue is to publish any research results or a review dealing with any area of magnetochemistry and/or any research subject connected with Prof. Mitra’s research interests.

Prof. Dr. Carlos J. Gómez García
Prof. Dr. Ashutosh Ghosh
Dr. Dipali Sadhukhan
Guest Editors

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Keywords

  • Coordination chemistry
  • Transition metal-Schiff base complexes
  • X-ray crystallography
  • magnetochemistry
  • spectroscopic techniques
  • catalysis
  • DFT analysis and biological activity of coordination complexes

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Published Papers (10 papers)

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Research

11 pages, 2435 KiB  
Article
Field Induced Single Ion Magnetic Behaviour in Square-Pyramidal Cobalt(II) Complexes with Easy-Plane Magnetic Anisotropy
by Amit Kumar Mondal, Arpan Mondal and Sanjit Konar
Magnetochemistry 2019, 5(1), 12; https://doi.org/10.3390/magnetochemistry5010012 - 2 Feb 2019
Cited by 15 | Viewed by 4352
Abstract
Two penta-coordinate CoII complexes with formulae [Co(14-TMC)Cl](BF4) (1, 14-TMC = 1,4,8,11-Tetramethyl-1,4,8,11-tetraazacyclotetradecane) and [Co(12-TBC)Cl](ClO4)·(MeCN) (2, 12-TBC = 1,4,7,10-Tetrabenzyl-1,4,7,10-tetraazacyclododecane) were synthesized and characterized. Structural analysis revealed that ligand coordinates to the CoII centre in a [...] Read more.
Two penta-coordinate CoII complexes with formulae [Co(14-TMC)Cl](BF4) (1, 14-TMC = 1,4,8,11-Tetramethyl-1,4,8,11-tetraazacyclotetradecane) and [Co(12-TBC)Cl](ClO4)·(MeCN) (2, 12-TBC = 1,4,7,10-Tetrabenzyl-1,4,7,10-tetraazacyclododecane) were synthesized and characterized. Structural analysis revealed that ligand coordinates to the CoII centre in a tetradentate fashion and the fifth position is occupied by chloride ion and the geometries around CoII centres are best described as distorted square pyramidal. Detailed magnetic measurements disclose the presence of significant easy-plane magnetic anisotropy and field induced slow magnetic relaxation behaviours of the studied complexes. More insight into the magnetic anisotropy has been given using ab initio theory calculations, which agree well with the experimental values and further confirmed the easy-plane magnetic anisotropy. Full article
(This article belongs to the Special Issue A Themed Issue in Honor of Late Professor Samiran Mitra)
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14 pages, 2247 KiB  
Article
Field Induced Slow Magnetic Relaxation in a Non Kramers Tb(III) Based Single Chain Magnet
by Ajit Kumar Kharwar, Arpan Mondal and Sanjit Konar
Magnetochemistry 2018, 4(4), 59; https://doi.org/10.3390/magnetochemistry4040059 - 19 Dec 2018
Cited by 9 | Viewed by 4508
Abstract
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 [...] Read more.
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. Full article
(This article belongs to the Special Issue A Themed Issue in Honor of Late Professor Samiran Mitra)
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15 pages, 3280 KiB  
Article
Two Dimensional Magnetic Coordination Polymers Formed by Lanthanoids and Chlorocyananilato
by Samia Benmansour, Antonio Hernández-Paredes and Carlos J. Gómez-García
Magnetochemistry 2018, 4(4), 58; https://doi.org/10.3390/magnetochemistry4040058 - 12 Dec 2018
Cited by 19 | Viewed by 3328
Abstract
Here we show the important role played by the size of the lanthanoid and the solvent used in the final structures of several two-dimensional magnetic coordination polymers with the ligand chlorocyananilato, (C6O4(CN)Cl)2−. With this aim we have [...] Read more.
Here we show the important role played by the size of the lanthanoid and the solvent used in the final structures of several two-dimensional magnetic coordination polymers with the ligand chlorocyananilato, (C6O4(CN)Cl)2−. With this aim we have prepared five compounds: [Nd2(C6O4(CN)Cl)3(DMF)6] (1) (DMF = dimethylformamide), [Dy2(C6O4(CN)Cl)3(DMF)6]·4H2O (2), [Ho2(C6O4(CN)Cl)3(DMF)6]·2H2O (3), and [Ln2(C6O4(CN)Cl)3(DMSO)6] with Ln = Ce (4) and Nd (5) (DMSO = dimethylsulfoxide). These compounds are formed by two dimensional networks with a (6,3)-topology but, depending on the size of the lanthanoid and on the solvent used, show important structural differences, including the size, shape, distortion and content of the cavities as well as the flatness of the layers. The comparison of compounds 13 and 45 shows the role played by the size of the lanthanoid while keeping constant the solvent, whereas, the comparison of compounds 1 and 5 shows the role of the solvent (DMF vs. DMSO) while keeping constant the lanthanoid. The magnetic properties of all of them show the absence of noticeable magnetic interactions, in agreement with previous results that can be explained by the internal character of the 4f electron and the weak magnetic coupling mediated by these anilato-based ligands. Full article
(This article belongs to the Special Issue A Themed Issue in Honor of Late Professor Samiran Mitra)
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11 pages, 2220 KiB  
Article
Synthesis, Characterization and Magnetic Studies of a Tetranuclear Manganese(II/IV) Compound Incorporating an Amino-Alcohol Derived Schiff Base
by Madhusudan Nandy, Shyamapada Shit, Georgina Rosair and Carlos J. Gómez-García
Magnetochemistry 2018, 4(4), 57; https://doi.org/10.3390/magnetochemistry4040057 - 11 Dec 2018
Cited by 1 | Viewed by 3010
Abstract
A new tetranuclear mixed-valence manganese(II/IV) compound [MnIIMnIV3(μ-Cl)33-O)(L)3] (1) (where H3L = (3E)-3-((Z)-4-hydroxy-4-phenylbut-3-en-2-ylideneamino)propane-1,2-diol) has been synthesized and characterized by different physicochemical methods. Single crystal X-ray diffraction analysis reveals that [...] Read more.
A new tetranuclear mixed-valence manganese(II/IV) compound [MnIIMnIV3(μ-Cl)33-O)(L)3] (1) (where H3L = (3E)-3-((Z)-4-hydroxy-4-phenylbut-3-en-2-ylideneamino)propane-1,2-diol) has been synthesized and characterized by different physicochemical methods. Single crystal X-ray diffraction analysis reveals that 1 is a tetrahedral cluster consisting of a Mn4Cl3O4 core in which the only Mn(II) ion is joined through three μ2-O bridges to an equilateral triangle of Mn(IV) ions, which are connected by a μ3-O and three μ2-Cl bridges. The redox behavior of 1 was studied by cyclic voltammetry. Variable temperature magnetic susceptibility measurements of 1 revealed predominant antiferromagnetic coupling inside the Mn4Cl3O4 cluster. Full article
(This article belongs to the Special Issue A Themed Issue in Honor of Late Professor Samiran Mitra)
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12 pages, 3448 KiB  
Article
A Co(II)-Hydrazone Schiff Base Single Ion Magnet Exhibiting Field Induced Slow Relaxation Dynamics
by Dipali Sadhukhan, Prithwi Ghosh, Carlos J. Gómez-García and Mathieu Rouzieres
Magnetochemistry 2018, 4(4), 56; https://doi.org/10.3390/magnetochemistry4040056 - 7 Dec 2018
Cited by 6 | Viewed by 3374
Abstract
An octahedral Co(II) complex with N′-(2-hydroxybenzylidene)acetohydrazide Schiff base ligand [HL] forms a 3D supramolecular assembly supported by non-coordinating ClO4 ions and H2O molecules. Individual spin centres are non-interacting and give rise to significant spin-orbit coupling, resulting in field [...] Read more.
An octahedral Co(II) complex with N′-(2-hydroxybenzylidene)acetohydrazide Schiff base ligand [HL] forms a 3D supramolecular assembly supported by non-coordinating ClO4 ions and H2O molecules. Individual spin centres are non-interacting and give rise to significant spin-orbit coupling, resulting in field induced slow magnetisation relaxation; which is characteristic of Single Ion Magnet (SIM) behaviour. Full article
(This article belongs to the Special Issue A Themed Issue in Honor of Late Professor Samiran Mitra)
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19 pages, 2499 KiB  
Article
DFT Protocol for EPR Prediction of Paramagnetic Cu(II) Complexes and Application to Protein Binding Sites
by Giuseppe Sciortino, Giuseppe Lubinu, Jean-Didier Maréchal and Eugenio Garribba
Magnetochemistry 2018, 4(4), 55; https://doi.org/10.3390/magnetochemistry4040055 - 3 Dec 2018
Cited by 36 | Viewed by 7891
Abstract
With the aim to provide a general protocol to interpret electron paramagnetic resonance (EPR) spectra of paramagnetic copper(II) coordination compounds, density functional theory (DFT) calculations of spin Hamiltonian parameters g and A for fourteen Cu(II) complexes with different charges, donor sets, and geometry [...] Read more.
With the aim to provide a general protocol to interpret electron paramagnetic resonance (EPR) spectra of paramagnetic copper(II) coordination compounds, density functional theory (DFT) calculations of spin Hamiltonian parameters g and A for fourteen Cu(II) complexes with different charges, donor sets, and geometry were carried out using ORCA software. The performance of eleven functionals was tested, and on the basis of the mean absolute percent deviation (MAPD) and standard deviation (SD), the ranking of the functionals for Az is: B3LYP > B3PW91 ~ B3P86 > PBE0 > CAM-B3LYP > TPSSh > BH and HLYP > B2PLYP > MPW1PW91 > ω-B97x-D >> M06; and for gz is: PBE0 > BH and HLYP > B2PLYP > ω-B97x-D > B3PW91~B3LYP~B3P86 > CAM-B3LYP > TPSSh~MPW1PW91 >> M06. With B3LYP the MAPD with respect to A z exp t l is 8.6% with a SD of 4.2%, while with PBE0 the MAPD with respect to g z exp t l is 2.9% with a SD of 1.1%. The results of the validation confirm the fundamental role of the second order spin-orbit contribution to Az. The computational procedure was applied to predict the values of gz and Az of the adducts formed by Cu(II) with albumin and two fragments of prion protein, 106–126 and 180–193. Full article
(This article belongs to the Special Issue A Themed Issue in Honor of Late Professor Samiran Mitra)
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9 pages, 1472 KiB  
Article
Synthesis, Structure and Magnetic Study of a Di-Iron Complex Containing N-N Bridges
by Abhishikta Chatterjee, Laurence K. Thompson and Subrata K. Dey
Magnetochemistry 2018, 4(4), 53; https://doi.org/10.3390/magnetochemistry4040053 - 27 Nov 2018
Cited by 5 | Viewed by 3523
Abstract
The iron (II) coordination compound, {[Fe(3,6 pzdc)](H2O)2}2. (1) has been synthesized from a mixture of FeCl2.4H2O and pyridazinedicarboxylate (3,6 pzdc). The molecular structure of complex 1 was determined by single crystal [...] Read more.
The iron (II) coordination compound, {[Fe(3,6 pzdc)](H2O)2}2. (1) has been synthesized from a mixture of FeCl2.4H2O and pyridazinedicarboxylate (3,6 pzdc). The molecular structure of complex 1 was determined by single crystal X-ray diffraction study. It reveals that the dinuclear structure contains a pyridazine bridge in between the two metal centers. The variable temperature magnetic study results in g = 2.496(8), J = −2.50(8) cm−1, Ɵ = −0.1 K values, by fitting the magnetic data in a simple dinuclear Fe-Fe model which indicates that the major exchange pathway through the N-N bridge. Presence of dense H-bonding interaction leads to supramolecular network formation. Full article
(This article belongs to the Special Issue A Themed Issue in Honor of Late Professor Samiran Mitra)
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14 pages, 2764 KiB  
Article
Ni(II) Dimers of NNO Donor Tridentate Reduced Schiff Base Ligands as Alkali Metal Ion Capturing Agents: Syntheses, Crystal Structures and Magnetic Properties
by Monotosh Mondal, Maharudra Chakraborty, Michael G. B. Drew and Ashutosh Ghosh
Magnetochemistry 2018, 4(4), 51; https://doi.org/10.3390/magnetochemistry4040051 - 21 Nov 2018
Cited by 8 | Viewed by 3552
Abstract
Three trinuclear Ni(II)-Na(I) complexes, [Ni2(L1)2NaCl3(H2O)]·H2O (1), [Ni2(L2)2NaCl3(H2O)] (2), and [Ni2(L3)2NaCl3 [...] Read more.
Three trinuclear Ni(II)-Na(I) complexes, [Ni2(L1)2NaCl3(H2O)]·H2O (1), [Ni2(L2)2NaCl3(H2O)] (2), and [Ni2(L3)2NaCl3(OC4H10)] (3) have been synthesized using three different NNO donor tridentate reduced Schiff base ligands, HL1 = 2-[(3-methylamino-propylamino)-methyl]-phenol, HL2 = 2-[(3-methylamino-propylamino)-methyl]-4-chloro-phenol, and HL3 = 2-[(3-methylamino-propylamino)-methyl]-6-methoxy-phenol that had been structurally characterized. Among these complexes, 1 and 2 are isostructural in which dinuclearNi(II) units act as metalloligands to bind Na(I) ions via phenoxido and chlorido bridges. The Na(I) atom is five-coordinated, and the Ni(II) atom possesses hexacordinated distorted octahedral geometry. In contrast, in complex 3, two -OMe groups from the dinuclear Ni(II) unit also coordinate to Na(I) to make its geometry heptacordinated pentagonal bipyramidal. The magnetic measurements of complexes 13 indicate ferromagnetic interactions between dimeric Ni(II) units with J = 3.97 cm−1, 4.66 cm−1, and 5.50 cm−1 for 13, respectively, as is expected from their low phenoxido bridging angles (89.32°, 89.39°, and 87.32° for 13, respectively). The J values have been calculated by broken symmetry DFT method and found to be in good agreement with the experimental values. Full article
(This article belongs to the Special Issue A Themed Issue in Honor of Late Professor Samiran Mitra)
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11 pages, 2333 KiB  
Article
Synthesis, Crystal Structures, and Magnetic Properties of Lanthanide (III) Amino-Phosphonate Complexes
by Karzan H. Zangana
Magnetochemistry 2018, 4(3), 29; https://doi.org/10.3390/magnetochemistry4030029 - 22 Jun 2018
Cited by 6 | Viewed by 4288
Abstract
Two isostructural lanthanide amino-phosphonate complexes [Ln103-OH)3(µ-OH)(CO3)2(O2CtBu)15(O3PC6H10NH2)3(O3PC6H10NH3)2(H2 [...] Read more.
Two isostructural lanthanide amino-phosphonate complexes [Ln103-OH)3(µ-OH)(CO3)2(O2CtBu)15(O3PC6H10NH2)3(O3PC6H10NH3)2(H2O)2][Et2NH2] (Ln = Gd(III), 1 and Tb(III), 2) have been obtained through reflux reactions of lanthanide pivalates with, a functionalized phosphonate, (1-amino-1-cyclohexyl)phosphonic acid and diethylamine (Et2NH) in acetonitrile (MeCN) at 90 °C. Both compounds have been characterized with elemental analysis, single-crystal X-ray diffraction methods, and magnetic measurements. The molecular structure of compounds 1 and 2 reveal two highly unsymmetrical complexes comprising ten lanthanide metal centers, where the lanthanide metal ion centers in the cages are linked through pivalate units and further interconnected by CPO3 tetrahedra to build the crystal structure. The magnetic behavior of 1 and 2 was investigated between ambient temperature and ca. 2 K, the magnetic measurements for compound 1 suggests antiferromagnetic interactions between the Gd(III) metal ion centers at low temperatures. The large number of isotropic Gd(III) ions comprising 1 makes it a candidate for magnetocaloric applications, thus the magnetocaloric properties of this molecular cage were investigated indirectly through isothermal magnetisation curves. The magnetic entropy change was found to be 34.5 J kg−1K−1, making 1 a plausible candidate in magnetic cooling applications. Full article
(This article belongs to the Special Issue A Themed Issue in Honor of Late Professor Samiran Mitra)
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13 pages, 3320 KiB  
Article
Cu(II)–N6-Alkyladenine Complexes: Synthesis, X-ray Characterization and Magnetic Properties
by María Soledad Martínez, Antonio Bauzá, Amparo Caubet, Ángel García-Raso, Ángel Terrón, Juan J. Fiol, Elies Molins, Miquel Barceló-Oliver and Antonio Frontera
Magnetochemistry 2018, 4(2), 24; https://doi.org/10.3390/magnetochemistry4020024 - 23 May 2018
Cited by 2 | Viewed by 4321
Abstract
Three new dinuclear copper(II) complexes [Cu2(μ–HLn)2(μ-Cl)2Cl2]Cl2 (13) have been synthesized and structurally characterized by single-crystal X-ray diffraction, where HLx, (HL1 = N6-propyladeninium, HL [...] Read more.
Three new dinuclear copper(II) complexes [Cu2(μ–HLn)2(μ-Cl)2Cl2]Cl2 (13) have been synthesized and structurally characterized by single-crystal X-ray diffraction, where HLx, (HL1 = N6-propyladeninium, HL2 = N6-butyladeninium and HL3 = N6-isobutyladeninium) are N6-alkyl bidentate NN donor adenine bases. Complexes 13 exhibit a coplanar arrangement of both N6-alkyladeninium moieties with UD conformation, with the terms U(up) or D(down) referring to the coordination of each pyrimidinic N3 atoms to the upper or lower metal center. In the three complexes, both copper atoms are five-coordinated (N2Cl3 donor set), resembling a compressed trigonal bipyramid. Each adenine moiety is protonated in N1 and the positive charge balanced by chloride counterions. Magnetic measurements of complexes 1 and 3 in the 2–300 K temperature range indicate antiferromagnetic coupling with J = −156.1(7) and J = −151(2) cm−1, respectively. Density functional theory calculations have also been performed in order to estimate the exchange coupling constants in these complexes. The theoretically calculated J values are in good agreement with the experimental values. Full article
(This article belongs to the Special Issue A Themed Issue in Honor of Late Professor Samiran Mitra)
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