0000000001299106

AUTHOR

Shouvik Chattopadhyay

An unusual magnetic response in a π-stacked 66-dia net structure of [4 + 2] copper(II) cubane

A phenoxo bridged antiferromagnetic copper(II) cubane, features a π-stacked 66 -dia net framework, which creates long range ferromagnetic ordering, as evidenced from a coercivity maximum (~2000 Oe) at 20K with very unusual saturation magnetization. peerReviewed

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Magnetic Properties of End-to-End Azide-Bridged Tetranuclear Mixed-Valence Cobalt(III)/Cobalt(II) Complexes with Reduced Schiff Base Blocking Ligands and DFT Study.

Two tetranuclear mixed-valence cobalt(III/II) complexes having the general formula [(μ1,3-N3){CoII(Ln)(μ-O2CC6H4NO2)CoIII(N3)}2]PF6 (where H2L1 and H2L2 are two reduced Schiff base ligands) have been synthesized and characterized. The structures of both complexes show cobalt(II) and cobalt(III) centers with a distorted octahedral geometry with cobalt(III) and cobalt(II) centers located at the inner N2O2 and outer O4 cavities of the reduced Schiff base ligands, respectively. The oxidation states of both cobalt centers have been confirmed by bond valence sum (BVS) calculations. The magnetic properties show that both compounds behave as cobalt(II) dimers connected through an end-to-end azido b…

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An unusual magnetic response in a π-stacked 66-dia net structure of [4 + 2] copper(II) cubane

A phenoxo bridged antiferromagnetic copper(II) cubane features a π-stacked 66-dia net framework and creates long range ferromagnetic ordering, as evidenced from a coercivity maximum (∼2000 Oe) at 20 K with very unusual saturation magnetization.

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Anion modulated structural variations in copper(II) complexes with a semicarbazone Schiff base: Synthesis, characterization and self assembly

Abstract Two copper(II) complexes, [Cu(L)N3]n (1) and [Cu(HL)2](I3)ClO4 (2), where HL = 2-pyridylaldehydesemicarbazone, have been prepared and characterized by elemental analysis, IR and UV–Vis spectroscopy and single crystal X-ray diffraction studies. Complex 1 crystallizes in monoclinic space group P21/a, whereas, complex 2 crystallizes in triclinic space group P-1. Complex 1 is a stair-like coordination polymer with square pyramidal geometry of copper(II), whereas, complex 2 is a mononuclear cationic bis-ligand complex of octahedral copper(II). Lower coordination ability of tri-iodide or perchlorate compared to azide may be related with variations of the structures of the complexes.

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Synthesis, structure and magnetic characterization of a dinuclear and two mononuclear iron(III) complexes with N,O-donor Schiff base ligands

Abstract One centrosymmetric dinuclear and two mononuclear iron(III) Schiff base complexes, [(µ-OMe)2Fe2(L1)2(N3)2] (1) {HL1 = 2-((2-(dimethylamino)ethylimino)methyl)-6-ethoxyphenol}, [FeL2(OH2)(N3)]·CH3OH (2) {H2L2 = N,N′-bis(3-ethoxysalicylidene)propane-1,3-diamine} and [FeL3(OH2)(NCS)]·2H2O (3) {H2L3 = N,N′-bis(3-methoxysalicylidene)propane-1,3-diamine}, have been synthesized and characterized by elemental analysis and spectral studies. X-ray diffraction analysis was used to determine the structures of all three complexes. Variable temperature (2–300 K) magnetic susceptibility (χ) data of complex 1 show that both iron(III) centres in the complex are in a high spin configuration (S = 5/2)…

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Bis (μ-tetrazolato-NN′) bridged dinuclear nickel(II) Schiff base complexes: Tandem synthesis, structure and self assembly

Abstract Two new bis(μ-tetrazolato-NN′) bridged dinuclear nickel(II) Schiff base complexes [Ni2L12(PTZ)2]·2(CH3)2SO·2.69H2O (1) and 2[Ni2L22(PTZ)2]·3H2O (2) (HL1 and HL2 are Schiff bases, HL1 = 2-((2-(dimethylamino)ethylimino)methyl)phenol, HL2 = 2-((2-(methylamino)ethylimino)methyl)-6-methoxyphenol and HPTZ is 5-pyrazinyltetrazole) have been synthesized via [3+2] cyclo-addition of 2-cyanopyrazine and sodium azide in presence of nickel(II) acetate tetrahydrate and the respective Schiff bases. The structures of the complexes are confirmed by single crystal X-ray diffraction analysis. Both complexes show fluorescence. The change in the denticity of the Schiff base blocking ligand is shown to …

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Copper(II) complexes with tridentate N2O donor Schiff base isomers: Modulation of molecular and crystalline architectures through supramolecular interactions

Abstract Four copper(II) complexes, [Cu(L1)(μ-Cl)]n (1), [Cu2(L2)2(μ-Cl)2] (2), [Cu(L1)(μ1,5-NCNCN)]n (3) and [Cu(L2)(μ1,5-NCNCN)]n (4), where HL1 = 1-[(2-dimethylamino-ethylimino)-methyl]-naphthalen-2-ol and HL2 = 1-[(2-ethylamino-ethylimino)-methyl]-naphthalen-2-ol, acting as tridentate N2O donor ligands, have been prepared and characterized by elemental analysis, IR and UV–Vis spectroscopy and single crystal X-ray diffraction studies. Complexes 1, 3 and 4 show polymeric chain structures, whereas 2 has a double chloride bridged dimeric structure. The existence of C–H⋯π interactions between the dimeric units of 2 gives rise to a 2D supramolecular network. Complex 3 shows a zipper structure…

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Synthesis, characterization and self-assembly of three dicyanamide bridged polynuclear copper(II) complexes with N2O donor tridentate Schiff bases as blocking ligands

Three copper(II) complexes [Cu(L1)(μ1,5-dca)]n (1), [Cu(L2)(μ1,5-dca)]n (2) and [Cu(L3)(μ1,5-dca)]n (3) [where HL1 = (1-(2-(dimethylamino)ethylimino)ethyl) naphthalene-1-ol, HL2 = (1-(2-(methylamino)ethylimino)ethyl) naphthalene-1-ol and HL3 = (1-(2-(ethylamino)ethylimino)ethyl)naphthalene-1-ol] have been synthesized and characterized by elemental analysis, IR and UV–Vis spectroscopy. The structure of each complex has been confirmed by single-crystal X-ray diffraction studies. In all three complexes, copper(II) centres are bridged by dicyanamide in end to end fashion. Complexes 1 and 2 are zigzag polymers, whereas complex 3 is a helical one. The weak forces like C–H⋯π and π⋯π interactions i…

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Field-induced single molecule magnet behavior of a dinuclear cobalt(II) complex: a combined experimental and theoretical study.

Two dinuclear cobalt(ii) complexes, [(dmso)CoIIL1(μ-(m-NO2)C6H4COO)CoII(NCS)] (1) and [(dmso)CoIIL2(μ-(m-NO2)C6H4COO)CoII(NCS)] (2) [dmso = dimethylsulfoxide, H2L1 = (2,2-dimethyl-1,3-propanediyl)bis(iminomethylene)bis(6-methoxyphenol) and H2L2 = (2,2-dimethyl-1,3-propanediyl)bis(iminomethylene)bis(6-ethoxyphenol)] have been synthesized and structurally characterized by single-crystal X-ray diffraction, magnetic-susceptibility measurements and various spectroscopic techniques. Each complex contains a cobalt(ii) center with a slightly distorted octahedral geometry and a second cobalt(ii) center with a distorted trigonal prismatic one. To obtain insight into the physical nature of weak non-co…

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Field-induced ferromagnetism due to magneto-striction in 1-D helical chains

Two homochiral copper(II) helices, [Cu(μ1,3-N3)(L1)]n (1) and [Cu(μ1,3-NCO)(L2)]n (2), with end-to-end pseudohalide bridges, were synthesized using two N2O donor achiral Schiff bases via spontaneous chiral resolution. Field-induced ferromagnetic ordering due to magneto-striction in homochiral 1-D helix [Cu(μ1,3-N3)(L1)]n (1) is reported for the first time. At temperatures below 5.5 K, under a magnetic field of 1 T, orthogonality between the magnetic orbitals of copper centres increases significantly due to the contraction of lattice parameters, giving rise to long-range ferromagnetic ordering in the helical chain. The magneto-dielectric results are also indicative of the observed magneto-st…

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Formation of a novel ferromagnetic end-to-end cyanate bridged homochiral helical copper(ii) Schiff base complex via spontaneous symmetry breaking

A homochiral helical coordination polymer of copper(II) has been synthesized using achiral precursors via spontaneous symmetry breaking and has been confirmed by single crystal X-ray diffraction and solid-state CD spectroscopy. The variable temperature magnetic measurements indicate the presence of weak ferromagnetic exchange interactions mediated by end-to-end cyanate bridges (J = +0.12 cm(-1)).

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Asymmetric bis-(μ1,1-azido) bridged dinuclear copper(II) complex with N2O donor Schiff base: synthesis, structure and magnetic study

A copper(II) complex, [Cu2(L)2(N3)2] [where HL = 2-((3-(methylamino)propylimino)methyl)-6-methoxyphenol] has been synthesized and characterized by elemental analysis, IR, UV–vis and fluorescence spectroscopy, and single-crystal X-ray diffraction studies. The complex crystallizes in the trigonal space group R. The deprotonated tridentate Schiff base occupies three coordination sites of copper(II). The fourth coordination site is occupied by an azide. A symmetry-related azide from a different molecule coordinates with the fifth site of copper(II), thereby forming a double end-on azide-bridged centrosymmetric dimer. Variable temperature solid–state magnetic studies between 2 and 300 K were car…

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Synthesis, characterization and magnetic study of two new octahedral iron(III) complexes with pendant zwitterionic Schiff bases

Two Schiff bases, HL1 [2-((3-(dimethylamino)propylimino)methyl)-5-bromophenol] and HL2 [2-((2-(diethylamino)ethylimino)methyl)-6-methoxyphenol], have been employed to prepare two new octahedral iron(III) complexes, [Fe(HL1)2(N3)2]ClO4·2H2O (1) and [Fe(HL2)2(NCS)2]ClO4·H2O (2). Both complexes are characterized by spectral and elemental analyses. Single crystal X-ray diffraction studies confirm their structures. In both complexes, Schiff bases are trapped in their zwitterionic forms and coordinated to iron(III) only through the imine nitrogen and phenoxo oxygen, i.e., they behave as bi-dentate ligands, keeping the remaining potential donor sites pendant. The measurement of χM vs. T for both c…

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Hydrogen bond mediated intermolecular magnetic coupling in mononuclear high spin iron(iii) Schiff base complexes: synthesis, structure and magnetic study with theoretical insight

The crystal structure and magnetic properties of two mononuclear iron(III) Schiff base complexes, [FeL1(NCS)2] (1), HL1 = 2-[1-[[2-[(2-aminoethyl)amino]ethyl]imino]ethyl]phenol and [FeL2(N3)Cl] (2), HL2 = 2-(-1-(2-(2-aminoethylamino)ethylimino)ethyl)-4-methylphenol are reported. Each complex contains a Fe(III) ion surrounded by a N3O Schiff base ligand and two NCS− ligands (in 1) or one N3− and one Cl− ligands (in 2). The magnetic properties can be well reproduced with zero field splittings in the high spin S = 5/2 Fe(III) ions and weak intermolecular Fe–Fe interactions mediated by hydrogen bonds. This intermolecular antiferromagnetic interaction has been validated by using DFT calculations…

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Observation of novel oxygen⋯oxygen interaction in supramolecular assembly of cobalt(III) Schiff base complexes: a combined experimental and computational study

Two mononuclear cobalt(III) Schiff base complexes with azide [Co(L)(N3)(L0 )] (1) and [Co(L)(N3)(L00)] (2) {where HL ¼ 1-((2-(diethylamino)ethylimino)methyl)naphthalene-2-ol, HL0 ¼ 2-hydroxy-1-naphthaldehyde and HL00 ¼ acetylacetone} have been synthesized and characterized by elemental analysis, IR and UV-Vis spectroscopy and single crystal X-ray diffraction studies. Both complexes show mononuclear structures with azide as terminal coligand. Structural features have been examined in detail that reveal the formation of interesting supramolecular networks generated through non-covalent forces including hydrogen bonding, C–H/H–C and C–H/p interactions. These interactions have been studied ener…

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Synthesis, crystal structure and magnetic properties of two alternating double μ1,1 and μ1,3 azido bridged Cu(ii) and Ni(ii) chains

Two new alternating μ1,1- and μ1,3-azido bridged chains, [Cu(N3)2(mtn)]n (1) and [Ni(N3)2(mtn)]n (2) where mtn = N-methyl-1,3-propanediamine, have been synthesized and characterized by single crystal X-ray diffraction. In both complexes, each metal atom is coordinated to six nitrogen atoms from four azide anions and one N-methyl-1,3-propanediamine molecule in a distorted octahedral geometry. In 1, the basal-apical double μ1,1-azido bridged Cu(ii)-dimers are connected through two asymmetric μ1,3-N3 bridges to form a 1D chain in which one of the azide acts as a μ1,1,3 bridge while the other one is terminal. The structure of 2 is very similar but one of the azide ions acts as μ1,1 and the othe…

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CCDC 1053244: Experimental Crystal Structure Determination

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CCDC 1019456: Experimental Crystal Structure Determination

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CCDC 1812958: Experimental Crystal Structure Determination

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CCDC 2036381: Experimental Crystal Structure Determination

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CCDC 991416: Experimental Crystal Structure Determination

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CCDC 1976309: Experimental Crystal Structure Determination

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CCDC 1406302: Experimental Crystal Structure Determination

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CCDC 1406301: Experimental Crystal Structure Determination

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CCDC 1024471: Experimental Crystal Structure Determination

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CCDC 1053245: Experimental Crystal Structure Determination

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CCDC 1047382: Experimental Crystal Structure Determination

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CCDC 1021604: Experimental Crystal Structure Determination

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CCDC 1053247: Experimental Crystal Structure Determination

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CCDC 2036380: Experimental Crystal Structure Determination

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CCDC 1021611: Experimental Crystal Structure Determination

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CCDC 984094: Experimental Crystal Structure Determination

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CCDC 1412636: Experimental Crystal Structure Determination

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CCDC 1007150: Experimental Crystal Structure Determination

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CCDC 1812959: Experimental Crystal Structure Determination

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CCDC 922454: Experimental Crystal Structure Determination

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CCDC 1579669: Experimental Crystal Structure Determination

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CCDC 974904: Experimental Crystal Structure Determination

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CCDC 922456: Experimental Crystal Structure Determination

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CCDC 984093: Experimental Crystal Structure Determination

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CCDC 1923203: Experimental Crystal Structure Determination

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CCDC 1053243: Experimental Crystal Structure Determination

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CCDC 922453: Experimental Crystal Structure Determination

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CCDC 922455: Experimental Crystal Structure Determination

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CCDC 1047381: Experimental Crystal Structure Determination

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CCDC 1024473: Experimental Crystal Structure Determination

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CCDC 1923202: Experimental Crystal Structure Determination

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CCDC 974903: Experimental Crystal Structure Determination

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CCDC 1976308: Experimental Crystal Structure Determination

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CCDC 1409357: Experimental Crystal Structure Determination

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CCDC 1409356: Experimental Crystal Structure Determination

Related Article: Anik Bhattacharyya, Biswa Nath Ghosh, Kari Rissanen, Shouvik Chattopadhyay|2016|Polyhedron|117|138|doi:10.1016/j.poly.2016.04.037

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