Spin crossover Fe(ii) complexes of a cross-bridged cyclam derivative

The asymmetric unit of the title complex, [Sb(C44H28N4)Cl2][Sb2Cl8]0.5·CH2Cl2, is composed of a SbV complex cation wherein the Sb atom is hexacoordinated by four N atoms of the pyrrole rings of the tetraphenylporphyrinate (TPP) ligands and two chloride ions, a half di-μ-chlorido-bis[trichloridoantimonate(III)] counter-anion and a dichloromethane solvent molecule. In the cation, the average Sb—N distance is 2.066 (2) Å, while the Sb—Cl distances are 2.3410 (11) and 2.3639 (12) Å. The central unit of the cation, SbN4C20, is far from being planar, with deviations of atoms from the least-squares plane ranging from −0.110 (4) to 0.124 (4) Å. The Sb—Cl distances in the anion, which is located about an inversion center, lie in the wide range 2.3715 (13)–2.7489 (13) Å, the longest distances being between the Sb and bridging Cl atoms. The crystal structure is stabilized by intermolecular C—H...Cl interactions involving the cations, the anions and the solvent molecules. The solvent molecule is disordered over two orientations in a 0.901 (13):0.099 (13) ratio.

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A Variety of Spin-Crossover Behaviors Depending on the Counter Anion: Two-Dimensional Complexes Constructed by NH⋅⋅⋅Cl− Hydrogen Bonds, [FeIIH3LMe]Cl⋅X (X = PF6−, AsF6−, SbF6−, CF3SO3−; H3LMe = Tris[2-{[(2-methylimidazol-4-yl)methylidene]amino}ethyl]amine)

Chemistry - A European Journal ◽

10.1002/chem.200500972 ◽

2006 ◽

Vol 12 (17) ◽

pp. 4536-4549 ◽

Cited By ~ 133

Author(s):

Masahiro Yamada ◽

Hiroaki Hagiwara ◽

Haruna Torigoe ◽

Naohide Matsumoto ◽

Masaaki Kojima ◽

...

Keyword(s):

Hydrogen Bonds ◽

Spin Crossover ◽

Two Dimensional ◽

Counter Anion ◽

Ethyl Amine

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STRUCTURE AND SPECTRAL-LUMUINESCENT PROPERTIES OF LANTHANIDE-CONTAINING COMPLEXES WITH AZACROWN CALIXARENES

Ukrainian Chemistry Journal ◽

10.33609/2708-129x.87.10.2021.103-115 ◽

2021 ◽

Vol 87 (10) ◽

pp. 103-115

Author(s):

Serhii Smola ◽

Natalia Rusakova ◽

Olena Alekseeva ◽

Stepan Basok ◽

Tatiana Kirichenko ◽

...

Keyword(s):

Mass Spectroscopy ◽

Lanthanide Complexes ◽

Solvent Molecule ◽

Azacrown Ether ◽

Counter Anion

Lanthanide complexes with calix[4]arenes lower rim substituted with two azacrown ether fragments are reported. The size of the substituent cavity varied from 4 to 6 heteroatoms. The complexes were analyzed by means of IR, NMR, ESI mass spectroscopy. It is assumed that the coordination of Ln(III) ions occurs through the donor atoms of the lower rim; the counter anion and solvent molecule are also coordinated. Lanthanide-centered characteristic luminescence was observed in Eu(III), Tb(III) and Yb(III) complexes. The most efficient 4f-luminescence is observed for terbium-containing complexes with benzo-crown-derived ligands. The pathways of the sensitization of 4f-luminescence are discussed.

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(μ-Acetato-κ2O:O′)[μ-2,6-bis({bis[(pyridin-2-yl-κN)methyl]amino-κN}methyl)-4-methylphenolato-κ2O:O](methanol-κO)dizinc bis(perchlorate)

Acta Crystallographica Section E Structure Reports Online ◽

10.1107/s1600536814004279 ◽

2014 ◽

Vol 70 (4) ◽

pp. m120-m121

Author(s):

Biswanath Das ◽

Matti Haukka ◽

Ebbe Nordlander

Keyword(s):

Hydrogen Bond ◽

Solvent Molecule ◽

Title Complex ◽

Acetate Group ◽

Counter Anion ◽

Present Structure ◽

Octadentate Ligand

The binuclear title complex, [Zn2(C33H33N6O)(CH3COO2)(CH3OH)](ClO4)2, was synthesized by the reaction between 2,6-bis({[bis(pyridin-2-yl)methyl]amino}methyl)-4-methylphenol (H-BPMP), Zn(OAc)2and NaClO4. The two ZnIIions are bridged by the phenolate O atom of the octadentate ligand and the acetate group. An additional methanol ligand is terminally coordinated to one of the ZnIIions, rendering the whole structure unsymmetric. Other symmetric dizinc complexes of BPMP have been reported. However, to the best of our knowledge, the present structure, in which the two ZnIIions are distinguishable by the number of coordinating ligands and the coordination geometries (octahedral and square-pyramidal), is unique. The dizinc complex is a dication, and two perchlorate anions balance the charge. The –OH group of the coordinating methanol solvent molecule forms a hydrogen bond with a perchlorate counter-anion. One of the anions is disordered over two sets of sites with an occupancy ratio of 0.734 (2):0.266 (2).

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Impact of ligand spacer and counter-anion in selected 1D iron(II) spin crossover coordination polymers

ICAME 2011 ◽

10.1007/978-94-007-4762-3_34 ◽

2013 ◽

pp. 217-221

Author(s):

Marinela M. Dîrtu ◽

France Schmit ◽

Anil D. Naik ◽

Aurelian Rotaru ◽

Jacqueline Marchand-Brynaert ◽

...

Keyword(s):

Coordination Polymers ◽

Spin Crossover ◽

Counter Anion

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Isomerization effect of counter anion on the spin crossover transition in [Fe(4-NH2trz)3](CH3C6H4SO3)2·nH2O

Journal of Physics Conference Series ◽

10.1088/1742-6596/217/1/012128 ◽

2010 ◽

Vol 217 ◽

pp. 012128 ◽

Cited By ~ 4

Author(s):

A Sugahara ◽

M Enomoto ◽

N Kojima

Keyword(s):

Spin Crossover ◽

Counter Anion ◽

Crossover Transition

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Spin-crossover in an iron(iii) complex showing a broad thermal hysteresis

Dalton Transactions ◽

10.1039/d0dt03610b ◽

2021 ◽

Author(s):

Cyril Rajnák ◽

Romana Mičová ◽

Ján Moncoľ ◽

Ľubor Dlháň ◽

Christoph Krüger ◽

...

Keyword(s):

Schiff Base ◽

Schiff Base Ligand ◽

Spin Crossover ◽

Thermal Hysteresis ◽

Mononuclear Complex ◽

Hysteresis Width ◽

Thermally Induced

A pentadentate Schiff-base ligand 3,5Cl-L2− and NCSe− form a iron(iii) mononuclear complex [Fe(3,5Cl-L)(NCSe)], which shows a thermally induced spin crossover with a broad hysteresis width of 24 K between 123 K (warming) and 99 K (cooling).

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