RESUMEN
This work investigated the spin states of the cobalt(II) complexes [Co(L1)2](X)2 (1·X; L1 = 4'-(4-N,N'-diphenylaminophenyl)-2,2':6',2''-terpyridine, X = PF6, BPh4) and [Co(L2)2](X)2 (2·X; L2 = 4'-(4-N,N'-dimethylaminophenyl)-2,2':6',2''-terpyridine, X = PF6, BPh4) in the solid state and in solution. In the solid state, 1·PF6 and 2·PF6, both containing smaller PF6- counter anions, showed gradual spin-crossover. In contrast, 1·BPh4 and 2·BPh4 remained in the high-spin state over the temperature range of 5-400 K due to a lower degree of molecular cooperativity. Each of the cobalt(II) complexes exhibited effects of temperature and concentration on their absorption spectra that were related to the spin states in various organic solvents. This work provides new insights into the spectroscopic properties resulting from the spin states of cobalt(II) complexes in solution.
RESUMEN
Three Fe(III)-based coordination complexes [Fe(dqmp)2](NO3)·H2O (1), [Fe(dqmp)2](BF4)·2CH3COCH3 (2), and [Fe(dqmp)2](ClO4) (3) were synthesized from Fe(NO3)3·9H2O/Fe(ClO4)3·xH2O, NaBF4, and 2,4-dichloro-6-((quinoline-8-ylimino)methyl)phenol (Hdqmp) in methanol/acetone and characterized. The structures of complexes 1-3 were determined via single-crystal X-ray crystallography at 100 K and room temperature, and their magnetic properties in the solid and solution forms were investigated. All complexes showed meridional structures with two tridentate dqmp- ligands coordinated with Fe(III) cations. In the solid state, complex 1 showed an abrupt and complete spin crossover at 225 K, whereas complexes 2 and 3 exhibited an incomplete spin crossover at 135 and 150 K, respectively. In a dimethylformamide solution, the complexes showed counterion-dependent spin transitions. In contrast to the solid state, in solution, complex 1 did not exhibit complete spin crossover. However, complexes 2 and 3 showed more complete spin transitions in solutions than in the solid state. The relaxation times, T1 and T2, for 1 and 2 were determined and both increased with temperature from 220 to 380 K. The T1 of 1 was larger than that of 2 at 380 K, and the T1 values were larger than the T2 values.
RESUMEN
Two mononuclear Ni(II) complexes (1 and 2) have been found to display color changes upon coordination/decoordination of pyridine, resulting in their structural transformation between square-planar and octahedral geometries as well as a change in their spin state. Compound 1 changes between red (1r) and yellow (1y) upon exposure to or elimination of pyridine, while 2 undergoes a two-step transformation, changing orange 2o (S = 0) â gray 2g' (S = 1) â yellow 2y' (S = 1) depending on the reaction time. The first step (2o â 2g') takes less than 45 min, which is significantly faster than the previously reported reaction time of 1 day for a Ni(II) complex/pyridine vapor system. Compound 2o reacting with pyridine can be easily prepared by dispersing 2g in methanol instead of annealing at high temperatures (130 °C), which can be applied to develop chemical sensors for pyridine utilizing color changes and/or magnetic switching.
RESUMEN
An organic-inorganic hybrid metal halide (OIMH), namely the electron-deficient naphthalene diimide (NDI) and [CoCl4]2- hybrid (1), showed potential as a sensor for ammonia and amines, in addition to magnetic changes upon vapochromism. Crystal 1 exhibited thermosalient behavior such as leaping and movement, at around 130 °C, which could be explained to be associated with the removal of water molecules from the crystal lattice as shown by TGA and DSC. Compound 1 changed from green to black within 5 minutes when exposed to ammonia vapor, which was attributed to the radical formation in the NDI moiety as evidenced by ESR, and this phenomenon was preserved even when other mono- and di-alkylamines were applied. The exposure of 1 to ammonia resulted in a subsequent color alteration, progressing from black to a gradually dark orange after one day (1_NH3_1 day). This transformation was concomitant with the formation of [Co(NH3)6]3+ from [CoCl4]2-, leading to a modification of the magnetic properties from paramagnetic Co(II) (S = 3/2) to diamagnetic Co(III) (S = 0). Based on these findings, compound 1 represents the first example of an OIMH that exhibits thermosalient behaviour, color change, and magnetic conversion upon exposure to ammonia.
RESUMEN
Discrete spin crossover (SCO) heteronuclear cages are a rare class of materials which have potential use in next-generation molecular transport and catalysis. Previous investigations of cubic cage [Fe8 Pd6 L8 ]28+ constructed using semi-rigid metalloligands, found that FeII centers of the cage did not undergo spin transition. In this work, substitution of the secondary metal center at the face of the cage resulted in SCO behavior, evidenced by magnetic susceptibility, Mössbauer spectroscopy and single crystal X-ray diffraction. Structural comparisons of these two cages shed light on the possible interplay of inter- and intramolecular interactions associated with SCO in the NiII analogue, 1 ([Fe8 Ni6 L8 (CH3 CN)12 ]28+ ). The distorted octahedral coordination environment, as well as the occupation of the CH3 CN in the NiII axial positions of 1, prevented close packing of cages observed in the PdII analogue. This led to offset, distant packing arrangements whereby important areas within the cage underwent dramatic structural changes with the exhibition of SCO.
RESUMEN
A mixed valence tetranuclear iron complex [(Hpmide)FeII(NCSe)2FeIII(pmide)]2·5CH3OH (1) underwent oxidation and ligand exchange in the solid state (H2pmide = N-(2-pyridylmethyl)iminodiethanol). Upon air oxidation, 1 was converted into [(pmide)FeIII(NCSe)FeIII(pmide)]2(NCSe)2·2H2O (2), which was accompanied by deprotonation and ligand exchange through a single crystal-to-single-crystal transformation.
