Search results for "SSB"

Coexistence of spin-crossover and antiferromagnetic coupling phenomena in the novel dinuclear Fe(II) complex [Fe(dpa)(NCS)2]2bpym

2003

Abstract The iron(II) spin crossover dinuclear compound [Fe(dpa)(NCS) 2 ] 2 bpym where dpa = 2,2 ′ -dipyridylamine and bpym = 2,2 ′ -bipyrimidine has been synthesized and characterized. Variable-temperature magnetic susceptibility and 57 Fe Mossbauer spectroscopy data provide evidence for a rather complete and continuous S=2 ( HS )↔S=0 (LS) spin-crossover behavior taking place in the temperature range 400–50 K (T 1/2 =245 K ) without the presence of a plateau at 50% of conversion. The absence of such plateau, which is characteristic of all dinuclear compounds so far studied, is interpreted in terms of synergetic effect between intramolecular and intermolecular interactions.

Titelbild: Mixed Spin-State [HS-LS] Pairs in a Dinuclear Spin-Transition Complex: Confirmation by Variable-Temperature57Fe Mössbauer Spectroscopy (An…

2008

Cover Picture: Mixed Spin-State [HS-LS] Pairs in a Dinuclear Spin-Transition Complex: Confirmation by Variable-Temperature57Fe Mössbauer Spectroscopy…

2008

Mixed spin-state [HS-LS] pairs in a dinuclear spin-transition complex: confirmation by variable-temperature 57Fe Mössbauer spectroscopy.

2008

Exquisite sensitivity of Mossbauer spectroscopy for tiny local molecular distortion is demonstrated in [FeII2(pmat)2](BF4)4?DMF: high-spin (HS) iron(II) in [HS-HS] and in [LS-HS] (low-spin–high-spin) pairs is clearly distinguished (see picture) for the first time without the need to apply a magnetic field. This dinuclear complex clearly shows that spin crossover via a [LS-HS] species is promoted by the use of a highly constrained bridging ligand (the bis-terdentate pmat).

Preparation and structural studies on diorganotin(IV) complexes of N-nitroso-N-phenylhydroxylaminates

2007

Abstract Diorganotin(IV)-complexes of the N -nitroso- N -phenylhydroxylaminates (hereinafter cupf), Et 2 Sn(cupf) 2 ( 1 ), Bu 2 Sn(cupf) 2 ( 2 ), {[Bu 2 Sn(cupf)] 2 O} 2 ( 3 ), t -Bu 2 Sn(cupf) 2 ( 4 ) and Oc 2 Sn(cupf) 2 ( 5 , 6 ) were prepared and characterised by FT-IR and Mossbauer spectroscopic measurements. The binding modes of the ligand were identified by FT-IR spectroscopy, and it was found that the ligand is coordinated in chelating or bridging mode to the organotin(IV) center. The 119 Sn Mossbauer and FT-IR studies support the formation of trans -O h ( 1 – 6 ) structures. The X-ray diffraction analysis of 4 revealed that the tin centre is in a skew-trapezoidal geometry defined by…

Spin-Crossover and Liquid Crystal Properties in 2D Cyanide-Bridged FeII−MI/II Metalorganic Frameworks

2010

Novel two-dimensional heterometallic Fe(II)-M(Ni(II), Pd(II), Pt(II), Ag(I), and Au(I)) cyanide-bridged metalorganic frameworks exhibiting spin-crossover and liquid crystal properties, formulated as {FeL(2)[M(I/II)(CN)(x)](y)}·sH(2)O, where L are the ligands 4-(4-alkoxyphenyl)pyridine, 4-(3,4-dialkoxyphenyl)pyridine, and 4-(3,4,5-trisalkoxyphenyl)pyridine, have been synthesized and characterized. The physical characterization has been carried out by means of EXAFS, X-ray powder diffraction, magnetic susceptibility, differential scanning measurements, and Mössbauer spectroscopy. The 2D Fe(II) metallomesogens undergo incomplete and continuous thermally induced spin transition at T(1/2) ≈ 170 …

New insights on the electronic, magnetic, electric and molecular structure of a bis-(4-cyanopyridine) iron(III) complex with the meso-tetrakis(4-meth…

2019

International audience; We have successfully synthesized and characterized a new low-spin iron(III) bis(4-cyanopyridine) complex with a meso-porphyrin substituted in the para positions of the phenyls by the methoxy group, namely the bis(4-cyanopyridine)[(meso-tetrakis(4-metoxyphenylporphyrinato)]iron(III) trifluoromethanesulfonate chlorobenzene monosolvate complex with the formula [FeIII(TMPP)(4-CNpy)2]SO3CF3.C6H5Cl (I). This species was characterized through ultraviolet–visible, Fourier-transform infrared and Mössbauer spectroscopy as well as by SQUID magnetometry, cyclic voltammetry, and X-ray crystallography. These characterizations indicated that our synthetic heme model is a low-spin (…

Spectroscopic and DFT Characterization of a Highly Reactive Nonheme FeV–Oxo Intermediate

2018

The reaction of [(PyNMe3)FeII(CF3SO3)2], 1, with excess peracetic acid at −40 °C generates a highly reactive intermediate, 2b(PAA), that has the fastest rate to date for oxidizing cyclohexane by a nonheme iron species. It exhibits an intense 490 nm chromophore associated with an S = 1/2 EPR signal having g-values at 2.07, 2.01, and 1.94. This species was shown to be in a fast equilibrium with a second S = 1/2 species, 2a(PAA), assigned to a low-spin acylperoxoiron(III) center. Unfortunately, contaminants accompanying the 2(PAA) samples prevented determination of the iron oxidation state by Mossbauer spectroscopy. Use of MeO-PyNMe3 (an electron-enriched version of PyNMe3) and cyclohexyl pero…

Iron(II) metallomesogens based on symmetrical tripod ligands

2012

Abstract Novel mononuclear tripodand-based iron(II) complexes showing liquid crystal properties have been synthesized and characterized. These are based on ligands tris[3-aza-4-((5-Cn)(6-R-2-pyridyl))but-3-enyl]amine, where R = hydrogen or methyl, 1,3,5-cis,cis-tris[1-aza-2-((5-alkyloxy)(2-pyridyl))vinyl]cyclohexane and 2,2,2-tris(2-aza-3-((5-alkyloxy)(2-pyridyl))prop-2-enyl)ethane. The physical characterization has been carried out by means of single-crystal X-ray diffraction measurements, magnetic susceptibility, differential scanning calorimetry, X-ray powder diffraction and Mossbauer spectroscopy.

Homoleptic iron(II) complexes with the ionogenic ligand 6,6′-Bis(1H-tetrazol-5-yl)-2,2′-bipyridine: spin crossover behavior in a singular 2D spin cro…

2015

Deprotonation of the ionogenic tetradentate ligand 6,6′-bis(1H-tetrazol-5-yl)-2,2′-bipyridine [H2bipy(ttr)2] in the presence of FeII in solution has afforded an anionic mononuclear complex and a neutral two-dimensional coordination polymer formulated as, respectively, NEt3H{Fe[bipy(ttr)2][Hbipy(ttr)2]}·3MeOH (1) and {Fe[bipy(ttr)2]}n (2). The anions [Hbipy(ttr)2]− and [bipy(ttr)2]2– embrace the FeII centers defining discrete molecular units 1 with the FeII ion lying in a distorted bisdisphenoid dodecahedron, a rare example of octacoordination in the coordination environment of this cation. The magnetic behavior of 1 shows that the FeII is high-spin, and its Mössbauer spectrum is characteriz…