Ferrimagnetic Behavior ofmeso-Tetrakis(2,3,5,6-tetrafluoro-4-methoxyphenyl)porphyrinatomanganese(iii) tetracyanoethenide, [MnTF4OMePP][tcne]⋅2 PhMe: Structural Evidence for a Second-Order Crystallographic Phase Transition

Rittenberg, Durrell K.; Sugiura, Ken‐ichi; Sakata, Yoshiteru; Guzei, Ilia A.; Rheingold, Arnold L.; Miller, Joel S.

doi:10.1002/(sici)1521-3765(19990604)5:6<1874::aid-chem1874>3.0.co;2-2

Cited by 21 publications

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“…These changes are reversible. Although the details of this behaviour are unclear, it is attributable to the onset of a non-uniform 1-D chain and/or a phase transition, 15 and might be attributable to the short Fe-N TCNE coordination bonding.…”

Section: Spectroscopic Studiesmentioning

confidence: 99%

Structure, optical and magnetic behaviour of meso-tetraphenylporphyrinatoiron(III) tetracyanoethenide, [FeIII(TPP)]+[TCNE]˙− †

Mikami

Sugiura

Maruta

et al. 2001

J. Chem. Soc., Dalton Trans.

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The direct redox reaction between tetracyanoethylene (TCNE) and meso-tetraphenylporphyrinatoiron(), [Fe II (TPP)], formed the electron transfer salt (ETS) [Fe III (TPP)][TCNE], which has been structurally, spectroscopically, and magnetically characterized. It has an extended one-dimensional linear chain with coordination polymer motif comprised of [Fe III (TPP)] ϩ and bridging µ-[TCNE] Ϫ with Fe-N TCNE distance 1.889(2) Å. This coordination geometry is consistent with a low-spin iron() ion, i.e., one electron transfer from Fe II to TCNE produces S = 1/2 [Fe III (TPP)] ϩ having a (d xy ) 2 (d yz ,d zx ) 3 configuration and S = 1/2 [TCNE] Ϫ . 57 Fe Mössbauer data, δ = 0.28 mm s Ϫ1 and ∆E = 2.19 mm s Ϫ1 at 77 K, also support the low-spin state. The room temperature magnetic moment of the ETS, 1.20 µ B , arises from two S = 1/2 systems having antiferromagnetic coupling, Ϫ190 cm Ϫ1 (H = Ϫ2Σ J i j S i S j ).

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Section: Spectroscopic Studiesmentioning

confidence: 99%

Structure, optical and magnetic behaviour of meso-tetraphenylporphyrinatoiron(III) tetracyanoethenide, [FeIII(TPP)]+[TCNE]˙− †

Mikami

Sugiura

Maruta

et al. 2001

J. Chem. Soc., Dalton Trans.

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“…Since then additional porphyrin-based magnets have been prepared and characterized; however, a complete understanding of the magnetic behavior of this class of materials is still under investigation . Due to the relative ease of modifying the porphyrin structure, we − and others , have prepared a series of substituted tetraphenylporphyrin TCNE electron transfer salts with the hope of establishing a structure−function relationship.…”

Section: Introductionmentioning

confidence: 99%

Observation of Magnetic Ordering as High as 28 K for meso-Tetrakis(4-halophenyl)porphinatomanganese(III) Tetracyanoethenide, [MnTXPP][TCNE] (X = F, Br, I)

Rittenberg

Miller

1999

Inorg. Chem.

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The toluene solvates of meso-tetrakis(4-halophenyl)porphinatomanganese(III) tetracyanoethenide, [MnTFPP][TCNE] (1F), [MnTBrPP][TCNE] (1Br), and [MnTIPP][TCNE] (1I) have been prepared, and the magnetic and thermal properties have been determined and compared to those of [MnTClPP][TCNE] (1Cl). 1Br and 1I form uniform 1-D chains with each [TCNE](*)(-) being trans-&mgr;-N-sigma-bound to Mn(III) with Mn-N distances of 2.293 (1Br) and 2.276 (1I), which are a bit longer than 2.267 Å observed for 1Cl. The Mn-N-C angles are 167.2, 168.1, and 158.7, while intrachain Mn.Mn separations are 10.189, 10.277, and 10.101 Å. The magnetic susceptibilities for 1Br and 1I can be fit by the Curie-Weiss expression with high-temperature (T > 200 K) theta and low-temperature (T < 110 K) effective theta' values of -53 and 13 K and -79 and 30 K, respectively, compared to -60 and 13 K in 1Cl. theta is not observed for 1F; however, theta' is 70 K. The magnetic data are consistent with linear chain ferrimagnets composed of antiferromagnetically coupled S = 2 Mn(III) sites and S = (1)/(2) [TCNE](*)(-) sites with the antiferromagnetic intrachain coupling, J(intra/)k(B) (k(B) = Boltzmann's constant) determined from fits to the Seiden expression, of -225, -33, -30, and -53 K for the 1F, 1Cl, 1Br, and 1I, respectively. Hysteresis with coercive fields at 2 K of 20.0, 6.7, 4.0, and 15.9 kOe was observed for the 1F, 1Cl, 1Br, and 1I, respectively. Metamagnetic behavior is observed below 10 K for 1F, and below 5 K for both 1Br and 1I. The observed critical fields of 21.8, 6.8, 4.1, and 15.8 kOe were observed for 1F, 1Cl, 1Br, and 1I at 2 K, respectively. The ordering temperatures, T(c), determined from the maxima in the chi'(T) data taken at 10 Hz, are 28.0, 8.8, 8.0, and 6.5 K for 1F, 1Cl, 1Br, and 1I, respectively. The 28 K T(c) for 1F is the highest reported for this family of magnets.

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“…These deviations are difficult to identify, as they could originate in various computational and/or experimental sources (possible experimental sources could be: (a) a poor quality of the experimental magnetic data or the models used to obtain the experimental J AB parameters, (b) the use of high temperature structures, because the thermal ). 39 Interestingly, a linear fitting of the computed versus the experimental data has a similar slope (0.18 in the CASSCF, 0.25 in the CASPT2, and 0.35 in the B3LYP sets). The computed and experimental values of J AB , as a function of the a angle and the d29 dihedral angle, are shown in Fig.…”

Section: Calibration Of the Theoretical Calculation Of J Ab On [Mn(po...mentioning

confidence: 72%

Analysis of the magneto-structural correlations in the meso-tetraphenylporphyrinatomanganese(iii) tetracyanoethenide family of molecule-based magnets

2006

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Ferrimagnetic Behavior ofmeso-Tetrakis(2,3,5,6-tetrafluoro-4-methoxyphenyl)porphyrinatomanganese(iii) tetracyanoethenide, [MnTF4OMePP][tcne]⋅2 PhMe: Structural Evidence for a Second-Order Crystallographic Phase Transition

Cited by 21 publications

References 0 publications

Structure, optical and magnetic behaviour of meso-tetraphenylporphyrinatoiron(III) tetracyanoethenide, [FeIII(TPP)]+[TCNE]˙− †

Structure, optical and magnetic behaviour of meso-tetraphenylporphyrinatoiron(III) tetracyanoethenide, [FeIII(TPP)]+[TCNE]˙− †

Observation of Magnetic Ordering as High as 28 K for meso-Tetrakis(4-halophenyl)porphinatomanganese(III) Tetracyanoethenide, [MnTXPP][TCNE] (X = F, Br, I)

Analysis of the magneto-structural correlations in the meso-tetraphenylporphyrinatomanganese(iii) tetracyanoethenide family of molecule-based magnets

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