Field-induced single-ion magnet based on a quasi-octahedral Co(II) complex with mixed sulfur-oxygen coordination environment.

Synthesis and characterization of structure and magnetic properties of the quasi-octahedral complex (pipH2)[Co(TDA)2] 2H2O (I), (pipH22+ = piperazine dication, TDA2- = thiodiacetic anion) are described. X-ray diffraction studies reveal the first coordination sphere of the Co(II) ion, consisting of two chelating tridentate TDA ligands with a mixed sulfur-oxygen strongly elongated octahedral coordination environment. SQUID magnetometry, frequency-domain Fourier-transform (FD-FT) THz-EPR spectroscopy, and high-level ab initio SA-CASSCF/NEVPT2 quantum chemical calculations reveal a strong "easy-plane" type magnetic anisotropy (D ≈ +54 cm-1) of complex I. The complex shows field-induced slow relaxation of magnetization at an applied DC field of 1000 Oe.

High resolution electron paramagnetic resonance spectroscopy of septet pyridyl-2,4,6-trinitrene in solid argon: Fine-structure parameters of six electron-spin cluster.

The high resolution 9 GHz electron paramagnetic resonance (EPR) spectrum of septet pyridyl-2,4,6-trinitrene was recorded after the photolysis of 2,4,6-triazido-3,5-dichloropyridine in solid argon matrix at 15 K. Owing to the high resolution of the experimental EPR spectrum, the zero-field splitting parameters of the septet trinitrene were determined with a high accuracy: D(s)=-0.1019+/-0.0004 cm(-1) and E(s)=0.003 25+/-0.000 15 cm(-1). All EPR transitions of the septet trinitrene were, for the first, unambiguously assigned based on the eigenfield calculations of the Zeeman energy levels. The spectrum of the septet trinitrene represents a new type of EPR spectra of septet spin states with nonzero zero-field splitting parameter E(s). The nonvanishing parameter E(s) of the septet trinitrene arises due to magnetic nonequivalence of three triplet centers in the molecule and is manifested in the appearance in the spectrum of separate x and y transitions. The septet spin states of this type display at very low magnetic fields two intense z transitions since the mid R:3D(s)mid R: energy gap between zero-field energy levels W(+/-1) and W(+/-2) fits the quantum of microwave irradiation of a 9 GHz EPR spectrometer. Analysis of the magnetic parameters shows that semiempirical description of the fine-structure tensor for six electron-spin cluster in the septet trinitrene is appropriate for precise estimations of the parameter D(s) but it is too crude to estimate small value of the parameter E(s).

High resolution electron paramagnetic resonance spectroscopy of quintet pyridyl-2,6-dinitrene in solid argon: magnetic properties and molecular structure.

The high resolution X-band electron para magnetic resonance (EPR) spectrum of quintet pyridyl-2,6-dinitrene was recorded after the photolysis of 4-amino-2,6-diazido-3,5-dichloropyridine in solid argon matrix at 15 K. This spectrum represents a new type of powder EPR spectra that are characteristic for quintet spin states with zero-field splitting parameters |E(q)/D(q)| approximately 1/4. All EPR lines of the quintet dinitrene were unambiguously assigned based on the eigenfield calculations of the Zeeman energy levels and angular dependencies of resonance magnetic fields. Owing to the high resolution of the experimental EPR spectrum, zero-field splitting parameters of the quintet dinitrene were determined with a high accuracy: D(q)=0.2100+/-0.0005 cm(-1) and E(q)=-0.0560+/-0.0002 cm(-1). These parameters provide correct information regarding the molecular angle Theta and distance r between two triplet sites in the molecule of quintet dinitrene. The measured molecular angle Theta=114.2 degrees+/-0.2 degrees is in excellent agreement with results of the density functional theory calculations. The analysis of the magnetic parameters shows that the spin population on the nitrene units in the quintet dinitrene is greater than that on the nitrene unit in the triplet nitrene.

High resolution EPR spectroscopy of C(60)F and C(70)F in solid argon: reassignment of C(70)F regioisomers.

Free radicals C(60)F and C(70)F were generated in solid argon by means of chemical reaction of photogenerated fluorine atoms with isolated fullerene molecules (C(60) or C(70)). High resolution anisotropic electron paramagnetic resonance (EPR) spectra of C(60)F and C(70)F at low temperature have been obtained for the first time. The spectrum of C(60)F is characterized by an axially symmetric hyperfine interaction on (19)F nucleus. The hyperfine coupling constants A(iso)=202.8 MHz (Fermi contact interaction) and A(dip)=51.8 MHz (electron-nuclear magnetic-dipole interaction) have been measured for C(60)F in solid argon. Quantum chemical calculations using hybrid density-functional models (either PBE0 or B3LYP) with high-quality basis sets give a theoretical estimate of the hyperfine coupling constants in good agreement with the measurements. The electron spin density distribution in C(60)F is theoretically characterized using the Hirshfeld atomic partitioning scheme. Unlike C(60), five isomers of C(70)F can in principle be produced by the attachment of a fluorine atom to one of the five distinct carbon atoms of the C(70) molecule (denoted A, B, C, D, and E, from pole to equator). The measured high resolution EPR spectrum of the C(70)+F reaction products is interpreted to show the presence of only three regioisomers of C(70)F. Based on the comparison of the measured hyperfine constants with those estimated by the quantum chemical calculation, an assignment of the spectra to the isomers (A, C, and D) is made, which differs strongly from the previous one [J. R. Morton, K. F. Preston, and F. Negri, Chem. Phys. Lett. 221, 59 (1994)]. The new assignment would allow the conclusion that the low-temperature attachment of F atom to the asymmetric C=C bonds of C(70) molecule, namely, C(A)[Double Bond]C(B) and C(D)=C(E), shows remarkably high selectivity, producing only one of the two isomers in each case, A and D, respectively. Theoretical investigation of the reaction mechanism is made, and it shows that the attachment reaction should have no barrier in the gas phase. The thermodynamic equilibration of the C(70)F isomers is excluded by the high activation energy ( approximately 30 kcal/mol) for the F atom shifts. The explanation of the high selectivity presents a challenge for theoretical modeling.

Infrared and EPR Spectroscopic Studies of 2-C(2)H(2)F and 1-C(2)H(2)F Radicals Isolated in Solid Argon.

2-fluorovinyl radicals were generated in solid argon by solid-state chemical reactions of mobile F atoms with acetylene and its deuterated analogues. Highly resolved EPR spectra of the stabilized radicals CHF&dbond;(*)CH, CDF&dbond;(*)CD, CHF&dbond;(*)CD, and CDF&dbond;(*)CH were obtained for the first time. The observed spectra were assigned to cis-2-fluorovinyl radical based on excellent agreement between the measured (a(F) = 6.50, a(betaH) = 3.86, a(alphaH) = 0.25 mT) hyperfine constants and those calculated using density functional (B3LYP) theory. Analogous experiments carried out using infrared spectroscopy yielded a complete assignment of the vibrational frequencies. An unusual reversible photochemical conversion is observed in which cis-2-fluorovinyl radicals can be partially converted to 1-fluorovinyl radicals by pulsed laser photolysis at 532 nm. Photolysis at 355 nm converts 1-fluorovinyl back to cis-2-fluorovinyl. High-resolution EPR and infrared spectra of 1-fluorovinyl were obtained for the first time. The measured hyperfine constants (a(F) = 13.71, a(H1) = 4.21, a(H2) = 1.16 mT) are in good agreement with calculated values. Copyright 2001 Academic Press.