EPR and ENDOR study of porphyrins and their covalently linked dimers in the photoexcited triplet state

The triplet states of several substituted porphyrins (Tetraphenylporphyrin (H₂TPP), Zinc-Tetramethylporphyrin (ZnTMP), Octaethylporphyrin (H₂OEP) and the Dication of H₂TPP (H₄TPP²⁺)) and two covalently linked dimers with H₂TPP-subunits in disordered solid solution were studied by EPR and ENDOR at liquid helium temperature. The measurement yields theA _zz component of the hyperfine tensors of all α-protons in the reference frame of the zero field splitting tensor. Dipolar and isotropic contributions toA _zz are discussed and spin densities derived. The spin densities are compared with results of all-valence-electrons self-consistent field molecular orbital calculations (RHF-INDO/S). One of the dimers shows indications of triplet energy transfer between the porphyrin subunits. The order of magnitude of the transfer rate is estimated to be 5 · 10⁵ s^?1.     

Impurity in three substitutional locations: Single-crystal EPR study of VO(II) in zinc maleate tetrahydrate

Single-crystal EPR study of VO(II)-doped zinc maleate tetrahydrate has been carried out at room temperature. Four types of impurities have been identified in the single-crystal spectra with intensity ratio of 11:5:2:1. However, the analysis has been done only for the three most intense resonances. The evaluated spin Hamiltonian parameters (A in units of mT) from single-crystal rotations are site I: g_xx=1.981, g_yy=1.971, g_zz=1.939; A_xx=7.43, A_yy=7.70, A_zz=18.7; site II: g_xx=1.973, g_yy=1.966, g_zz=1.939; A_xx=7.08, A_yy=7.22, A_zz=18.5; site III: g_xx=1.978, g_yy=1.977, g_zz=1.951; A_xx=7.11, A_yy=7.32, A_zz=18.3.The powder spectrum gives only one set of g and A values, confirming the presence of only one chemically equivalent site. The paramagnetic impurity, VO(II), has entered the lattice substitutionally for all the three sites. The superhyperfine structure, in the intensity ratio of 1:4:6:4:1, arising from the protons of the water ligands, has been found in one site. The admixture coefficients have been calculated and the complex is found to be fairly covalent in nature.     

Observation of three sites for vanadyl in a biomineral, zinc sodium phosphate hexahydrate: an EPR investigation

Single crystal EPR study has been carried at room temperature for VO(II) doped zinc sodium phosphate hexahydrate. Single crystal rotations in each of the three mutually orthogonal crystallographic planes namely bc, ac, and ab indicate three chemically inequivalent sites, with intensity ratios of 25:13:1. The spin Hamiltonian parameters obtained for the two intense sites are: Site I: g_xx=1.983, g_yy=1.985, g_zz=1.933; A_xx=7.39 mT, A_yy=7.15 mT, A_zz=19.03 mT; Site. II: g_xx=1.985, g_yy=1.985, g_zz=1.937; A_xx=7.36 mT, A_yy=7.25 mT, A_zz=18.67 mT. The two VO bond directions in the two sites are approximately at right angles to each other. The powder spectrum clearly indicates two chemically inequivalent sites, confirming the single crystal analysis. Admixture coefficients, Fermi contact, and dipolar interaction terms have also been evaluated.     

Local31P and distant31P and195Pt ENDOR studies of powdered samples of Bis(O,O′-disubstituted-dithiophosphato)copper(II) complexes magnetically diluted in the corresponding Pd(II) and Pt(II) host lattices

ENDOR studies on bis(dithiophosphato)copper(II) complexes magnetically diluted in the corresponding Pd(II) and Pt(II) host lattices performed with the use of the method of “polycrystalline ENDOR crystallography” are reported. In these samples well resolved local³¹P (A_iso ca. 29 MHz and A_aniso ca. 0.9 MHz) as wel1 as distant³¹P (A _iso ca. 1.3 and 5.5 MHz and A_aniso ca. 0.2 and 0.4 MHz) and¹⁹⁵Pt (A_iso ca. 3.1 MHz and A_aniso ca. 0.2 MHz) ENDOR transitions are recorded. It is shown that the directions of the main values of A_aniso for all local³¹P and distant³¹P and¹⁹⁵Pt ENDOR transitions are parallel. Comparison of these results with those reported about the same complexes but diluted in other host lattices shows that there is no difference in the EPR and local³¹P ENDOR parameters thus suggesting that the structure of the paramagnetic complex remains unchanged. It is found that distant ENDOR transitions appear only in the case when the host lattice contains one molecule in the unit cell, i.e., when all molecules are parallel to each other. Using the obtained data from local and distant³¹P ENDOR transitions some structural features of Cu(dtp)₂ as well as Pd(dtp)₂ and Pt(dtp)₂ complexes are found for the first time.     

Influence of hydrogen bonds on the electronicg-tensor and13C-hyperfine tensors of13C-labeled ubiquinones — EPR and ENDOR study

Selectively^l3C-labeled ubiquinone anion radicals in protic and aprotic solvents are investigated by EPR and ENDOR spectroscopy, yielding information about the effect of hydrogen bonds on the electronicg-tensor and the carbonyl carbon¹³C-hf tensors. Formation of the hydrogen bonds alter theg-tensor significantly to lower values and increases theA _zz , component of the^l3C-hf tensor. Both effects can be explained by electrostatic interactions between the positively charged hydrogen and the electrons at the carbonyl oxygen leading to a redistribution of charge and π-spin density. Two different hydrogen bonds were obtained for UQ ₀ ^? which are in agreement with the results of DFT (density functional theory) calculations.     

A New Paramagnetic Nitrogen Center in Natural Titanium-Containing Diamonds

A new type of nitrogen-related center in natural diamond labeled NU1 is identified as a 〈100〉 split interstitial configuration by means of electron paramagnetic resonance (EPR) and photoluminescence (PL) techniques. In PL this center is seen as an electron-vibration system with a zero-phonon line at 485 nm in the crystals containing S1/OK1 and 440.3 nm/N3 centers. NU1 EPR spectra are described by a spin-Hamiltonian with parameters: S = ½, I = 1 and A _xx (N) = 22.5 G, A _yy (N) = 19.5 G, A _zz (N) = 20.55 G, g _xx  = 2.0043, g _yy  = 2.0032, g _zz  = 2.0020. Directions of A _zz and g _zz coincide and correspond to [001]. The directions of A _xx and A _yy coincide with those of g _xx and g _yy and correspond to [110] and [?110], respectively. Analysis of the phonon structure of the NU1 center suggested that titanium can be the second atom together with nitrogen in the structure of a split interstitial.     

ESR studies of Cu2+ doped in SrC4H4O6·3H2O single crystals

Electron spin resonance spectra of Cu²⁺ doped in single crystals of strontium tartrate trihydrate grown by a diffusion technique have been investigated at 77K. Copper enters the lattice substitutionally and is trapped at two magnetically inequivalent sites. ESR measurements gave the following values for the spin-Hamiltonian parameters. Cu²⁺(I): g_gg = 2.0380, g_yy = 2.1317, g_zz = 2.3918 and A_xx = 26.3 G, A_yy = 56.3 G, A_zz = 110.8 G. Cu²⁺(II): g_xx = 2.0497, g_yy = 2.1297, g_zz = 2.3706 and A_xx = 19.2 G, A_yy = 61.4 G, A_zz = 107.2 G.     

Optically detected E.P.R. and low-field ENDOR of triplet benzophenone

The ENDOR spectrum of ¹³C substituted (carbonyl carbon) triplet excited benzophenone was studied at ca. 100 G applied magnetic field by means of optical detection. The benzophenone was substitutionally dissolved in dibromodiphenylether (DDE). The ENDOR transitions and the E.P.R. transitions were studied as a function of applied field direction in the ab and bc crystal planes. The angle ? between the line joining the phenyl group centres and a principal axis of the fine structure tensor was found to be 23·6° ± 0·02° (standard deviation limited to one set of measurements). The principal axes of the ¹³C hyperfine tensor were within experimental error (±10°) coincident with the fine structure axes. The principal values of the hyperfine tensor were found to be : |A_xx /h| = 43·16 ± 1·84, |A_yy /th| = 22·66 ± 2·50, |A_zz /h| = 10·25 ± 1·30 MHz. The low-field ENDOR does not provide an indication of the signs of these tensor elements, so the value of the isotropic coupling constant cannot be measured. Two values of the anisotropic (dipole) hyperfine tensor elements were deduced on the assumption that the transitions frequencies are mainly determined by interactions between the nuclear spin and electron density on the carbonyl carbon atom. These values were (i) A _xx / ^d /h = 17·82, A_yy /h = -22·68, A_zz /h = -15·14 MHz and (ii) A_xx /h = 39·73, A_yy /h = -26·09, A_zz /h = -13·63 MHz. Set (ii) is consistent with recent calculations of the spin density distribution in triplet benzophenone in which the orbital spin densities are 0·64 for the carbonyl carbon π-orbital, 0·17 for the oxygen π-orbital, and 0·88 for the non-bonding orbital on oxygen (all expressed as fractions of one electron).

Isotope effects on the fine structure constants of triplet benzophenone were measured and found to be consistent with the changes occurring in the spin-orbit coupling with the ground state.

The kinetic parameters for the excitation and de-excitation of the triplet substates were deduced from transient ODMR studies of benzophenone in DDE. The T_z spin state is mainly populated (85–88 per cent) and this is also the most strongly radiative state (k_z ^r = 0·88). The steady-state populations of the three triplet levels are similar.     

ESR of X-ray induced centre in CaF2:Gd crystals

An ESR centre with orthorhombic symmetry was induced in CaF₂:Gd crystals by X-ray irradiation after heat treatment at 900°C. The observed ESR spectrum has resolved shfs in particular crystal directions. Spin Hamiltonian analysis indicates that the ESR centre is a hole trapped at an oxygen substituted for a fluorine site and interacts mainly with two nearby fluorine ions located along the crystal [001] direction. The determined spin Hamiltonian parameters are g_xx = 2.0036, g_yy = 2.0159, g_zz = 2.0306, A_xx = 22.5, A_yy = 5.6 and A_zz = 5.6 (G), respectively. A probable model is discussed by considering both the angular dependence of the ESR lines and the local charge neutrality around the ESR centre.     

The bacteriochlorophylla cation radical revisited. An ENDOR and TRIPLE resonance study

The bacteriochlorophyll (BGhl)a cation radical is studied by cw-EPR and multinuclear ENDOR/TRIPLE resonance techniques in liquid solution yielding the hyperfine coupling constants (hfcs) for 12 protons, all 4 nitrogens and the central magnesium nucleus. The H hfcs are assigned to specific molecular positions by various experimental techniques including isotope substitution, H/D exchange experiments and comparison with bacteriochlorophyll derivatives. The determined temperature dependences of the H hfcs are measured and related to dynamical properties of the molecule in solution. The experimental hfcs compare well with those obtained from semiempirical molecular orbital calculations of the RHF-INDO/SP type. The importance of these results for BChl speciesin vivo, i.e., in the protein matrix, is discussed.     

Structural elucidation of Cu(II) ion doped in hexaaquozincdiaquobis(malonato)zincate host by EPR spectroscopy

In order to understand the structural behaviour of Cu(II) in a variety of ligand environments, single crystal electron paramagnetic resonance studies of Cu(II) doped in hexaaquazincdiaquabis(malonato)zincate [Zn(H₂O)₆][Zn(mal)₂(H₂O)₂] are carried out at 300 K. Angular variation of copper hyperfine lines in three orthogonal planes shows the presence of single site, with spin Hamiltonian parameters as g_xx=2.034, g_yy=2.159, g_zz=2.388, A_xx=3.39 mT, A_yy=4.89 mT and A_zz=13.72 mT. The g/A tensor direction cosines are compared with various Zn-O directions in the host lattice, which confirm that Cu(II) enters substitutionally in the lattice. The low value of A_zz has been explained by considering admixture of d_²x−²y ground state with d_²z excited state. EPR powder spectra at 300 and 77 K give identical spin Hamiltonian parameters (g_∥=2.367, g_⊥=2.088, A_∥=11.47 mT, A_⊥=2.63 mT). IR, UV-vis and powder XRD data confirm the structure and symmetry of the Cu(II) ion in the host lattice.     

High-field EPR-detected shifts of magnetic tensor components of spin label side chains reveal protein conformational changes: The proton entrance channel of bacteriorhodopsin

Continuous-wave high-field electron paramagnetic resonance (95 GHz, 3.4 T) is performed on a spin label side chain located at residue position 171 in the proton entrance channel of bacterior-hodopsin The conformational differences of three bacteriorhodopsin mutants, the single mutant F171C, the double mutant D96G/F171C, and the triple mutant D96G/F171C/F219L, are reflected in different g_xx and A_zz tensor component shifts of the nitroxide side chain. The most polar microenvironment is found in the single mutant, whereas the open proton entrance channel reported for the triple mutant allows a reorientation of the nitroxide group towards a microenvironment of lower polarity and/or reduced hydrogen bonding. The experimental data of the double mutant are explained by a light-independent equilibrium of two nitroxide orientations with different polarities of the local microenvironment. Upon illumination the spectrum of the single mutant revealsg _xx andA _zz tensor component shifts which resemble those determined for the triple mutant in the dark. This result provides strong evidence for a light-induced opening of the proton entrance channel of the single mutant similar to that found in the unilluminated triple mutant, in agreement with electron diffraction data.     

EPR and optical investigation of VO(II) in Zn(C3H3O4)2(H2O)2 single crystals: An interstitial site

EPR spectroscopic investigations on single crystals of diaquabis[malonato(1-)-κ²O,O′] zinc(II) doped with VO(II) ion have been carried out at X-band frequencies and at 300 K. The single crystal, rotated along the three mutually orthogonally axes, has yielded spin-Hamiltonian parameters g and A as: g_xx=1.980, g_yy=1.972, g_zz=1.937 and A_xx=8.4, A_yy=6.1, A_zz=18.1 mT, respectively. These spin-Hamiltonian parameters reflect a slight deviation from axial symmetry to rhombic, which is elucidated by the interstitial occupation of vanadyl ions. The isofrequency plots and powder EPR spectrum have been simulated. The percentage of metal-oxygen bond has been estimated. The optical absorption spectrum exhibits four bands at 257, 592, 720 and 764 nm suggesting a C_4v symmetry. The admixture coefficients and bonding parameters have also been calculated by collaborating EPR data with optical data.     

XRD, TDPAC and LAPW study of Hf10B2 under high pressure

The crystallographic structure and electronic properties of Hf¹⁰B₂ were studied as a function of pressure by combining X-ray diffraction measurements with full potential linearized augmented plane wave (LAPW) calculations. No phase transition was observed up to a pressure of 30.8 GPa, with a total volume contraction of V/V ₀?=?0.85 and a bulk modulus value of B ₀?=?232 ±13 GPa. The calculated V _zz value at the hafnium site is linearly increasing as a function of the pressure induced volume reduction, while the V _zz value at the boron site stays almost zero. The major contribution to the V _zz value at the hafnium site comes from a p–p contribution next to the probe nucleus, with a relatively large d–d contribution of about 25%. This unusual large d–d contribution arises from the hafnium p–d electrons coupling.     

Azurin-Solvent interaction: an ESR spin labeling investigation

We have investigated by means of electron spin resonance (ESR) spectroscopy using two spin labels, Iodoacetamido-proxyl and 3-Maleimido-proxyl, the dynamics of two different regious around the active site of azurin, a copper containing blue protein. The ESR measurements of spin labeled azurin have been carried out in the 110–300 K temperature range on wet (H₂O, D₂O and ethanol/water mixtures) and lyophilized samples. The behaviours of the outer hyperfine splitting separation, 2A′ _zz , of the ESR spectravs temperature of the lyophilized, and fully hydrated azurin in H₂O and D₂O suggest that the two spin labels are located in regions of the protein surface with different dynamics and polarity. Moreover, all differences in the 2A′ _zz values shown by the spin labeled azurin in normal and heavy water as well as the temperature behaviour disappear when azurin is in ethanol/water mixtures. The results are discussed in terms of a close correlation between the molecular dynamics of the protein fragments to which the two spin labels are bound and the properties of the solvent used.     

EPR studies of Cu2+ in anhydrous sodium oxalate

Electron paramagnetic resonance spectra of Cu²⁺ doped in single crystal of anhydrous sodium oxalate grown by slow evaporation from saturated aqueous solutions have been investigated. EPR measurements gave the following values for the spin Hamiltonian parameters: g_xx = g_yy = 2.0741, g_zz = 2.3253, A_xx = A_yy = ?14.9G and A_zz = ?147.7 G. The principal axes of the hyperfine coupling and g tensors are spatially coincident. Using the optical absorption energy values given for a similar complex we have estimated the values of the bonding parameters and orbital-reduction factors for the system under investigation.     

Die D(d,p)H3-Reaktion mit polarisierten Deuteronen beiĒ d =80 keV

The tensor analyzing powersA _zz ,A _xx?tyy andA _xz of the D(d, p)H³ reaction are measured atē _d =80 keV. It is shown, that the polarization effects at this energy are of the same magnitude as the deviation of the isotropy, using unpolarized deuterons to initiate the reaction.     

Liquid-phase EPR, ENDOR, and TRIPLE resonance studies on corrole and isocorrole cation radicals

The “Contracted Porphyrins” corrole and the recently synthesized isocorrole (as octaethyl derivatives) represent novel porphyrinoid macrocycles of biochemical interest. The radical cations of the free-bases of both corrole and its isomer are studied by EPR, ENDOR, and TRIPLE resonance in liquid solution to measure isotropic hyperfine couplings including signs. They yield detailed information of the electronic structure of the radical cations. The experimental findings are compared with results of all-valence-electrons self-consistent field molecular orbital calculations (RHF-INDO/SP). The comparison shows that the free-bases of corrole and isocorrole undergo protonation when oxidized to cation radicals in CH₂Cl₂ solution. Excellent agreement of the measured and calculated spin density distributions is achieved for the protonated dication radicals, which exhibit the C₂ symmetry observed for the hyperfine structure. The analysis of the hyperfine data discriminates against NH tautomerism as the sole source for an effective C₂ symmetry of the macrocycle.     

The electric fieldgradient at Cd-impurities in heavy rare earth metals

The static electric quadrupole interaction of¹¹¹Cd in the heavy rare metals Gd, Tb, Ho and Er has been studied at room temperature by time differential perturbed angular correlation techniques. From these measurements the effective electric field-gradient,V _zz ^eff , at the Cd-site was derived on a relative scale. The lattice contributions,V _zz ^lat , to the total electric fieldgradient have been determined by lattice-sum calculations. The ratioα=V _zz ^eff /V _zz ^lat , which to a certain extent represents the conduction electron contribution to the electric fieldgradient, decreases with increasing atomic number. Possible reasons for this behaviour are discussed.     

Electron spin resonance studies of chlorine centres in irradiated chlorine-doped Na2SO4 single crystals

The nature of paramagnetic centres trapped in X-irradiated Na₂SO₄ single crystals containing chlorine as impurity has been determined from E.S.R. measurements both at room and liquid nitrogen temperatures. ClO₃, ClO₂, SO₄ ^- and O₃ ^- are the paramagnetic centres identified. The g and A parameters of ClO₃ change considerably between 298 K and 77 K. Thus the parameters of ClO₃ obtained at 298 K are g_xx = 2·0123, g_yy = 2·0143, g_zz = 2·0206 G and those of the A-tensor are A_xx = 97, A_yy = 100 and A_zz = 112 G. The parameters obtained for the same centre at 77 K are g_xx = 2·0132, g_yy = 2·0173, g_zz = 2·0073 G and those of the A-tensor are A_xx = 130·6, A_yy = 146·3 and A_zz = 181·2 G. The temperature variation of the principal values are determined in the temperature range between 298 K and 77 K. These data can be interpreted on the assumption that ClO₃ undergoes libration at room temperature, which is frozen out reversibly on cooling. The structure and mechanism of these defects are discussed further.