Unusual cis-diprotonated forms and fluorescent aggregates of non-peripherally alkoxy-substituted metallophthalocyanines.

Protonation and aggregation of two metallophthalocyanines (zinc and magnesium) non-peripherally substituted with 1,4,7-trioxanonyl moieties were studied by steady-state and time-resolved optical spectroscopy. Both compounds are easily protonated in organic solvents, but the central metal ion strongly affects the character of this process. In particular, the magnesium derivative forms the cis-diprotonated isomer observed for the first time in phthalocyanines, in contrast to its zinc counterpart which forms the typical trans-diprotonated isomer. In addition, studies performed on phthalocyanines substituted with n-butoxy groups at their non-peripheral positions indicated that the formation of the cis-diprotonated forms is a more common feature of alkoxy-substituted magnesium metallophthalocyanines, in contrast to derivatives with other metal ions. The cis-diprotonated forms of the magnesium derivatives are formed at much lower proton concentrations than the trans-diprotonated forms of their zinc counterparts. The cis-isomers were also found to have more advantageous photophysical properties for photoactive applications than the trans-isomers. Aggregation studies of the trioxanonyl phthalocyanines revealed that the magnesium derivative aggregates much more easily in non-coordinating solvents than its zinc counterpart. Both the derivatives form fluorescent aggregates, which is typically attributed to the presence of oxygen-to-metal intermolecular coordination preventing the formation of non-fluorescent face-to-face stacks. The results indicate that the oxygen-to-metal coordination plays a significant role in the studied systems and the stronger oxygen-coordination ability of magnesium ions compared to zinc ions may underlie the observed differences between the phthalocyanines metallated with these two ions.

ESR lineshape and 1H spin-lattice relaxation dispersion in propylene glycol solutions of nitroxide radicals--joint analysis.

Electron Spin Resonance (ESR) spectroscopy and Nuclear Magnetic Relaxation Dispersion (NMRD) experiments are reported for propylene glycol solutions of the nitroxide radical: 4-oxo-TEMPO-d16 containing (15)N and (14)N isotopes. The NMRD experiments refer to (1)H spin-lattice relaxation measurements in a broad frequency range (10 kHz-20 MHz). A joint analysis of the ESR and NMRD data is performed. The ESR lineshapes give access to the nitrogen hyperfine tensor components and the rotational correlation time of the paramagnetic molecule. The NMRD data are interpreted in terms of the theory of paramagnetic relaxation enhancement in solutions of nitroxide radicals, recently presented by Kruk et al. [J. Chem. Phys. 138, 124506 (2013)]. The theory includes the effect of the electron spin relaxation on the (1)H relaxation of the solvent. The (1)H relaxation is caused by dipole-dipole interactions between the electron spin of the radical and the proton spins of the solvent molecules. These interactions are modulated by three dynamic processes: relative translational dynamics of the involved molecules, molecular rotation, and electron spin relaxation. The sensitivity to rotation originates from the non-central positions of the interacting spin in the molecules. The electronic relaxation is assumed to stem from the electron spin-nitrogen spin hyperfine coupling, modulated by rotation of the radical molecule. For the interpretation of the NMRD data, we use the nitrogen hyperfine coupling tensor obtained from ESR and fit the other relevant parameters. The consistency of the unified analysis of ESR and NMRD, evaluated by the agreement between the rotational correlation times obtained from ESR and NMRD, respectively, and the agreement of the translation diffusion coefficients with literature values obtained for pure propylene glycol, is demonstrated to be satisfactory.

Suppression of Raman electron spin relaxation of radicals in crystals. Comparison of Cu2+ and free radical relaxation in triglycine sulfate and Tutton salt single crystals.

Electron spin-lattice relaxation was measured by the electron spin echo method in a broad temperature range above 4.2 K for Cu(2+) ions and free radicals produced by ionizing radiation in triglycine sulfate (TGS) and Tutton salt (NH4)(2)Zn(SO4)2 ⋅ 6H2O crystals. Localization of the paramagnetic centres in the crystal unit cells was determined from continuous wave electron paramagnetic resonance spectra. Various spin relaxation processes and mechanisms are outlined. Cu(2+) ions relax fast via two-phonon Raman processes in both crystals involving the whole phonon spectrum of the host lattice. This relaxation is slightly slower for TGS where Cu(2+) ions are in the interstitial position. The ordinary Raman processes do not contribute to the radical relaxation which relaxes via the local phonon mode. The local mode lies within the acoustic phonon band for radicals in TGS but within the optical phonon range in (NH4)(2)Zn(SO4)2 ⋅ 6H2O. In the latter the cross-relaxation was considered. A lack of phonons around the radical molecules suggested a local crystal amorphisation produced by x- or γ-rays.

Dynamical properties and instability of local fluorite BaF(2) structure around doped Mn(2+) ions-EPR and electron spin echo studies.

The electron paramagnetic resonance (EPR) and electron spin echo (ESE) were measured at the X-band for Mn(2+) in a BaF(2) crystal in the temperature range 4.2-300 K. In addition to the cubic symmetry centre, two other lower concentration tetragonal centres were identified. Temperature variations and computer simulation of the EPR spectrum confirm that the cubic symmetry of the MnF(8) centre is deformed to two T(d) tetrahedra of different dimensions at around 45 K. Electron spin relaxation was measured in the temperature range 4.2-35 K, where the ESE signal was detectable. For higher temperature the Mn(2+) dynamics produces homogeneously broadened EPR lines. At the lowest temperatures the spin-lattice relaxation is governed by ordinary phonon processes with 1/T(1)∼T(5). The efficiency of these processes rapidly decreases and at about 11 K a local mode of energy 17 cm(-1) becomes the relaxation mechanism. Phase relaxation observed as ESE signal dephasing indicates that after the local deformation jumps (tunnelling with frequency 4 × 10(8) s(-1)) between the two tetrahedral configurations appear, with the energy barrier being the local mode energy. This motion is directly visible as a resonance-type enhancement of the ESE dephasing rate 1/T(M) around 11 K. Only the cubic centre displays the above dynamics.

Molecular structure and dynamics of off-center Cu(2+) ions and strongly coupled Cu(2+)-Cu(2+) pairs in BaF(2) crystals: electron paramagnetic resonance and electron spin relaxation studies.

X-band and Q-band electron paramagnetic resonance (EPR) spectra of Cu(2+) in BaF(2) crystal were recorded in the temperature range of 4.2-200 K. Spin-Hamiltonian parameters of single Cu(2+) complexes and of Cu(2+)-Cu(2+) pairs were derived and discussed. A special attention was paid to the dimeric species. Their molecular ground state configuration was found as having antiferromagnetic intradimer coupling with the singlet-triplet splitting J=-35 cm(-1). The zero-field splitting being D=0.0365 cm(-1) at 4.2 K increases with temperature as an effect of thermal population of excited dimer configurations. Electron spin echo (ESE) method was used for measurements of electron spin lattice and phase relaxation. The spin-lattice relaxation data show that except for coupling to the host lattice phonons the Cu(2+) ions are involved in local mode motions with energy of 82 cm(-1). Phase relaxation (ESE dephasing) of single Cu(2+) ions is due to spin diffusion at low temperatures. This relaxation is hampered for temperatures higher than 30 K due to the triplet state population of neighboring Cu(2+)-Cu(2+) dimers, which disturb dipolar coupling between Cu(2+) ions. For higher temperatures the relaxation is dominated by Raman T(1) processes. Fourier transform ESE spectrum displays dipolar Cu-F splitting which allowed determination of the off-center shift of Cu(2+) as delta(s)=0.132 nm. The dynamical effects observed in EPR spectra and in electron spin relaxation both for single Cu(2+) ions and Cu(2+)-Cu(2+) pairs are discussed as due to jumps between six off-center positions in the crystal unit cell and jumps between various dimer configurations.

Electron spin echo of Cu(2+) in the triglycine sulfate crystal family (TGS, TGSe, TGFB): electron spin-lattice relaxation, Debye temperature and spin-phonon coupling.

The electron spin-lattice relaxation of Cu(2+) has been studied by the electron spin echo technique in the temperature range 4.2-115 K in triglycine sulfate (TGS) family crystals. Assuming that the relaxation is due to Raman relaxation processes the Debye temperature Θ(D) was determined as 190 K for TGS, 168 K for triglycine selenate (TGSe) and 179 K for triglycine fluoroberyllate (TGFB). We also calculated the Θ(D) values from the sound velocities derived from available elastic constants. The elastic Debye temperatures were found as 348 K for TGS, 288 K for TGSe and 372 K for TGFB. The results shown good agreement with specific heat data for TGS. The elastic Θ(D) are considerably larger than those determined from the Raman spin-lattice relaxation. The possible reasons for this discrepancy are discussed. We propose to use a modified expression describing two-phonon Raman relaxation with a single variable only (Θ(D)) after elimination of the sound velocity. Moreover, we show that the relaxation data can be fitted using the elastic Debye temperature value as a constant with an additional relaxation process contributing at low temperatures. This mechanism can be related to a local mode of the Cu(2+) defect in the host lattice. Electron paramagnetic resonance g-factors and hyperfine splitting were analysed in terms of the molecular orbital theory and the d-orbital energies and covalency factors of the Cu(gly)(2) complexes were found. Using the structural data and calculated orbital energies the spin-phonon coupling matrix element of the second-order Raman process was calculated as 553 cm(-1) for TGS, 742 cm(-1) for TGSe and 569 cm(-1) for TGFB.