Search Results (7)

The effects of photochemical reactions induced by UV radiation in solutions of metal phthalocyanines were carried out to determine the factors that might influence the photostability of photosensitized phthalocyanines. Three different indium phthalocyanines, including the diindium triple-decker phthalocyanine, In₂Pc₃ (1), sandwich indium phthalocyanine, InPc₂ (2) and iodoindium phthalocyanine, InPcI (3) in benzene, N,N-dimethylformamide (DMF), dimethyl sulfoxide (DMSO), dichloromethane (DCM) and 1-chloronaphtalene, were studied. The rate of decay of absorption is explained by a decomposition reaction that is of first-order kinetics with respect to the phthalocyanine concentration. In general, the presence of ligand I⁻ in phthalocyanine InPcI enhances the rate of decomposition. The kinetics of the degradation process proved to depend on the molecular structure of the complex and seems to be controlled by interactions of the macrocycle bridging nitrogen atoms with the solvent molecules. The indium phthalocyanines in benzene displayed the capacity for singlet oxygen generation. Full article

Effectively regulating the rotary motions of molecular rotors through external stimuli poses a tremendous challenge. Herein, a new type of molecular rotor based on azobenzene-strapped mixed (phthalocyaninato)(porphyrinato) rare earth triple-decker complex Azo-1 is reported. Electronic absorption and ¹H NMR spectra manifested the reversible isomerization of the rotor Azo-1 between the trans configuration and the cis configuration. The rotational behavior of phthalocyanine rotator in two configurations were investigated by VT-¹H NMR experiments, and the results indicated that the phthalocyanine rotator possessed a smaller rotational energy barrier in the cis isomer than in the trans isomer, which was also supported by DFT calculations. This result demonstrates that the rotation of phthalocyanine rotator in (phthalocyaninato)(porphyrinato) rare earth triple-decker complex can be successfully modulated by photo-isomerization via altering irradiation. Full article

¹H-NMR spectroscopy of lanthanide complexes is a powerful tool for deriving spectral–structural correlations, which provide a clear link between the symmetry of the coordination environment of paramagnetic metal centers and their magnetic properties. In this work, we have first synthesized a series of homo- (M = M* = Dy) and heteronuclear (M ≠ M* = Dy/Y and Dy/Tb) triple-decker complexes [(BuO)₈Pc]M[(BuO)₈Pc]M*[(15C5)₄Pc], where BuO- and 15C5- are, respectively, butoxy and 15-crown-5 substituents on phthalocyanine (Pc) ligands. We provide an algorithmic approach to assigning the ¹H-NMR spectra of these complexes and extracting the axial component of the magnetic susceptibility tensor, ${\chi }_{ax}$. We show how this term is related to the nature of the lanthanide ion and the shape of its coordination polyhedron, providing an experimental basis for further theoretical interpretation of the revealed correlations. Full article

In the present work, we report the synthesis of isomeric heteronuclear terbium(III) and yttrium(III) triple-decker phthalocyaninates [(BuO)₈Pc]M[(BuO)₈Pc]M*[(15C5)₄Pc] (M = Tb, M* = Y or M = Y, M* = Tb, [(BuO)₈Pc]²⁻–octa-n-butoxyphthalocyaninato-ligand, [(15C5)₄Pc]²⁻–tetra-15-crown-5-phthalocyaninato-ligand). We show that these complexes undergo solvation-induced switching: the conformers in which both metal centers are in square-antiprismatic environments are stabilized in toluene, whereas in dichloromethane, the metal centers M and M* are in distorted prismatic and antiprismatic environments, respectively. This conclusion follows from the detailed analysis of lanthanide-induced shifts in ¹H NMR spectra, which makes it possible to extract the axial component of the magnetic susceptibility tensor ${\mathsf{\chi }}_{\mathrm{ax}}^{\mathrm{Tb}}$ and to show that this term is particularly sensitive to conformational switching when terbium(III) ion is placed in the switchable “M” site. This result provides a new tool for controlling the magnetic properties of lanthanide complexes with phthalocyanine ligands. Full article

Binuclear heteroleptic triple-decker terbium(III) phthalocyaninate (Pc)Tb[(15C5)₄Pc]Tb(Pc), where Pc²⁻ is phthalocyaninate dianion and 15C5 is a 15-crown-5 moiety, has been synthesized as a solvent-free powder (1) and a well-defined crystal solvate with o-dichlorobenzene (Pc)Tb[(15C5)₄Pc]Tb(Pc)⋅6C₆H₄Cl₂ (2). In the crystal structure of 2, the Tb-N(Pc) distances to the nitrogen atoms in the outer and inner decks are 2.350–2.367(4) and 2.583–2.598(4) Å, respectively, and the Tb–Tb distance is 3.4667(3) Å. The twist angle between the outer and the inner decks is 42.6°. The magnetic properties were studied for both 1 and 2. The χ_MT magnitude of 23.3 emu⋅K/mol at 300 K indicates a contribution of two Tb^III centers with the ⁷F₆ ground state. The χ_MT product increases with decreasing temperature to reach 38.5 emu⋅K/mol at 2 K. This is indicative of ferromagnetic coupling between Tb^III spins in accordance with previous data for triple-decker lanthanide phthalocyaninates of a dipolar nature. Both forms show a single-molecule magnet (SMM) behavior manifesting the in-phase (χ′) and out-of-phase (χ″) AC susceptibility signals in an oscillating field of 3 Oe with estimated effective spin-reversal energy barriers (U_eff) of 222(9) and 93(7) cm⁻¹ for 1 and 2, respectively. The compounds show narrow hysteresis loops in the −1 – +1 kOe range, and the splitting between the zero-field-cooling and field-cooling curves is observed below 6 K. Thus, in spite of similar static magnetic characteristics, each form of the Tb(III) complex shows a different dynamic SMM behavior. Full article

The detailed knowledge about the structure of multinuclear paramagnetic lanthanide complexes for the targeted design of these compounds with special magnetic, sensory, optical and electronic properties is a very important task. At the same time, establishing the structure of such multinuclear paramagnetic lanthanide complexes in solution, using NMR is a difficult task, since several paramagnetic centers act simultaneously on the resulting chemical shift of a particular nucleus. In this paper, we have demonstrated the possibility of molecular structure determination in solution on the example of binuclear triple-decker lanthanide(III) complexes with tetra-15-crown-5-phthalocyanine Ln₂[(15C5)₄Pc]₃ {where Ln = Tb (1) and Dy (2)} by quantitative analysis of the pseudo-contact lanthanide-induced shifts (LIS). The symmetry of complexes was used for the simplification of the calculation of pseudo-contact shifts on the base of the expression for the magnetic susceptibility tensor in the arbitrary oriented magnetic axis system. Good agreement between the calculated and experimental shifts in the ¹H NMR spectra indicates the similarity of the structure for the complexes 1 and 2 in solution of CDCl₃ and the structure in the crystalline phase, found from the data of the X-ray structural study of the similar complex Lu₂[(15C5)₄Pc]₃. The described approach can be useful for LIS analysis of other polynuclear symmetric lanthanide complexes. Full article

Double- and triple-decker lanthanide phthalocyaninates exhibit unique physical-chemical properties, particularly single-molecule magnetism. Among other factors, the magnetic properties of these sandwiches depend on their conformational state, which is determined via the skew angle of the phthalocyanine ligands. Thus, in the present work we report the comprehensive conformational study of substituted terbium(III) and yttrium(III) trisphthalocyaninates in solution depending on the substituents at the periphery of molecules, redox-states and nature of solvents. Conjunction of UV-vis-NIR spectroscopy and quantum-chemical calculations within simplified time-dependent DFT in Tamm–Dancoff approximation provided the spectroscopic signatures of staggered and gauche conformations of trisphthalocyaninates. Altogether, it allowed us to demonstrate that the butoxy-substituted complex behaves as a molecular switcher with controllable conformational state, while the crown-substituted triple-decker complex maintains a staggered conformation regardless of external factors. The analysis of noncovalent interactions within the reduced density gradient approach allowed to shed light on the nature of factors stabilizing certain conformers. Full article