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A series of the new monophthalocyaninato lanthanide complexes, [Ln(Pc)(cyclen)]Cl (Ln = Y, Tb, Dy, Ho, Er, Tm, and Yb; Pc = phthalocyaninato; cyclen = 1,4,7,10-tetraazacyclododecane) was synthesized and characterized. The crystallographic study of monophthalocyaninato complexes with a capping macrocyclic ligand having no π-conjugation while keeping the 4-fold symmetry is presented for the first time. All the six complexes were crystallized in a tetragonal structure of the I4mm space group. In addition to this, the Tb complex exhibited a triclinic crystal structure of the P1 space group. All of the complexes are isostructural, where both Pc and cyclen are coordinated to an Ln3+ ion giving an eight-coordinate square-antiprismatic geometry. The skew angle between the Pc and cyclen ligands was 45° in the tetragonal crystals and 41.5° in the triclinic crystal. The metal–nitrogen bond lengths were shorter on the Pc ligand side than cyclen side, presumably due to the difference in the charges of the ligands and...

Syntheses of a novel pseudotetrahedral four-coordinate mononuclear Co(II) complex that has two halved phthalocyanine moieties as the ligands, [Co(half-Pc)2] (1), and its magnetic properties as a single molecule magnet (SMM) are reported. A one pot reaction of phthalonitrile and lithium methoxide followed by the coordination to a Co(II) ion gave 1 as an orange solid in a moderate yield. X-ray crystallography on 1 reveals tetragonally distorted coordination geometry around the Co(II) ion. The M- HT-1 plots suggest that 1 has large axial magnetic anisotropy. The ac magnetic susceptibility data of the magnetically diluted 1 (dil.1) clearly show that the complex acts as an SMM even in the absence of the external static magnetic field ( Hdc). The influence of intermolecular and intramolecular interactions for the magnetic relaxation behaviors has been discussed by comparison of the magnetic data of 1 and dil.1. The Orbach process is suggested as the predominant mechanism of magnetic relaxations in the high-temperature range, and the Arrhenius plots provide the effective relaxation energy barrier and pre-exponential factor of Ueff = 54.0 cm-1 and τ0 = 3.17 × 10-10 s, respectively. The direct estimation of the axial anisotropic parameter of 1 was successfully performed by high-field, multifrequency ESR measurements up to 55 T and 2.5 THz. The evaluated axial zero-field splitting (ZFS) energy of 57.0 cm-1 is comparable to the Ueff energy, confirming that the magnetic relaxations are initiated by the thermal excitation from the ground | M S⟩ = |±3/2⟩ states to the |±1/2⟩ states in the high-temperature range. The results of the ab initio calculations based on the CAS(7,5) SCF wave functions indicate that the ground states of 1 consist mainly of | M S⟩ = |±3/2⟩ states, while the first excited states are the mixture of | M S⟩ = |+1/2⟩ and |-1/2⟩.

Interactions of three different types of electronic angular momenta, namely, spin, orbital, and total angular momenta from different origins in a photoexcited neutral bis(phthalocyaninato)terbium single-molecule magnet (Pc2Tb, where Pc2- denotes a phthalocyaninato anion) have been studied. We have conducted varied-temperature and varied-magnetic-field magnetic circular dichroism (MCD) measurements on the highest occupied molecular orbital-lowest unoccupied molecular orbital electronic transition in the ligand side of the neutral Pc2Tb to reveal the quantum nature of the system composed of a π-radical with a spin angular momentum S, the 4f system with a total angular momentum J, and the cyclic π conjugate system with a photoinduced orbital angular momentum L. We have constructed a new theoretical model that gives a quantitative agreement to the temperature and magnetic field dependence of MCD. The theoretical analysis revealed that the system takes eight quantum states that can be expressed as | J z S z L z⟩ = |±±±⟩, where the three angular momenta are quantized along the fourfold symmetry axis. Thus, we have identified the existence of the magnetic interactions among the three angular momenta and quantitatively determined their magnitudes for the first time.

A series of heavy lanthanide(III) and yttrium(III) monoporphyrinato complexes formulated in [Ln(TPP)(cyclen)]Cl (Ln = Tb, Dy, Ho, Er, Tm, Yb, and Y; TPP = 5,10,15,20-tetraphenylporphyrinato), with cyclen, 1,4,7,10-tetraazacyclododecane, as a capping ligand, have been prepared in mild conditions and studied using single-crystal X-ray diffraction crystallography. The complexes exhibit an electronic absorption band (B(0,0)) in the range of 421–423 nm, showing a bathochromic shift associated with the increase of the ionic radii of the lanthanide, as well as two peaks of Q(1,0) and Q(0,0) bands between 548–586 nm. All of the complexes are isostructural, where both TPP and cyclen are coordinated to a lanthanide(III) or yttrium(III) ion giving an eight-coordinate square-antiprismatic (SAP) geometry (average skew angles are in the range of 43.01°–43.67°). The mean plane of the four nitrogen atoms of TPP (N4t) and that of the cyclen (N4c) are virtually parallel with a dihedral angle of less than 1°. The lanthanide...

Mixed condensation of tetramethylsuccinonitrile and either 2,3-dicyano-5,6-diethylpyrazine, 2,3-dicyanopyridine, or 3,4-pyridinedicarboximide in the presence of nickel chloride forms novel pyrazine-, 2,3-pyridine-, or 3,4-pyridine-ring-fused tetraazachlorin (TAC), tetraazabacteriochlorin (TABC), and tetraazaisobacteriochlorin (TAiBC) derivatives. All possible structural isomers were separated using repeated thin-layer chromatography and have been investigated by absorption and magnetic circular dichroism spectroscopy. Similarly to previously reported TAC analogues, the TAC and TABC derivatives show large splitting of the Q band, while a single, intense absorption band is observed for the TAiBC derivatives. Although the absorption spectra are practically identical in shape for the separated structural isomers of TACs and TABCs, the Q-band maxima of the TAiBCs depend significantly on their structures. The observed spectroscopic properties were interpreted on the basis of electrochemical data and the results of (time-dependent) DFT calculations.

Three isomeric 2[Pd(II)-Ni(II)] metal complexes, derived from indoleninyl meso-substituted dibenzotetraaza[14]annulene, were synthesized. The resulting dimers feature Ni···Ni or, alternatively, Ni···π interactions in staggered or slipped cofacial structures. A remarkable insertion of palladium into two different C-H bonds yielded a 4[Pd(II)-Ni(II)] rectangular complex with dimensions of 8.73 × 10.38 Å.

Magnetic relaxations arising from spin-phonon interactions for a magnetically diluted double-decker terbium phthalocyanine single molecule magnet, dil1, in the nonthermally activated temperature range have been investigated. While the relaxation time, τ, is independent of the external static magnetic field, H(dc), in the high temperature range, where linear relationships between -ln τ and T(-1) are observed in the Arrhenius plot, magnetic field dependences for τ are observed in the lower temperature range. The τ(-1) vs H(dc) plot at 12 K fits the quadric curve when H(dc) < 12 kOe, while linear relationships are observed in the τ(-1) vs T plots in the temperature range of 12-20 K. These results indicate that the direct process is the dominant magnetic relaxation pathway in the nonthermally activated temperature range, while the contribution from the Raman process, if any, is not observable. We emphasize in this paper that the contribution from the thermal relaxation processes and the quantum tunneling of magnetizations (QTMs) to the experimentally observed magnetic relaxations must be evaluated carefully in order to avoid confusion between the thermal and quantum-mechanical relaxation pathways.

A series of dialkoxy-substituted copper phthalocyanine (CuPc) precursors (4a-4d) have been prepared by treating phthalonitrile with the corresponding lithium alkoxide under mild conditions. The precursors exhibited high solubilities in common organic solvents, including acetone, toluene, tetrahydrofuran (THF), CH(2)Cl(2), and CHCl(3). Elongation of the alkoxy chains improved the solubilities of the precursors effectively, and accordingly, the butoxy-substituted derivative (4d) showed the highest solubility among 4a-4d. X-ray crystallography clarified that the conjugated skeletons of 4a-4d are all isostructural, and have two alkoxy groups in a syn-conformation fashion, leading to highly bent structures. Thermal conversions of the precursors examined by thermogravimetry (TG) and differential thermal analysis (DTA) demonstrate that 4a was converted into CuPc via two distinct exothermic processes in the 200-250 °C temperature range, while 4d exhibits only one exothermic signal in the DTA. In the field emission scanning electron microscopy (FESEM) images of 4a, the presence of two types of distinct crystal morphology (prismatic and plate-like crystals) can be recognized, implying that the two observed exothermic processes in the DTA can be attributed to the different crystal morphologies of the samples rather than the step-by-step elimination of the alkoxy groups. The thermal formation of CuPc from the precursors has been unambiguously confirmed by X-ray powder diffraction, UV-vis spectroscopy, and elemental analysis. The precursors were converted into CuPc at lower temperature with increasing chain length, presumably because of the increased void volume in the crystals. Thermal conversion performed in the solution phase results in a bright blue-colored solution with prominent absorption bands in the 650-700 nm region, strongly supporting the formation of CuPc.

Mixed condensation of 1,2-dicyanofullerene (1) and 4,5-dibutyloxyphthalonitrile (2a) in the presence of vanadium(III) chloride (VCl 3 ) in quinoline forms the hexabutyloxy-substituted tribenzotetraazachlorin (TBTAC) - fullerene (C 60 ) vanadyl complex (3). UV-vis absorption and magnetic circular dichroism (MCD) spectroscopy demonstrated that 3 shows two intense Q-band components, whereas the previously reported nickel complex possessing the identical peripheral substituents (4) shows one intense and two medium-intense bands in the 600-800 nm region, indicating that the electronic mixing states of 3 are different from those of the nickel complex (4). The metal effects on electronic structures of the conjugates were interpreted using density functional theory (DFT) calculations.

cis-3,4-Dicyano-3-hexene undergoes cyclotrimerization with BCl3 to form the new subtriazaporphyrin chloro[hexaethylsubtriazaporphyrinato]boron(III). The hydroxo derivative of this macrocycle has also been made, and the X-ray crystal structure of the hydroxy form was determined. Electronic absorption and magnetic circular dichroism spectra of the hydroxo monomer species were interpreted using time-dependent density functional theory calculations.

Two novel homoleptic diazaporphyrinato lanthanide sandwich com-plexes M(2)(DAP)(3) [M = Ce (1), Eu (2); DAP= 2,8,12,18-tetra-ethyl-3,7,13,17-tetramethyl-5,15-diazaporphyrinate] were synthesized by a one-pot reaction of the corresponding M(acac)(3).nH(2)O (acac = acetylacetonate) with metal-free D(2)(h) type diazaporphyrin, H(2)DAP. The spectroscopic and electrochemical properties are compared with those of complexes based on D(4)(h) symmetry porphyrin ligands.

The electronic absorption and magnetic circular dichroism spectral data of a phthalocyanine dicopper complex that is deduced to be very planar and to share a common benzene ring have been studied by band deconvolution analysis. The results were compared with those of the molecular orbital (MO) calculations within the framework of the Pariser−Parr−Pople (PPP) approximation. The results of the band deconvolution analysis are in good agreement with those of the PPP calculations, allowing many bands to be reasonably assigned on the basis of the MO calculations. The validity of the PPP method for the MO calculation of large molecules is also emphasized.