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Absorption and MCD spectra of the two-electron oxidized lutetium phthalocyanine trimer [(Pc)Lu(CRPc)Lu(Pc)]²⁺ (Pc ≡ phthalocyanine;CRPc ≡ 15-crown-5-substituted Pc) as well as the MCD spectrum of the oxidized lutetium Pc dimer [Lu(Pc)₂]⁺ are reported. These ‘two-electron-deficient’ Pc stacks show absorption bands in the NIR region whose intensities are comparable with those of the Q bands. The band of [Lu(Pc)₂]⁺ showed only an MCD B term with no A term contribution, from which we assign the band to a non-degenerate transition whose transition moments are perpendicular to the Pc planes. In both trimer and dimer cases the excitation energy is higher than that of the corresponding NIR band in the ‘one-electron-deficient’ Pc stack [(Pc)Lu(CRPc)Lu(Pc)]⁺ or [Lu(Pc)₂], but the magnitudes of the shift were significantly different (1500 cm⁻¹ in the trimer and 4500 cm⁻¹ in the dimer). The energy shifts are shown to be represented by a pair of two-electron repulsion integrals in a localized orbital basis. The model reproduced well the direction and magnitude of the shifts using numerical values of the integrals.

This paper reviews the studies on the electronic structures and spectroscopic properties of sandwich-type complexes M(Pc)₂ and M₂(Pc)₃. The subjects discussed are as follows. (1) Electronic spectra of closed-shell Pc dimers and trimers. The complexes with closed-shell systems, such as [Lu(Pc)₂]⁻, Sn(Pc)₂ and Lu₂(Pc)₃, can be thought of as stacked systems composed only of Pc²⁻. The excited states of these complexes can be described by locally excited and charge transfer configurations. The coupling terms of the configurations are written using orbitals localized on each Pc ring. Assignments of the observed absorption bands are discussed. Computational studies on the band assignments were carried out using a localized molecular orbital (LO) basis which maximizes orbital populations on one of the Pc rings. (2) Electronic structures of πelectron-deficient Pc dimers and trimers. Oxidation of [Lu(Pc)₂]⁻ or Lu₂(Pc)₃ yields systems with π-electron deficiency or π-hole(s) residing on multiple Pc sites. The delocalized nature of the π-hole in Lu(Pc)₂ is elucidated by comparison of the electronic spectra of symmetric and asymmetric dimers composed of Pc and Nc(H₂Nc ≡ naphthalocyanine). The band assignments of the dimer radicals are discussed. The Pc trimer radical shows an intense absorption band at about 5000 cm⁻¹, which is 2000 cm⁻¹ lower than the valence resonance band of Lu(Pc)₂. The two-electron-deficient complexes [Lu(Pc)₂]⁺ and [Lu₂(Pc)₃]²⁺ also show intense near-IR bands at higher energy than the corresponding monoradical species. The interactions that determine the excitation energies of the near-IR bands of the π-electron-deficient species are elucidated.

The discovery and characterization of the first example of a bis-cadmiumtris-phthalocyanine triple-decker sandwich complex is reviewed. The compound, with each Pc ring substituted at the eight non-peripheral positions with hexyl chains, was obtained unexpectedly during recrystallization of the corresponding monomeric 1,4,8,11,15,18,22,25-octa-hexyl cadmium phthalocyanine from CH₂Cl₂ and methanol. The scope for obtaining further examples of this new class of complex bearing different ring substituents is also described. A feature of the compounds is that they give an EPR signal. An electrochemical study has shown that the rest state of the core of the sandwich structure is a dianion arising from the imbalance of the charges on the two cadmium atoms and the three Pc^2- ligands. This is a spin 0 species. It is proposed that the free radical character arises because the potential for the first one-electron oxidation is unusually low for a phthalocyanine, allowing for the partial presence of the spin ½ species for non-peripherally substituted complexes and a more extensive presence of the EPR active redox state for peripherally substituted analogs. Results of chemical oxidation using iodine are also discussed. A spectroscopic and electrochemical study on the monomeric precursors revealed the mode of formation of the triple-decker complexes. It has been established that octa-alkyl cadmium phthalocyanines unexpectedly exist very predominantly as dimeric structures in CH₂Cl₂ and these are proposed to be intermediates in the formation of the triple-decker complexes. Results from a series of cross experiments using differently substituted Pcs indicate that cadmium can be scrambled between a CdPc and a metal-free Pc. Furthermore, when either species is added to a solution of a triple-decker complex, the ligand from the added species becomes incorporated into new "mixed" triple-decker complexes. From these results it is proposed that the triple-decker structures are formed by self-assembly processes and that they can disassemble and reassemble in the solution phase. Preliminary measurements have identified ring substitution patterns that lead to higher oligomers.

A novel one-pot method for the regioselective preparation of early heteroleptic lanthanide (porphyrinato)(phthalocyaninato) complexes of double- and triple-decker structure [(Por)Ln(Pc) and (Por)Ln(Pc)Ln(Por), respectively] is developed. Sandwich-type complexes are synthesized for La, Ce and Pr following this procedure, with yields up to 30%. Tetrakis(15-crown-5)-phthalocyanine [(15C5)₄PcH₂] and tetrakis-meso-(4-methoxyphenyl)-porphyrin (An₄PH₂) are used as macrocyclic tetrapyrrolic ligands. The complexes are widely characterized with various physico-chemical methods (NMR and UV-vis spectroscopy, MALDI-TOF mass spectrometry). Quantum chemistry calculations for intermediates of the process are performed. The results of calculations explain the high regioselectivity of the triple-decker complex formation in the developed method.

Solvation-induced switching between staggered and gauche conformers of europium(III) triple-decker complexes with $n$-butoxy- and crown-substituted phthalocyanine ligands [(BuO)₈Pc]${}^{2-}$and [(15C5)₄Pc]${}^{2-}$was studied by UV-Vis and ¹H-NMR in toluene and chloroform media. The crown-substituted complex Eu₂[(15C5)₄Pc]₃ was conformationally invariant, adopting the staggered arrangement of adjacent ligands in both solvents. In contrast, in the case of butoxy-substituted complex Eu₂[(BuO)₈Pc]₃, the staggered and gauche forms were stabilized in toluene and chloroform, respectively. These conclusions could easily be drawn from the UV-Vis data. In contrast, a comparison of the ¹H-NMR spectra of the complexes in both solvents showed that the spectral manifestation of conformational switching was obscured by media effects, although some characteristic spectral patterns of each conformation could still be identified on the example of the complex with hexa-$n$-butoxy-15-crown-5-phthalocyanine ligands Eu₂[(BuO)₆(15C5)Pc]₃.