A series of 14 heteroleptic rare earth sandwich complexes [M(III)-(nc)(oep)] (M=Y, La-Lu except Ce and Pm; nc=2,3-naphthalocyaninate; oep = octaethylporphyrinate) have been prepared by a one-pot procedure from corresponding [M(acac)3] . nH2O (acac = acetylacetonate), metal-free porphyrin H2(oep), and naphthalonitrile the presence of 1,8-diazabicyclo[5,4,0]undec-7-ene (DBU) in n-octanol. The molecular structures of four of these complexes (M = Sm, Gd, Y, Lu) are isostructural, exhibiting a slightly distorted square antiprismatic geometry with two domed ligands. The interplanar distance decreases from 2.823 to 2.646 A along the series as a result of lanthanide contraction. The whole series of complexes have also been characterized spectroscopically. All the electronic absorptions, except the two B-bands due to nc and the oep rings, are metal-dependent, indicating that there are substantial pi-pi interactions. The hole or the unpaired electron in these double-deckers is delocalized over both macrocyclic ligands, as evidenced by the co-appearance of the IR marker bands for the nc*- (1315-1325 cm(-1)) and oep*- (1510-1531 cm(-1)) T radical ions. Three one-electron oxidation couples and up to three one-electron reduction couples have been revealed by electrochemical methods. All the potentials are linearly dependent on the size of the metal center. The changes in absorption spectra during the first electro-oxidation and reduction of the La(III), Eu(III), and Y(III) double-deckers have also been studied spectroelectrochemically. The spectral data recorded for [M(III)(nc)(oep)]-(M = Y, La-Lu except Ce and Pm) reduced chemically with hydrazine hydrate are in accord with those obtained by spectroelectrochemical methods. The first heteroleptic naphthalocyaninate-containing triple-deckers [M(III)2(nc)-(oep)2] (M = Nd, Eu) have also been prepared by a raise-by-one-story method by using [M(III)(nc)(oep)] (M = Nd, Eu), [M(acac)3] . nH2O (M = Nd, Eu), and H2(oep) as starting materials. The compounds adopt a symmetrical triple-decker structure with two outer oep rings and one inner nc ring, which has been confirmed by 'H NMR spectroscopy and X-ray structural determination of the Nd complex. Both compounds give a near-IR absorption at 1021 nm (for M=Nd) or 1101 nm (for M = Eu), which has rarely been observed for neutral (or hole-free) triple-decker complexes and can be ascribed to the lowest-energy Q'(0, 0) transition. Similarly to the double-decker analogues. these triple-decker complexes undergo a series of one-electron transfer processes with a relatively small potential gap (1.1 -1.2 V) between the first oxidation and the first reduction.

Several cofacial phthalocyanines (Pcs) with an Si−Si linkage were obtained by one‐step condensation of 1H‐isoindole‐1,3(2H)‐diimine with hexachlorodisilane as template in quinoline. They were characterized by gel‐permeation chromatography, IR, NMR spectroscopy, and mass spectrometry, and cyclic voltammetry. The results strongly suggest that we indeed obtained Pc dimers directly linked by an Si−Si bond using this novel concept of utilizing a compound/salt with an element–element bond as a template. The cofacial dimer structures are reasonably supported by X‐ray absorption near‐edge structure (XANES), electronic absorption and magnetic circular dichroism (MCD) spectra, and molecular orbital (MO) calculations. Interestingly, they show an electronic absorption spectrum very similar to that of silicon tetrabenztriazacorrole (SiTBC).

Bis(substituted-2,3-naphthalocyaninato)europium(III) complexes: bis(octakis(dodecylthio)-2,3-naphthalocyaninato)europium(III) (Eu[2,3-Nc(SC12H25)8]2, 1) and bis(tetra-tert-butyl-2,3- naphthalocyaninato)europium(III) (Eu[2,3-Nc(t-Bu)4]2, 2) have been synthesized by cyclic tetramerization of naphthalonitriles with Eu(acac)3.H2O in the presence of 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) in refluxing n-octanol. These compounds were characterized by UV-visible, magnetic circular dichroism (MCD), near-IR, IR, EPR, and mass spectroscopies. The absorption and MCD spectra of 1 showed splitting of the Q band, with peaks at 700 and 784 nm, red shifted from the Q band of 2 at 763 nm. The absorption and MCD spectral band deconvolution calculations of complex 1 gave two A terms in the Q-band region. The A terms are assigned to 2A2-->2E1 transitions. Cyclic voltammograms of 1 and 2 showed reversible oxidation couples at E1/2 = -0.28 V (for 2) and -0.25 V (for 1) vs ferrocenium/ferrocene (Fc+/Fc). The second oxidation exhibited a complicated behavior for both complexes. The reduction couples for 2 were observed at E1/2 = -0.61, -1.64, -1.97, and -2.42 V, and for 1 they were observed at E1/2 = -0.62, -1.60, -1.86, and -2.27 V vs Fc+/Fc. Spectral changes observed on chemical oxidation and reduction of the complexes are presented, and the behaviors of 1 and 2 are compared.

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