Studies of “Pinwheel‐Like” Bis[1,8,15,22‐tetrakis(3‐pentyloxy)phthalocyaninato] Rare Earth(III) Double‐Decker Complexes

Abstract

Homoleptic bis(phthalocyaninato) rare-earth double-deckers complexes [M(III)[Pc(alpha-OC5H11)4]2] (M = Eu, Y, Lu; Pc(alpha-OC5H11)4 = 1,8,15,22-tetrakis(3-pentyloxy)phthalocyaninate) have been prepared by treating the metal-free phthalocyanine H2Pc(alpha-OC5H11)4 with the corresponding M(acac)3.nH2O (acac = acetylacetonate) in refluxing n-octanol. Due to the C4h symmetry of the Pc(alpha-OC5H11)4 ligand and the double-decker structure, all the reactions give a mixture of two stereoisomers with C4h and D4 symmetry. The former isomer, which is a major product, can be partially separated by recrystallization due to its higher crystallinity. The molecular structure of the major isomer of the Y analogue has been determined by single-crystal X-ray diffraction analysis. The metal center is eight-coordinate bound to the isoindole nitrogen atoms of the two phthalocyaninato ligands, forming a distorted square antiprism. Such an arrangement leads to an interesting pinwheel structure when viewed along the C4 axis, which assumes a very unusual S8 symmetry. The major isomers of all these double-deckers have also been characterized with a wide range of spectroscopic methods. A systematic investigation of their electronic absorption and electrochemical data reveals that the pi-pi interaction between the two Pc(alpha-OC5H11)4 rings is weaker than that for the corresponding unsubstituted or beta-substituted bis(phthalocyaninato) analogues.

Heteroleptic protonated bis(phthalocyaninato) rare earth compounds containing 1,4,8,11,15,18,22,25-octa(butyloxy)-phthalocyanine ligand

“…1,4,8,11,15,18,22,25-octa(butyloxy)-phthalocyanine ligand. It is noteworthy that all the works about bis(phthalocyaninato) rare earth complexes reported thus far dealt with unsubstituted or peripherally substituted phthalocyanines except M(Pc)[Pc(␣-OC 4 H 9 ) 4 ] and M[Pc(␣-OC 4 H 9 ) 4 ] 2 in which the 1, 8,15,22-tetrakis(3-pentyloxy)phthalocyanine is contained [6,7]. The compounds described herein are the first example of bis(phthalocyaninato) rare earth(III) complexes containing phthalocyanines with eight substituents at nonperipheral positions.…”

Synthesis, spectroscopic properties and electrochemistry of (2,9,16,23-tetrasubstituted phthalocyaninato) erbium complexes

“…In order to enhance the performance of the material, one way is to introduce different kinds of substituents onto the phthalocyanine ring so that the properties of phthalocyanines can be significantly altered [10]. In this paper, we present two homoleptic bis(phthalocyaninato) erbium(III) complexes and two halfsandwich phthalocyaninato erbium(III) complexes with n-pentyloxy or tert-butyl substituents which are highly soluble in common organic solvents.…”

Distribution of the unpaired electron in neutral bis(phthalocyaninato) yttrium double-deckers: An experimental and theoretical combinative investigation

“…2750−3000 cm -1 in the IR spectra of 2-5, which disappear in the unsubstituted double-decker complex 1. It is worth noting that in the IR spectra of all the double-deckers 1-5, a medium-tostrong band is observed in the range of 1319-1322 cm -1 , which is a diagnostic marker band for the phthalocyanine p-radical anion [24], adding more evidence for the unpaired electron nature of these double-decker complexes.…”