Synthesis and electrochemistry of double-decker lanthanoid (III) phthalocyanine complexes

Correlations between electrochemical and spectral properties of alkyl-substituted diphthalocyanine lanthanide complexes

“…Electronic absorption spectrum of (Et 8 Pc) 2 Lu in the near IR region (CHCl 3 ). 12 8 ν•10 -3 /cm -1 1.0 0.5 D tronic effects of the substituents. Although it seems quite possible that the position of this band in the series of the complexes considered is additionally determined by the steric effects of the substituents too.…”

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

“…Their spectra show a typical Soret band at ca. 330 nm and two Q bands at 686-690 and 755-765 nm (Table 2) just like those of reduced double-decker [M III (Pc) 2 ] − [11] and [M III (Pc*) 2 ] − [12]. But the typical near IR band with wavelength larger than 1380 nm in the near IR region which is highly characteristic for the neutral single-hole bis(phthalocyaninato) rare earth(III) compounds due to an electron transition from the second occupied HOMO to the first semi-occupied HOMO was not observed.…”

“…However, heteroleptic bis(phthalocyaninato) rare earth compounds were isolated in the protonated form H{M(Pc)[Pc(␣-OC 4 H 9 ) 8 ]} in the present case. Obviously, the incorporation of 1,4, 8,11,15,18,22,25-octa(butyloxy)-phthalocyanine ligand into the double-decker molecules stabilized the protonated form of bis(phthalocyaninato) rare earth. These protonated double-deckers can be considered as a kind of weak acid.…”

“…In the present work, the so-called raise-byone-story method [3] has been employed to prepare the non-peripherally substituted phthalocyanine-containing heteroleptic bis(phthalocyaninato) rare earth complexes. Treatment of M(Pc)(acac) with metal-free 1,4, 8,11,15,18,22,25-octa(butyloxy)-phthalocyanine gives the heteroleptic doubledecker compounds in relatively high yields. Surprisingly, although the protonated reduced species have been demonstrated to be the intermediate, all the reported bis(phthalocyaninato) rare earth(III) compounds obtained thus far according to the above-described preparation and isolation procedure have been isolated in the neutral form [1].…”

The optical limiting of blue and green ytterbium double-decker phthalocyanines in solution and in poly(acrylic acid) as thin films

“…Double-or triple-decker phthalocyanines exhibiting characteristic optical and electronic properties can be employed in fields that include as electronic materials [1], sensors [2], electronic displays [3,4], organic field-effect transistors [5][6][7], single molecule magnets [8][9][10][11], self-assembly [12] and nonlinear optics [13]. Lanthanide bisphthalocyanine (LnPc 2 ) complexes exist as green (neutral) or blue (reduced) forms.…”