Lutetium diphthalocyanine

Liu Y, Shigehara K and Yamada A 1989 Purification of lutetium diphthalocyanine and electrochromism of its Langmuir-Blodgett films Thin Soiid Fiims 179 303-8... 

The same color variety is not typical with inorganic insertion/extraction materials blue is a common transmitted color. However, rare-earth diphthalocyanine complexes have been discussed, and these exhibit a wide variety of colors as a function of potential (73—75). Lutetium diphthalocyanine [12369-74-3] has been studied the most. It is an ion-insertion/extraction material that does not fit into any one of the groups herein but has been classed with the organics in reviews. Films of this complex, and also erbium diphthalocyanine [11060-87-0] have been prepared successfiiUy by vacuum sublimation and even embodied in soHd-state cells (76,77). 

One of the few studies that have been performed is the work of Cheng and Schiffrin [6] at the interface between water and 1,2-dichloro-ethane. The reactant in the aqueous phase was the [Fe(CN)g]3-,/4 couple, and a few different couples (e.g., lutetium diphthalocyanine) were employed in the organic phase. While the reaction rates could be measured by impedance spectroscopy (see Chapter 13), and were clearly... 

Many other organic materials have been deposited by evaporation in vacuo but usually form either a polycrystalline or an amorphous structure. However, Hoshi et al. [424] have made some progress in depositing epitaxial films of lutetium diphthalocyanine on to single crystals of potassium bromide. Here again the temperature of the substrate is critical but only relatively small areas of continuous crystal have been obtained. 

Figure 4.38 The structure of HLu(Pc)2 [61b]. (Reprinted with permission from J. Fischer, R. Weiss, et al, Synthesis, structure and spectroscopic properties of the reduced and reduced protonated forms of lutetium diphthalocyanine, Inorganic Chemistry, 27, no. 7, 1287-1291, 1988. 1988 American Chemical Society.)...

The reaction between lutetium (III) acetate and 1,2-dicyanobenzene in refluxing 1-hexanol in the presence of DBU gave the lutetium diphthalocyanine... 

The presence of a multicolour electrochromic effect in rare-earth diphthalo-cyanines was first reported in 1970 by Moskalev et al. . Lutetium diphthalocyanine, LuH(Pc)2, has been studied extensively at Rockwell International Corporation by Nicholson and co-workers . This material may display different colours when polarized either anodically (red, orange) or cathodically (blue, violet) from its initial rest potential. The initially green complex film is obtained by vacuum evaporation. The anodic reaction occurs by the insertion of anions into the film and extraction of electrons rather than by loss of protons. The cathodic reaction, leading to blue and violet products, occurs by the insertion of cations. When protons are present in the electrolyte, the reaction is the following . 

The rather rarely used lutetium diphthalocyanine [Lu(III)2-68] was shown to be able to undergo a successful but very slow oxidative electropolymerization process under a continuous potential cycling carried out during several hours... 

Moore, D.J. and T.F. Guarr (1991). Electrochromic properties of electrodeposited lutetium diphthalocyanine thin films. J. Electroanal. Chem. 314, 313-321. 

LUer M., Ckizien Y. and Courtot-Coupez J. (1983) "Electrochemical Behaviour of Lutetium diphthalocyanine in Methylene Chloride". 

In contrast to the cited above data, it was reported [28] that in the synthesis of lutetium diphthalocyanine by Kirin s method the complex LuPc2 is formed. The product does not contain an amide proton N-H. The structure of complex is confirmed by the mass-spectrometry data besides the elemental analysis. In the spectrum of... 

Synthesis of Double-decker Lutetium(lll) Diphthalocyanine with Crown-Ether Substituents b/s tetra[(benzo-15-crown-5)-4 -yl-oxymethyl]phthalocyaninato lutetium(lll) [118d]... 

HGURE 8.1. Formal potentials of redox species in W, NB and DCE versus NHE. Abbreviations ZnTMPyP = zinc tetra-7V-methyl-4-pyridium porphyrin, DcMFc = decamethylfetrocene, TCNQ = 7,7,8,8-tetracyanoquinodimethane, DiMFc = dimethylferrocene, Fc = ferrocene, RuTPP(py)2 = bisfpyridine) meso-tetraphenylporphyrinato ruthenium(II), SnPc2 = tin(IV) diphthalocyanine, LuPc2 = lutetium(in) di]dithalo-cyanine, DiFcET = diferrocenylethane, TAA = tris(4-methoxyphenyl)amine, TPB = tetraphenylborate, TBrPA = tris(4-bromophenyl)amine, TCIPB = tetrakis(4-chlorophenyl)borate. The data is from Ref. [26], except where otherwise noted Ref. [6], Ref. [29], Ref. [30], Ref. [31], Ref. [32]. Reprinted from Ref. [28], with permission from the Polarographic Society of Japan. 

By using cyclic voltammetry, Schiffrin and coworkers [26, 186, 187, 189] studied electron transfer across the water-1,2-dichloroethane interface between the redox couple FefCNls /Fe(CN)6 in water, and lutetium(III) [186] and tin(IV) [26, 187] diphthalocyanines and bis(pyridine)-me50-tetraphenylporphyrinato-iron(II) or ru-thenium(III) [189] in the organic solvent. An essential advantage of these systems is that none of the reactants or products can cross the interface and interfere with the electron transfer reaction, which could be clearly demonstrated. Owing to a much higher concentration of the aqueous redox couple, the pseudo-first order electron transfer reactions could be analyzed with the help of the Nicholson-Shain theory. However, though they have all appeared to be quasireversible, kinetic analysis was restricted to an evaluation of the apparent standard rate constant o. which was found to be of the order of 10 cm s [186, 189]. Marcus [199] has derived a relationship between the pseudo-first-order rate constant for the reaction (8) and the rate... 

In this chapter, a correlation between the ionic radius of the metal-complexing in double-decker phthalocyanines and positions of maxima Q-bands in the electronic absorption spectra were determined in dimethylformamide and chloroform. The increasing of ionic radius from holmium to lutetium caused a regular change in the position of the maxima Q-bands in the absorption spectra. The behavior of metal diphthalocyaninates in supramolecular systems was also investigated. It was revealed that a new band shifted to the red region appeared in absorption spectra of sandwich phthalocyaninates of lutetium, etbium and ytteibium in albumin solution. This particular behavior allows us to consider phthalocyanines as prototype of sensitive biosensor system. 

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