Darstellung und Eigenschaften der Diphthalocyaninate des Yttriums und Indiums

Abstract

Blaue Di(phthalocyaninato(2–))metallate des dreiwertigen Yttriums und Indiums werden durch die Reaktion von Yttriumacetat und wasserfreiem Indiumchlorid mit geschmolzenem Phthalodinitril in Gegenwart von Kaliummethylat dargestellt und als Komplexsalze voluminöser organischer Kationen isoliert. Die anodische Oxydation von (nBu4N)[M(Pc2−)2] (M = Y, In) liefert Kristalle von grünem, paramagnetischem Di(phthalocyaninato)metall(III)‐dichlormethan‐Solvat, [M(Pc)2] · CH2Cl2 (μeff = 1,8/1,9 B.M. (Y/In)). Rotbraunes Di(phthalocyaninato)metall(III)‐polybromid, [M(Pc−)2]Brx wird durch die Oxydation mit überschüssigem Brom präpariert. Die Redoxeigenschaften der Di(phthalocyaninato)metallate(III) werden mit der zyklischen Voltammetrie und Differenzpulspolarographie untersucht. Ein quasi‐reversibler (ΔE ≃ 60 mV) Einelektronen‐Prozeß bei 0,09 V (Y) und −0,07 V (In) wird dem Redoxpaar [M(Pc2−)2]−/[M(Pc)2] zugeordnet. Weiterhin wird über die elektronischen Absorptions‐sowie MIR/FIR‐ und Resonanz‐Raman‐Spektren berichtet. Die charakteristischen Merkmale der drei verschiedenen Oxydationszustände werden in Abhängigkeit vom Radius und der Elektronenkonfiguration des Metallions diskutiert.

Infra-red spectroscopic characteristics of naphthalocyanine in bis(naphthalocyaninato) rare earth complexes peripherally substituted with thiophenyl derivatives

“…5. These results agree well with the change of the unsubstituted bis(phthalocyaninato) compounds M(Pc) 2 [32][33][34][35][36][37][38]. The rest important vibrations are the aza and isoindole stretching at 1437-1475 cm À1 and the naphthalene stretching at 1578-1581 cm À1 and 1600-1725 cm À1 .…”

Double-decker Yttrium(III) Complexes with Phthalocyaninato and Porphyrinato Ligands

“…The electronic absorption spectra of 1-9 were also measured ( Table 1). The data for the known compounds 1 [21] and 6 [19] were fully consistent with those reported previously. The UV-vis and near-IR spectra of the homoleptic (2 and 3) and heteroleptic (4 and 5) bis(phthalocyaninato) complexes closely resembled the spectra of analogous Eu(III) and Gd(III) complexes [7,24] and could be assigned in the same manner.…”

“…Yttrium, which has a smaller ionic radius than the lanthanides (except Lu), also forms double-decker complexes, but examples are scarce. To our knowledge, only a few yttrium complexes, namely Y(P) 2 (P = Pc [17,20,21], Por [18,22,23]) and Y(Pc)(TPP) [19], have appeared in the literature, and heteroleptic complexes with a substituted phthalocyaninato ligand are extremely rare [14]. Very recently we have developed a useful procedure to prepare heteroleptic sandwiches Eu(P)(Pc) (P = Pc*(C 7 H 15 ) 8 , Pc*(OC 5 H 11 ) 8 , Por) which involves the cyclic tetramerization of phthalonitriles induced by the half-sandwich lanthanide complexes M(P)(acac) (P = Pc, Por) [24,25].…”

Dinuclear RhII-Phthalocyaninates with a Rh-Rh Single Bond: X-ray Crystal Structure of Di(pyridinephthalocyaninato(2-)rhodium(II))

“…[7], In [7]) and [{Ru(py)pc 2-} 2 (µ-C)] [16] 574,732,756,874,914,1003,1069,1125,1166,1287,1327,1376,1417,1458,1504,1609.…”

“…Mononuclear type I chelates are by far the most studied class of diphthalocyaninates and have been reported for ter-and quadrivalent lanthanides [5], some actinides [6], tervalent Y [5a,7], In [7,8], Bi [9] and quadrivalent Sn [10], Ti [11] and Zr [12]. From the extensively studied molecular structures it is known that the voluminous metal ion with ionic radius r M > 0.7 Å , essentially not fitting into the pc 2-core, is eight-fold coordinated by the isoindole N atoms (N iso ) of two frequently staggered (skew angle 39 ² π ² 45°) saucer shaped pc 2-ligands.…”