Sandwich-type heteroleptic phthalocyaninato and porphyrinato metal complexes

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

“…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].…”

“…Apart from their intrinsic interest, the chemistry of these compounds has been investigated with the goal of developing novel materials for practical applications based on the unique optical and electrical properties of these sandwich complexes. The heteroleptic analogues containing different tetrapyrrole ligands [14,15], in particular those with mixed phthalocyaninato and porphyrinato ligands, are of particular interest, because the very different spectroscopic properties of the ligands allow a study of the electronic interactions between the p-systems. Although a substantial number of such heteroleptic sandwich compounds have been synthesized recently, most of them are confined to lanthanide and group 4 transition metal complexes with unsubstituted phthalocyanine [14].…”

“…The heteroleptic analogues containing different tetrapyrrole ligands [14,15], in particular those with mixed phthalocyaninato and porphyrinato ligands, are of particular interest, because the very different spectroscopic properties of the ligands allow a study of the electronic interactions between the p-systems. Although a substantial number of such heteroleptic sandwich compounds have been synthesized recently, most of them are confined to lanthanide and group 4 transition metal complexes with unsubstituted phthalocyanine [14]. It has been reported that the electrochemical, spectroscopic and other physical properties of these double-decker complexes are related to the inter-ring distance in the molecule, which is determined by the ionic radius of the central metal ion and the strength of the metal-ligand bonds [3,[16][17][18][19].…”

The First Example of Near-Infrared 4f Luminescence of Sandwich-Type Lanthanide Phthalocyaninates

“…[7][8][9] The lanthanide ion in investigated complexes can be located directly at porphyrin N 4 coordination cavity [10][11][12] or bound by chelating peripheral substituents of a porphyrin. [13] Although there are many reports on the synthesis and physico-chemical properties of lanthanide complexes with phthalocyaninesanalogues of porphyrins, [14][15][16][17][18] but number of works devoted to investigation of 4f luminescence in these compounds are limited. [19][20][21] Higher thermal stability of phthalocyanines compared to porphyrins, ability of these molecules to self-assembling due to stacking interactions between aromatic rings makes them attractive for spectroscopic investigations and optical applications.…”

The Role of Oxygen in Electrochemical Reduction of Double-Decker Phthalocyaninates of Lanthanides

“…[1][2][3][4] Sandwich double-and triple-decker lanthanides complexes are special type of phthalocyanine compounds due to unique electronic, optical, and physico-chemical properties that are determined by strong intramolecular π-π interactions between ligands. [5][6][7][8] Electrochromism, which is characteristic for sandwich lanthanide phthalocyaninates, [9][10][11][12][13] provides ability for their application in production of displays for electronic devices. Some groups note high prospects of employment of large set of electrochemically reversible redox-transitions in sandwich complexes of lanthanides for multibit information recording.…”