Synthesis of lutetium octaalkylthiotetraazaporphyrin complexes

Historic overview and new developments in synthetic methods for preparation of the rare-earth tetrapyrrolic complexes

“…Kirin and Moskalev also pointed out that because of the large ionic radii and high coordination numbers of the rare-earth ions, the formation of the double-decker rare-earth phthalocyanine compounds could be achieved under specific reaction conditions [20,21]. During the next 50 years, it was confirmed that rare-earth ions are capable of the formation of phthalocyanine single-, double, and triple-decker complexes and their analogues [22][23][24][25][26][27][28][29][30][31][32][33]. One of the interesting recent discoveries was the preparation and characterization of heteronuclear (rareearth / cadmium) multiple-decker complexes, which contain up to six Pc ligands [34][35][36][37][38][39][40][41][42].…”

“…This contribution compiles the work developed on the rare-earth porphyrinoids reported by several groups around the world. 8 In order to avoid confusion in terminology [23,25,29], the following definitions will be used in this review: (i) multiple-decker homoleptic complexes are those with identical ligands;…”

“…Indeed, the general reaction between metal-free Pc analogues or Pors with rare-earth chlorides, acetates, and -diketonates results in the formation of the lutetium tetra(t-Bu)-substituted pyrazinoporphyrazine 23 [114], lutetium octaphenyl-, octaethythio-, and octadecylthiosubstituted TAPs 24 [114,115], lutetium 1,2-Nc 13 [116,117] and tetra(t-Bu)-substituted 2,3-Nc [120] ( Figure 6), as well as a variety of rare-earth mesosubstituted single-decker Por complexes [121124]. DMF [114], DMSO [114,115,118,120], or octanol [115] were used as solvents in these reactions. Interestingly, lutetium insertion into the octaalkyl-substituted TAP macrocycle resulted in the formation of complex 24 even at room temperature.…”

“…In the case of 1,2-Nc derivatives, each of the individual macrocycles can form four positional isomers of C 4h , D 2h , C 2v , C s symmetry and thus complex 104 should also consist of numerous positional isomers, which will be challenging to separate using conventional purification methods. Neodymium and europium double-decker 1,2-Ncs 104 are also discussed in [95], but synthetic conditions and yields of the target compounds were not clearly reported. Phenyl-substituted double-decker 2,3-Ncs 105 could be prepared in 55-63% yields [124] using a general method developed for the preparation of their unsubstituted analogues 84 (Table 4).…”

Sandwich-Type Lanthanide(III) Dinaphthalocyanine Complexes Possessing an Intensive Absorption in the Near IR Region: Synthesis and Investigation of Properties

“…This method considerably differs from the synthesis in solution [11][12][13] since the starting nitrile serves simultaneously as the reagent and the reaction medium. According to this method, the synthesis of dinaphthalocyanines 2-4 was performed by melting of a mixture of dinitrile 1 with the corresponding lanthanide acetates by the gradual increase of temperature from 220 to 310 °C and by keeping at this temperature until the reaction mixture was solidified (~2 h).…”