Synthesis and characterization of heteroleptic rare earth double-decker complexes involving tetradiazepinoporphyrazine and phthalocyanine macrocycles

Abstract

Reaction of (2,3,9,10,16,17,23,24-octabutylphthalocyaninato)lanthanide(III) acetylacetonates (BuPcLn(acac), 1a–c, Ln = Lu (a), Eu (b), La (c)) with tetrakis(5,7-bis(4-tert-butylphenyl)-6H-1,4-diazepino)[2,3-b,g,l,q]porphyrazine ligand (tBuPhDzPzH2, 2) produced sandwich compounds (tBuPhDzPz)Ln(BuPc) (3a–c), which represent first heteroleptic double-deckers incorporating...

Rare-earth based tetrapyrrolic sandwiches: chemistry, materials and applications

“…In the case of mixed ligand complexes [( t BuPh) 8 DZPz]M(Pc) , M = La, Eu and Lu, spontaneous aggregation due to inversion of diazepine ring was observed even for anionic forms. 146 In contrast to homoleptic complexes these double-deckers could form only dimeric species, which were observed by NMR spectroscopy. Tendency to aggregation followed the growth of the ionic radius of lanthanide ion due to an increase of interligand distance, weakening of intramolecular CH…N interactions and facilitation of diazepine ring inversion.…”

Luminescent Complexes of Europium (III) with 2-(Phenylethynyl)-1,10-phenanthroline: The Role of the Counterions

“…Last decades, it has been proved that the DFT/TD-DFT approach is successful for investigation of the structure and spectroscopic properties even of very large complexes containing rare earth elements [ 54 , 55 , 56 ]. The advantage of the DFT/TF-DFT approach is that it is reasonable time-consuming and requires relatively low computational cost, while its disadvantage is that the results are quantitatively dependent on the choice of the DFT functional.…”

Electronic and steric effects controlling monomer–dimer self-assembly in 6H-1,4-diazepinoporphyrazines: an experimental and theoretical study

“…Similar to phthalocyanines, the UV-vis spectra of the resulting oxidized forms are characterized by a split Q-band; however, a characteristic absorption in the region of 400–600 nm corresponding to the presence of the radical forms is absent. Similar to the sandwich complexes of 6 H -1,4-diazepinoporphyrazines with lanthanides, 31 this is due to the stronger aggregation of the oxidized cationic forms of 6 H -1,4-diazepinoporphyrazine metal complexes as compared to phthalocyanine analogues.…”

“…This journal is © The Royal Society of Chemistry 2023 presence of the radical forms is absent. Similar to the sandwich complexes of 6H-1,4-diazepinoporphyrazines with lanthanides, 31 this is due to the stronger aggregation of the oxidized cationic forms of 6H-1,4-diazepinoporphyrazine metal complexes as compared to phthalocyanine analogues.…”

“…Thus, the characteristics of the resonance signals of diastereotopic CH 2 protons can be used as an instrument for the identification of the dimeric/monomeric form of 6H-1,4-diazepinefused porphyrazines in solution (Table S1 †). 6,14,[17][18][19][20][31][32][33][34][35][36][37]…”