Synthesis and properties of lanthanide complexes with tetrapyrazinoporphyrazine and its substituted derivatives

Tetrapyrazinoporphyrazines and their metal derivatives. Part I: Synthesis and basic structural information

“…The Al III complex [TPyz1PzAl (OH)] was prepared [122] with 80% yield by template cyclotetramerization of the dinitrile Pyz1 with AlCl 3 in 1,2-dichlorobenzene in the presence of ammonium molybdate. The lanthanide complexes [TPyz1PzLn (acac)] with Ln = Er III , Tm III , Yb III , Lu III [78] and [TPyz1PzLu(Cl)] [188] were also obtained in similar yields (60-75%) in the complexation reaction between [TPyz1PzH 2 ] and the corresponding lanthanide acetylacetonate or chloride. The sandwich complex [(TPyz1Pz) 2 Lu] has been prepared from the dinitrile precursor by the "isoindoline" method [188].…”

“…The Zn II complexes of symmetrical 3-pyridyl substituted TPyzPz [121] and non-symmetrical TPyzPzs with four 2-thienyl rings [121], also in combination with 3-pyridyl radicals [121] and maleimide moieties [180], were also later reported by this group [118]. Complexes of octa(2-pyridyl)substituted TPyzPzs with Er III and Yb III were briefly reported by Russian authors [78]. Further, the metal free TPyzPzs bearing 2-thienyl or oligo-2,5-thienyl (bis-and tris-) moieties and the corresponding Zn II and Cu II complexes were also announced as perspective organic conducting materials [203] but no characterization details were reported.…”

“…To date the metal free species [TPyz27PzH 2 ] [116] and its complexes with Mg II [67,123], transition metals (Fe II [198,199] [74], lanthanides (Er III , Tm III , Yb III , Lu III [78,201]) were synthesized and characterized to a different extent. The complexes were prepared by direct template cyclotetramerization of the dinitrile in the presence of the corresponding metal salt in a melt or in the solvent ( A c c e p t e d M a n u s c r i p free species [TPyz27PzH 2 ] was prepared either by reaction of the dinitrile precursor with Li in amyl alcohol or, better, through the demetallation of the Mg II complex upon reprecipitation from sulfuric acid [116].…”

“…The sandwich Yb III complex [(TPyzPz) 2 Yb] was also reported [77] and preparation of other lanthanoid complexes (M = Y III , La III , Nd III , Gd III , Dy III , Er III ) was mentioned in the same work. Mononuclear complexes of Er III and Lu III with axial chloride, acetate or acetylacetonate were synthesized by melting the diiminoimide 5 (Scheme 3) with corresponding metal salts at 200-210°C [78]. The metal free macrocycle [TPyzPzH 2 ] can be obtained either by demetallation of the Mg II complex [1,6], through the very labile intermediate dilithium(I) [2] or disodium(I) [79] derivatives, or directly from the corresponding diiminoimide 5 in dialkylaminoethanol [80,81].…”

Synthesis of Iron(II) Octachlorotetrapyrazinoporphyrazine, Molecular Structure and Optical Properties of the (X−)2FeTPyzPACl8 Dianions with Two Axial Anionic Ligands (X− = CN−, Cl−)

“…Now various methods for preparing substituted tetrapyrazinoporphyrazines with different donor substituents were developed. [22][23][24][25][26][27] Electron-withdrawing substituents such as cyano-, sulfophenyl-, 2-pyridyl and 2-(N-methyl)-pyridiniumyl are used to increase the acceptor ability of tetrapyrazinoporphyrazines. [21,[28][29][30][31] Molecular structure of pyridine substituted tetrapyrazinoporphyrazine is determined by single-crystal X-ray analysis for cobalt(II) tetrakis[5,6-di(2-pyridyl)-2,3-pyrazino}porphyrazine, Co II TPyzPAPy 8 .…”