Dianionic Titanyl and Vanadyl (Cation(+))(2)[(MO)-O-IV(Pc4-)](2-) Phthalocyanine Salts Containing Pc4- Macrocycles

作者：Konarev Dmitri V^*; Kuzmin Alexey V; Khasanov Salavat S; Litvinov Alexey L; Otsuka Akihiro; Yamochi Hideki; Kitagawa Hiroshi; Lyubovskaya Rimma N

来源：Chemistry-An Asian Journal, 2018, 13(12): 1552-1560.

DOI：10.1002/asia.201701754

• crystal structure
• dianionic salts of metal phthalocyanines
• Jahn-Teller distortion
• optical and magnetic properties
• titanyl and vanadyl phthalocyanines

In this study, the titanyl and vanadyl phthalocyanine (Pc) salts (Bu4N+)(2)[(MO)-O-IV(Pc4-)](2-) (M=Ti, V) and (Bu3MeP+)(2)[(MO)-O-IV(Pc4-)](2-) (M=Ti, V) with [(MO)-O-IV(Pc4-)](2-) dianions were synthesized and characterized. Reduction of (MO)-O-IV(Pc2-) carried out with an excess of sodium fluorenone ketyl in the presence of Bu4N+ or Bu3MeP+ is exclusive to the phthalocyanine centers, forming Pc4- species. During reduction, the metal +4 charge did not change, implying that Pc is an non-innocent ligand. The Pc negative charge increase caused the C-N(pyr) bonds to elongate and the C-N(imine) bonds to alternate, thus increasing the distortion of Pc. Jahn-Teller effects are significant in the [eg(*)](2) dianion ground state and can additionally distort the Pc macrocycles. Blueshifts of the Soret and Q-bands were observed in the UV/Vis/NIR when (MO)-O-IV(Pc2-) was reduced to [(MO)-O-IV(Pc.3-)](.-) and [(MO)-O-IV(Pc4-)](2-). From magnetic measurements, [(TiO)-O-IV(Pc4-)](2-) was found to be diamagnetic and (Bu4N+)(2)[(VO)-O-IV(Pc4-)](2-) and (Bu3MeP+)(2)[(VO)-O-IV(Pc4-)](2-) were found to have magnetic moments of 1.72-1.78(B) corresponding to an S=1/2 spin state owing to V-IV electron spin. As a result, two latter salts show EPR signals with V-IV hyperfine coupling.

• 出版日期2018-6-18