Molecular Design of Anionic Phthalocyanines with 蟺鈥撓€ Stacking Columnar Arrangement. Crystal Structures, Optical, and Magnetic Properties of Salts with the Iron(I) Hexadecachlorophthalocyanine Anions

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• 作者：Dmitri V. Konarev ; Leokadiya V. Zorina ; Manabu Ishikawa ; Salavat S. Khasanov ; Akihiro Otsuka ; Hideki Yamochi ; Gunzi Saito ; Rimma N. Lyubovskaya
• 刊名：Crystal Growth & Design
• 出版年：2013
• 出版时间：November 6, 2013
• 年：2013
• 卷：13
• 期：11
• 页码：4930-4939
• 全文大小：620K
• 年卷期：v.13,no.11(November 6, 2013)
• ISSN：1528-7505

文摘

Ionic compounds containing iron(I) hexadecachlorophthalocyanine anions have been obtained for the first time as single crystals: (PPN⁺){[Fe(I)Cl₁₆Pc(鈭?)]^{鈭?/sup>} (1), (Ph₃MeP+)₂{[Fe(I)Cl₁₆Pc(鈭?)]鈭?/sup>}(Br鈥?/sup>)路C₆H₄Cl₂ (2), and (PPN+)₂[Fe(I, II)Cl₁₆Pc(鈭?)]₃(2鈭?路4C₆H₄Cl₂ (3), where PPN+ is the cation of bis(triphenylphosphoranylidene)ammonium and Ph₃MeP+ is the triphenylmethylphosphonium cation. The [Fe(I)Cl₁₆Pc(鈭?)]鈭?/sup> anions form closely packed 蟺鈥撓€ stacking columns in 1鈥?b>3. Salts 1 and 2 with integer 鈭? charge on iron phthalocyanines have uniform and weakly dimerized columns, respectively. Salt 3 has two cations per three iron phthalocyanine molecules which are arranged in trimers within the columns. Different shift of phthalocyanines at the same interplanar distances of 3.33鈥?.38 脜 provides essentially shorter Fe路路路Fe distances in 3 (3.62鈥?.84 脜) than those in 1 and 2 (5.07鈥?.45 脜). Calculations show a strong LUMO鈥揕UMO overlapping between [Fe(I)Cl₁₆Pc(鈭?)]鈭?/sup> in 1鈥?b>3 with the overlap integrals of 4.1鈥?.6 脳 10鈥?. Weak signals attributed to the [Fe(II)Cl₁₆Pc(鈭?)]鈭?/sup> species with the delocalization of electron on the phthalocyanine macrocycles are observed in the EPR spectra of 1鈥?b>3. The content of this admixture is less than 1% in all salts. Nevertheless, static magnetic susceptibility measurements for 3 detected significant magnetization. The effective magnetic moment is 4.05 渭_B per formula unit at 300 K. It can originate from the spins localized on the iron atoms of [Fe(I)Cl₁₆Pc(鈭?)]鈭?/sup>. The Weiss temperature of 鈭?3 K in the 60鈥?00 K range indicates a strong antiferromagnetic interaction of spins which results in the decreases of magnetic moment of 3 with temperature below 220 K down to 2.72 渭_B at 6 K. Optical spectra of 1鈥?b>3 show bands ascribed to [Fe(I)Cl₁₆Pc(鈭?)]鈭?/sup> at 339鈥?49, 538鈥?48, 685鈥?91, and 805鈥?21 nm. The bands in the NIR range at 1740鈥?810 nm were attributed to charge transfer excitations within phthalocyanine columns associated with the unpaired electrons on the iron atoms.}