Tetrabutylammonium Salts of Aluminum(III) and Gallium(III) Phthalocyanine Radical Anions Bonded with Fluoren-9-olato(-) Anions and Indium(III) Phthalocyanine Bromide Radical Anions.

Title Tetrabutylammonium Salts of Aluminum(III) and Gallium(III) Phthalocyanine Radical Anions Bonded with Fluoren-9-olato(-) Anions and Indium(III) Phthalocyanine Bromide Radical Anions.
Authors D.V. Konarev; S.S. Khasanov; M. Ishikawa; Y. Nakano; A. Otsuka; H. Yamochi; G. Saito; R.N. Lyubovskaya
Journal Chem Asian J
DOI 10.1002/asia.201700138
Abstract

Reduction of aluminum(III), gallium(III), and indium(III) phthalocyanine chlorides by sodium fluorenone ketyl in the presence of tetrabutylammonium cations yielded crystalline salts of the type (Bu4 N(+) )2 [M(III) (HFl-O(-) )(Pc(.3-) )](.-) (Br(-) )?1.5?C6 H4 Cl2 [M=Al (1), Ga (2); HFl-O(-) =fluoren-9-olato(-) anion; Pc=phthalocyanine] and (Bu4 N(+) ) [In(III) Br(Pc(.3-) )](.-) ?0.875?C6 H4 Cl2 ?0.125?C6 H14 (3). The salts were found to contain Pc(.3-) radical anions with negatively charged phthalocyanine macrocycles, as evidenced by the presence of intense bands of Pc(.3-) in the near-IR region and a noticeable blueshift in both the Q and Soret bands of phthalocyanine. The metal(III) atoms coordinate HFl-O(-) anions in 1 and 2 with short Al-O and Ga-O bond lengths of 1.749(2) and 1.836(6)?Å, respectively. The C-O bonds [1.402(3) and 1.391(11)?Å in 1 and 2, respectively] in the HFl-O(-) anions are longer than the same bond in the fluorenone ketyl (1.27-1.31?Å). Salts 1-3 show effective magnetic moments of 1.72, 1.66, and 1.79??B at 300?K, respectively, owing to the presence of unpaired S=1/2 spins on Pc(.3-) . These spins are coupled antiferromagnetically with Weiss temperatures of -22, -14, and -30?K for 1-3, respectively. Coupling can occur in the corrugated two-dimensional phthalocyanine layers of 1 and 2 with an exchange interaction of J/kB =-0.9 and -1.1?K, respectively, and in the ?-stacking {[In(III) Br(Pc(.3-) )](.-) }2 dimers of 3 with an exchange interaction of J/kB =-10.8?K. The salts show intense electron paramagnetic resonance (EPR) signals attributed to Pc(.3-) . It was found that increasing the size of the central metal atom strongly broadened these EPR signals.

Citation D.V. Konarev; S.S. Khasanov; M. Ishikawa; Y. Nakano; A. Otsuka; H. Yamochi; G. Saito; R.N. Lyubovskaya.Tetrabutylammonium Salts of Aluminum(III) and Gallium(III) Phthalocyanine Radical Anions Bonded with Fluoren-9-olato(-) Anions and Indium(III) Phthalocyanine Bromide Radical Anions.. Chem Asian J. 2017;12(8):910919. doi:10.1002/asia.201700138

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Gallium

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