Coordination Complexes of Pentamethylcyclopentadienyl
Iridium(III) Diiodide with Tin(II) Phthalocyanine and Pentamethylcyclopentadienyl
Iridium(II) Halide with Fullerene
C<sub>60</sub><sup>–</sup> Anions
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Abstract
Synthetic
approaches to iridium complexes of metal phthalocyanines
(Pc) and fullerene anions have been developed to give three types
of complexes. The compound{(Cp*Ir<sup>III</sup>I<sub>2</sub>)Sn<sup>II</sup>Pc(2−)}·2C<sub>6</sub>H<sub>4</sub>Cl<sub>2</sub> (<b>1</b>) (Cp* is pentamethylcyclopentadienyl) is the first
crystalline complex of a metal phthalocyanine in which an iridium(III)
atom is bonded to the central tin(II) atom of Pc via a Sn–Ir
bond length of 2.58 Å. In (TBA<sup>+</sup>)(C<sub>60</sub><sup>•–</sup>){(Cp*Ir<sup>III</sup>I<sub>2</sub>)Sn<sup>II</sup>Pc(2−)}·0.5C<sub>6</sub>H<sub>14</sub> (<b>2</b>), the {(Cp*Ir<sup>III</sup>I<sub>2</sub>)Sn<sup>II</sup>Pc(2−)} units cocrystallize with (TBA<sup>+</sup>)(C<sub>60</sub><sup>•–</sup>) to form double chains of C<sub>60</sub><sup>•–</sup> anions and closely packed chains of {(Cp*Ir<sup>III</sup>I<sub>2</sub>)Sn<sup>II</sup>Pc(2−)}. Interactions
between the fullerene and phthalocyanine subsystems are realized through
π–π stacking of the Cp* groups of {(Cp*Ir<sup>III</sup>I<sub>2</sub>)Sn<sup>II</sup>Pc(2−)} and the C<sub>60</sub><sup>•–</sup> pentagons. Furthermore, the spins of
the C<sub>60</sub><sup>•–</sup> are strongly antiferromagnetically
coupled in the chains with an exchange interaction <i>J</i>/<i>k</i><sub>B</sub> = −31 K. Anionic (TBA<sup>+</sup>){(Cp*Ir<sup>II</sup>Cl)(η<sup>2</sup>-C<sub>60</sub><sup>–</sup>)}·1.34C<sub>6</sub>H<sub>4</sub>Cl<sub>2</sub> (<b>3</b>) and (TBA<sup>+</sup>){(Cp*Ir<sup>II</sup>I)(η<sup>2</sup>-C<sub>60</sub><sup>–</sup>)}·1.3C<sub>6</sub>H<sub>4</sub>Cl<sub>2</sub>·0.2C<sub>6</sub>H<sub>14</sub> (<b>4</b>) are the first transition metal complexes containing η<sup>2</sup>-bonded C<sub>60</sub><sup>–</sup> anions, with the
Cp*Ir<sup>II</sup>Cl and Cp*Ir<sup>II</sup>I units η<sup>2</sup>-coordinated to the 6–6 bonds of C<sub>60</sub><sup>–</sup>. Magnetic measurements indicate diamagnetism of the {(Cp*Ir<sup>II</sup>Cl)(η<sup>2</sup>-C<sub>60</sub><sup>–</sup>)} and {(Cp*Ir<sup>II</sup>I)(η<sup>2</sup>-C<sub>60</sub><sup>–</sup>)} anions due to the formation of a coordination bond
between two initially paramagnetic Cp*Ir<sup>II</sup>Cl or Cp*Ir<sup>II</sup>I groups and C<sub>60</sub><sup>•–</sup> units.
DFT calculations support a diamagnetic singlet ground state of <b>4</b>, in which the singlet–triplet energy gap is greater
than 0.8 eV. DFT calculations also indicate that the C<sub>60</sub> molecules are negatively charged