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Mutual stabilisation between MII4L6 tetrahedra and MIIX42- metallate guests.

ABSTRACT: A complex host-guest equilibrium employing metal ions incorporated into both the host and guest is discussed. MIIX42- metallate guests are shown to provide a good size and shape match for encapsulation within the M4L6 tetrahedral capsules, facilitating the generation of previously unreported Zn4L6 complexes. Displacement of the initial, primary template anion (ZnBr42-) by a secondary template anion (ClO4-) is shown to result in the formation of a pentagonal-prismatic Zn10L15 structure that incorporates both Br- and ClO4-. Furthermore, the formation of heterometallic complexes provides direct evidence for metal exchange between the guest and host complex.

SUBMITTER: Riddell IA

PROVIDER: S-EPMC5492872 | biostudies-literature | 2015 Jun

REPOSITORIES: biostudies-literature

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Mutual stabilisation between MII4L6 tetrahedra and MIIX42- metallate guests.

Riddell Imogen A IA Ronson Tanya K TK Nitschke Jonathan R JR

Chemical science 20150414 6

A complex host-guest equilibrium employing metal ions incorporated into both the host and guest is discussed. MIIX42- metallate guests are shown to provide a good size and shape match for encapsulation within the M4L6 tetrahedral capsules, facilitating the generation of previously unreported Zn4L6 complexes. Displacement of the initial, primary template anion (ZnBr42-) by a secondary template anion ...[more]

PMID: 28706711

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Project description:Neutral {CpFeII(CO)2[SnII(Pc•3-)]} {Cp is cyclopentadienyl (1, 2) or Cp* is pentamethylcyclopentadienyl (3); Pc: phthalocyanine}, {Cp*FeII(CO)2[SnII(Nc•3-)]} (4, Nc: naphthalocyanine), and {CpFeII(CO)2[SnII(TPP•3-)]} (5, TPP: tetraphenylporphyrin) complexes in which CpFeII(CO)2 fragments (Cp: Cp or Cp*) are coordinated to SnII(macrocycle•3-) have been obtained. The product complexes were obtained at the reaction of charge transfer from CpFeI(CO)2 (Cp: Cp or Cp*) to [SnII(macrocycle2-)] to form the diamagnetic FeII and paramagnetic radical trianionic macrocycles. As a result, these formally neutral complexes contain S = 1/2 spins delocalized over the macrocycles. This provides alternation of the C-Nimine or C-Cmeso bonds in the macrocycles, the appearance of new bands in the near-infrared spectra of the complexes, and blue shift of both Soret and Q-bands. The {CpFeII(CO)2SnII(macrocycle•3-)} units (Cp: Cp or Cp*, macrocycle: Pc or Nc) form closely packed π-stacking dimers in 1 and 3 or one-dimensional chains in 2 and 4 with effective π-π interaction between the macrocycles. Such packing allows strong antiferromagnetic coupling between S = 1/2 spins. Magnetic interaction can be described well by the Heisenberg model for the isolated dimers in 1 and 3 with exchange interaction J/k B = -78 and -85 K, respectively. Magnetic behavior of 2 and 4 is described well by the model that includes contributions from an antiferromagnetically coupled S = 1/2 dimer (J intra) and a Heisenberg S = 1/2 chain with alternating antiferromagnetic spin exchange between the neighbors (J inter). Compound 2 demonstrates large intradimer interaction of J intra/k B = -54 K and essentially weaker interdimer exchange interactions of J inter/k B = -6 K, whereas compound 4 shows strong magnetic coupling of spins within the dimers (J intra/k B = -170 K) as well as between the dimers (J inter/k B = -40 K). Compound {CpFeII(CO)2[SnII(TPP•3-)]} (5) shows no π-π interactions between the porphyrin macrocycles, and magnetic coupling is weak in this case (Weiss temperature is -5 K). Preparation of a similar complex with indium(III) chloride phthalocyanine yields {CpFe(CO)2[In(Pc2-)]} (6). In this complex, indium(III) atoms are reduced instead of the phthalocyanine macrocycles that explains electron paramagnetic resonance silence of 6 in the 4-295 K range.

Dataset Information

Mutual stabilisation between MII4L6 tetrahedra and MIIX42- metallate guests.

Publications

Mutual stabilisation between M<sup>II</sup><sub>4</sub>L<sub>6</sub> tetrahedra and M<sup>II</sup>X<sub>4</sub><sup>2-</sup> metallate guests.

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