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. 2018 Feb 16;24(10):2503-2508.
doi: 10.1002/chem.201705883. Epub 2018 Jan 25.

Anionic Hosts for the Incorporation of Cationic Guests

Eugenia Peresypkina  1   2 , Claudia Heindl  1 , Alexander Virovets  1   2 , Helena Brake  1 , Eric Mädl  1 , Manfred Scheer  1
Affiliations

Anionic Hosts for the Incorporation of Cationic Guests

Eugenia Peresypkina et al. Chemistry. .

Abstract

Pentaphosphaferrocene [Cp*Fe(η5 -P5 )] (1 a) represents an excellent building block for the template-directed synthesis of spherical supramolecules. Here, the self-assembly of 1 a with CuI and CuII halides in the presence of the template complexes [FeCp2 ][PF6 ], [CoCp2 ][PF6 ] and [CoCp2 ] is reported, testifying to the redox behavior of the formed supramolecules. The oxidation or reduction capacity of these reactive complexes does not inhibit their template impact and, for the first time, the cationic metallocene [CoCp2 ]+ is enclosed in unprecedented anionic organometallic hosts. Furthermore, the large variety of structural motifs, as icosahedral, trigonal antiprismatic, cuboidal and tetragonal antiprismatic arrangements of 1 a units are realized in the supramolecules [FeCp2 ]@[{1 a}12 (CuBr)17.3 ] (3), [CoCp2 ]+3 {[CoCp2 ]+ @[{1 a}8 Cu24.25 Br28.25 (CH3 CN)6 ]4- } (4), {[Cp2 Co]+ @[{1 a}8 (CuI)28 (CH3 CN)9.8 ]}{[Cp2 Co]+ @[{1 a)}8 Cu24.4 I26.4 (CH3 CN)8 ]2- } (5), and [{1 a}3 {(1 a)2 NH}3 Cu16 I10 (CH3 CN)7 ] (6), respectively.

Keywords: copper; host-guest chemistry; metallocenes; phosphaferrocene; supramolecular chemistry.

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Figures

Figure 1
Figure 1
Selected scaffolds of spherical supramolecules composed by 1 a: a) 80‐vertex scaffold incorporating o‐carborane; b) 90‐vertex scaffold incorporating [(CpCr)2(μ,η5‐As5)]; c) 100‐vertex scaffold incorporating a P4 molecule (only one position of the disordered P4 molecule is shown).
Figure 2
Figure 2
Schematic view of scaffolds (left), scaffolds (middle) and molecular structures (right) of the obtained supramolecules 3–6 with [FeCp2]/[CoCp2]/[CoCp2][PF6] as template. Hydrogen atoms, minor parts of disorder and solvent molecules are omitted for clarity. Incorporated templates are displayed in a space‐filling model.
Figure 3
Figure 3
Typical fragments in CuX frameworks (X=Br, I): Bowl‐like fragments (a) {Cu4Br5}− in the scaffold of 4 and (b) {Cu4I5(CH3CN)} in 5 a; caps (c) {Cu3Br4}− in 4 and (d) {Cu3Br(CH3CN)3}2+ in 6; and {Cu4I4(CH3CN)2} and {Cu6I5(CH3CN)2}− fragments in 5 a and 5 b.
Figure 4
Figure 4
Envelope conformation of six cyclo‐P5 rings in 6.
See this image and copyright information in PMC

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