Supramolekulare Aggregate heterogener Multiporphyrinanordnungen – die Strukturen von [{ZnII(tpp)}2(tpyp)] und dem Koordinationspolymer [{[MnIII(tpp)]2(tpyp)(ClO4)2}∞]

Abstract

46% des Kristallvolumens machen Kanäle aus: Aus [MnIII(tpp)]⋅ClO4 und tpyp bildet sich ein zweidimensionales Koordinationspolymer von außergewöhnlicher Regelmäßigkeit (siehe schematische Darstellung; tpp=Tetraphenylporphyrin, tpyp=Tetrapyridylporphyrin). Durch die Kristallpackung dieser Polymere entsteht eine offene Endlosstruktur mit Netzen rechtwinkliger Kanäle, die mit Nitrobenzol als Solvens gefüllt sind. Bei der Reaktion von [ZnII(tpp)] mit tpyp entstehen hingegen nur oligomere Strukturen.

Open Network Architectures from the Self‐Assembly of AgNO3 and 5,10,15,20‐Tetra(4‐pyridyl)porphyrin (H2tpyp) Building Blocks: The Exceptional Self‐Penetrating Topology of the 3D Network of [Ag8(ZnIItpyp)7(H2O)2](NO3)8

“…The pioneering work of Robson and co‐workers in this area has, indeed, shown that metalloporphyrins can give coordination networks with the CdSO 4 5a or the PtS topology5b by using Cd II centers (acting as linear spacers) or tetrahedral Cu I centers, respectively. Most of the reported frameworks contain external divalent metal ions, while species with trivalent6e, 8 or monovalent6a–d metal ions are more rare.…”

Crystal engineering of porphyrin framework solids

“…6). The binding energy of coordination bonds is typically within 120-250 kJ mol 21 , making them most effective in the synthesis of stable network arrays. Moreover, the carboxylic groups can be readily deprotonated in neutral and basic environments to yield anionic porphyrin units, and balance the charge introduced by the cationic metal bridges.…”

“…8a). 21 Its major significance lies in the fact that further metallation of the free-base porphyrins can result in continuous multiporphyrin patterns with different metal ions and oxidation states, which in turn can be useful in chargetransfer processes. Yet, such systems could not be crystallized as yet.…”

“…Fig.8Motifs of (a) mixed porphyrin networks of TPyP and MnTPP building blocks sustained by two-dimensional coordination,21 and (b) networks of alkylated monopyridyl-tris(hydroxyphenyl)porphyrin tessellated by chloride anions (green sheres) that hydrogen bond to OH-functions (red spheres) of three neighboring species 23. Hydrogen atoms are omitted for clarity.…”

Open Network Architectures from the Self‐Assembly of AgNO3 and 5,10,15,20‐Tetra(4‐pyridyl)porphyrin (H2tpyp) Building Blocks: The Exceptional Self‐Penetrating Topology of the 3D Network of [Ag8(ZnIItpyp)7(H2O)2](NO3)8

“…The pioneering work of Robson and co‐workers in this area has, indeed, shown that metalloporphyrins can give coordination networks with the CdSO 4 5a or the PtS topology5b by using Cd II centers (acting as linear spacers) or tetrahedral Cu I centers, respectively. Most of the reported frameworks contain external divalent metal ions, while species with trivalent6e, 8 or monovalent6a–d metal ions are more rare.…”