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1,2,4-Triphospholyl anions - versatile building blocks for the formation of 1D, 2D and 3D assemblies.

Heindl C, Peresypkina EV, Virovets AV, Komarov VY, Scheer M - Dalton Trans (2015)

Bottom Line: The potential of K[P3C2R2] (R = (t)Bu, Mes) as building blocks in metallo-supramolecular chemistry was investigated and self-assembly processes with Cu(i) halides resulted in the formation of a large variety of unprecedented one-, two- and even three-dimensional aggregates.Furthermore, the negative charge of the phospholyl ligand favoured the generation of cationic CuaXb (a > b, X = Cl, Br, I) assemblies, a challenging area within the well-studied coordination chemistry of CuX units.In addition, the 1D strands were also characterized in solution, revealing the presence of oligomeric units.

View Article: PubMed Central - PubMed

Affiliation: Institut für Anorganische Chemie, Universität Regensburg, Universitätsstr. 31, 93053 Regensburg, Germany. Manfred.Scheer@ur.de.

ABSTRACT
The potential of K[P3C2R2] (R = (t)Bu, Mes) as building blocks in metallo-supramolecular chemistry was investigated and self-assembly processes with Cu(i) halides resulted in the formation of a large variety of unprecedented one-, two- and even three-dimensional aggregates. The 3D networks showed an interesting topological similarity to allotropes of carbon: diamond and the theoretically proposed polybenzene. Furthermore, the negative charge of the phospholyl ligand favoured the generation of cationic CuaXb (a > b, X = Cl, Br, I) assemblies, a challenging area within the well-studied coordination chemistry of CuX units. In addition, the 1D strands were also characterized in solution, revealing the presence of oligomeric units.

No MeSH data available.


Related in: MedlinePlus

(a) Schematic representation of the structure of 7. (b) Section of the polymeric structure of 7. tBu ligands, H atoms, solvents and minor positions of disordered CH3CN are omitted for clarity.
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fig4: (a) Schematic representation of the structure of 7. (b) Section of the polymeric structure of 7. tBu ligands, H atoms, solvents and minor positions of disordered CH3CN are omitted for clarity.

Mentions: The 1D polymer 7 crystallizes as orange plates in the monoclinic space group P21/m and reveals a structural motif different from the other 1D polymers, since it contains 1b as a building block and it also differs from the general structural motif (Fig. 4). Due to the lower steric demand of the tBu group, the arrangement of three phospholyl rings close to each other is possible. They are connected by three Cu2-dimers (Cu···Cu 2.482(1)–2.496(1) Å), which form a triangular prism (P–Cu 2.325(1)–2.361(1) Å). The prism is capped by two μ3-Cl with μ3-Cl–Cu 2.390(1)–2.441(1) Å bond lengths. Each Cu atom additionally coordinates either Cl– or CH3CN moieties to reach a tetrahedral environment. Two of these three halides are terminals (η1-Cl–Cu 2.231(1) Å), while the third coordinates another copper atom (μ2-Cl–Cu 2.279(2)–2.300(2) Å), which is in turn bound to an isolated P atom of 1b. The remaining P atoms of the other two ligands prevent polymerization in other directions by coordination of terminal Cu(CH3CN)3 units (Cu–P 2.191(2) Å). Therefore, compound 7 displays a 1D polymer. The central assembly with 7 Cu+ and 6 Cl– can be regarded as an isomeric unit to the assembly in 6 and is another unprecedented example of a cationic CuaXb unit.


1,2,4-Triphospholyl anions - versatile building blocks for the formation of 1D, 2D and 3D assemblies.

Heindl C, Peresypkina EV, Virovets AV, Komarov VY, Scheer M - Dalton Trans (2015)

(a) Schematic representation of the structure of 7. (b) Section of the polymeric structure of 7. tBu ligands, H atoms, solvents and minor positions of disordered CH3CN are omitted for clarity.
© Copyright Policy - open-access
Related In: Results  -  Collection

License
Show All Figures
getmorefigures.php?uid=PMC4447064&req=5

fig4: (a) Schematic representation of the structure of 7. (b) Section of the polymeric structure of 7. tBu ligands, H atoms, solvents and minor positions of disordered CH3CN are omitted for clarity.
Mentions: The 1D polymer 7 crystallizes as orange plates in the monoclinic space group P21/m and reveals a structural motif different from the other 1D polymers, since it contains 1b as a building block and it also differs from the general structural motif (Fig. 4). Due to the lower steric demand of the tBu group, the arrangement of three phospholyl rings close to each other is possible. They are connected by three Cu2-dimers (Cu···Cu 2.482(1)–2.496(1) Å), which form a triangular prism (P–Cu 2.325(1)–2.361(1) Å). The prism is capped by two μ3-Cl with μ3-Cl–Cu 2.390(1)–2.441(1) Å bond lengths. Each Cu atom additionally coordinates either Cl– or CH3CN moieties to reach a tetrahedral environment. Two of these three halides are terminals (η1-Cl–Cu 2.231(1) Å), while the third coordinates another copper atom (μ2-Cl–Cu 2.279(2)–2.300(2) Å), which is in turn bound to an isolated P atom of 1b. The remaining P atoms of the other two ligands prevent polymerization in other directions by coordination of terminal Cu(CH3CN)3 units (Cu–P 2.191(2) Å). Therefore, compound 7 displays a 1D polymer. The central assembly with 7 Cu+ and 6 Cl– can be regarded as an isomeric unit to the assembly in 6 and is another unprecedented example of a cationic CuaXb unit.

Bottom Line: The potential of K[P3C2R2] (R = (t)Bu, Mes) as building blocks in metallo-supramolecular chemistry was investigated and self-assembly processes with Cu(i) halides resulted in the formation of a large variety of unprecedented one-, two- and even three-dimensional aggregates.Furthermore, the negative charge of the phospholyl ligand favoured the generation of cationic CuaXb (a > b, X = Cl, Br, I) assemblies, a challenging area within the well-studied coordination chemistry of CuX units.In addition, the 1D strands were also characterized in solution, revealing the presence of oligomeric units.

View Article: PubMed Central - PubMed

Affiliation: Institut für Anorganische Chemie, Universität Regensburg, Universitätsstr. 31, 93053 Regensburg, Germany. Manfred.Scheer@ur.de.

ABSTRACT
The potential of K[P3C2R2] (R = (t)Bu, Mes) as building blocks in metallo-supramolecular chemistry was investigated and self-assembly processes with Cu(i) halides resulted in the formation of a large variety of unprecedented one-, two- and even three-dimensional aggregates. The 3D networks showed an interesting topological similarity to allotropes of carbon: diamond and the theoretically proposed polybenzene. Furthermore, the negative charge of the phospholyl ligand favoured the generation of cationic CuaXb (a > b, X = Cl, Br, I) assemblies, a challenging area within the well-studied coordination chemistry of CuX units. In addition, the 1D strands were also characterized in solution, revealing the presence of oligomeric units.

No MeSH data available.


Related in: MedlinePlus