The flexible coordination behavior of Pn ligand complexes in solution is utilized to create unprecedented coordination networks. In combination with ditopic organic linker units, organometallic–organic hybrid compounds are accessible. Depending on the nature of the metal center, metallaparacyclophane‐like structures as well as 1D and 2D polymeric arrangements can be achieved.
A simple and straightforward approach to new polymetallic AgI and CuI supramolecules is presented. The reaction of N,P,N,P,N ligand 2 with AgI ions affords a trimetallic complex bearing a triangular Ag3 core; metallophilic interactions are stabilized by ligands that display a multiple bridging coordination mode as 10‐electron donors. Heteroleptic polymetallic AgI and CuI complexes based on ligand 2 and the 1,12‐diazaperylene (dape) ligand are obtained by an alternative molecular organization of the polymetallic arrays compared to that in homoleptic complexes of ligand 2.
The selective synthesis of a series of new "ladderlike" one-dimensional organometallic-organic hybrid polymers is shown. The polymers are obtained from the reaction of the diphosphorus ligand complex [Cp2Mo2(CO)4(η(2)-P2)] with the copper salt [Cu(CH3CN)4]BF4 in the presence of flexible organic bipyridyl linkers in high selectivity. This unique behaviour is supported by DFT calculations.
The reaction of the P ligand complex [Cp*Fe(η-P)] (1: Cp* = η-CMe) with CuCl in the presence of 4,4'-bipyridine or 1,2-di(4-pyridyl)ethylene leads to the formation of three unprecedented neutral 2D organometallic-organic hybrid networks, the constitutional isomers [CuCl{Cp*Fe(μ,η-P)}(μ,η-CHN)] (2 and 3) and the coordination polymer [(CuCl){Cp*Fe(μ,η-P)}(μ,η-CHN)] (4) with isomeric square (2 and 3) and honeycomb (4) layer topologies.
The
reaction of the silver salt Ag[Al{OC(CF3)3}4] (1) with the P2 ligand complex [Cp2Mo2(CO)4(η2-P2)] (2) and the organic ditopic linker trans-1,2-di(pyridine-4-yl)ethene (dpe) results in the
formation of four novel organometallic–organic hybrid compounds.
Depending on the reaction conditions, the two-dimensional networks
[{Cp2Mo2(CO)4(μ4,η1:1:2:2-P2)}(μ,η1:1-C12H10N2)Ag]n[Al{OC(CF3)3}4]n·0.075nCH2Cl2·1.425nC6H6 (3) and [{Cp2Mo2(CO)4(μ3,η2:2:2-P2)}2(μ,η1:1-C12H10N2)3Ag2]n[Al{OC(CF3)3}4]2n·2nC7H8 (4) are accessible. The latter
shows a two-dimensional (2D) → 2D interpenetration structure.
Furthermore, the formation of a unique three-dimensional polymer [{Cp2Mo2(CO)4(μ4,η1:1:2:2-P2)}(μ,η1:1-C12H10N2)Ag]n[Al{OC(CF3)3}4]n·0.3nCH2Cl2 (5b) together with another 2D polymer [{Cp2Mo2(CO)4(μ4,η1:1:2:2-P2)}(μ,η1:1-C12H10N2)3Ag2]n[Al{OC(CF3)3}4]2n·0.75CH2Cl2·0.5C7H8 (5a) was observed. In three of
these polymers, unprecedented organometallic nodes were realized including
one, two, or even four silver cations. All products were characterized
by X-ray structural analysis and classified by the structural characteristics
in three different network topologies.
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