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.

The three‐component reaction of the tetrahedral diphosphorus complex [Cp2Mo2(CO)4(η2‐P2)] (1), with Ag[BF4] (2) in the presence of 2,2′‐bipyrimidine (3) leads to the formation of the two novel two‐dimensional networks 4 and 5. Compound 4 is a new two‐dimensional organometallic‐organic hybrid polymer, while derivative 5 represents a unique two‐dimensional organometallic‐inorganic‐organic hybrid polymer. These results show the possibility of synthesizing a new class of coordination polymers, which could not be obtained from two‐component reactions with organic molecules in addition of metal ions.

An AgI dimer capped with labile organometallic diphosphorus ligands [Cp2Mo2(CO)4(η2‐P2)] (Cp=C5H5) acts as a highly pre‐organized molecular precursor to direct the construction of 1D or 2D, and 3D organometallic–organic hybrid coordination polymers upon reaction with ditopic pyridine‐based linkers. The formation of the supramolecular aggregates can be controlled by the stoichiometry of the organic molecules, and the mechanism is supported by DFT calculations.

A generally applicable method for the direct 3-N-arylation of flavins using arylboronic acids and copper acetate was developed. The reaction conditions were optimized considering the lability of flavins in basic conditions and thermal heating. Donorand acceptor-substituted arylboronic acids were used yielding 3-Narylflavins in moderate to good yields by C(aryl)-N(imide) bond formation. UV and fluorescence measurements indicate an orthogonal orientation of the additional aromatic substituent to the flavin ring system. The arene substituent is not electronically coupled to the flavin p-system in the ground state, but electron-rich arene substituents in 3-N position significantly reduce the flavin emission intensity.