Da-Qian Feng, Xiao-Ping Zhou, Ji Zheng, Guang-hui Chen, Xiao-Chun Huang and Dan Li*

Abstract: The reactions of CuBr2 with pyridyl 2,2′:6′,2′′-terpyridine ligands in methanol yielded four copper complexes under solvothermal conditions. The self-assembly processes were accompanied by designing bitopic precursor ligands and increasing the stoichiometric metal–ligand ratio. In the four resulting complexes, the pendant pyridyl groups of pyridylterpyridine were selectively in situ N-methylated and yielded the 4′-(N-methylpyridinium)-2,2′:6′,2′′-terpyridine cations, including the 2-position pyridyl group which is difficult to be N-alkylated due to the steric problem. Partial divalent copper atoms were reduced to cuprous ones in the solvothermal reactions, which made the mixed-valence copper atoms coexist in each compound. The mixed-valence complexes have a varied dimensionality (from 2D to 0D) and the CuIBr cluster, which can be controlled by changing the metal–ligand ratio. Theoretical studies show that the nucleophilic attack of the nitrogen atom in the pendant pyridyl is more facile than others of terpyridine. A possible mechanism was also proposed.

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