The heterobimetallic complexes [Cu(phen)(NC5H4HC=NC6H4C≡CC6H4C≡CRu(dppe)2Cl)]X (1 a‐4 a) and [Cu(bipy)(NC5H4H C=NC6H4C≡CC6H4C≡CRu(dppe)2Cl)]X (1 b‐4 b) (where X= I, ClO4, BF4, PF6; phen= 1, 10 phenanthroline, bipy= 2, 2′ bipyridine) have been prepared by the reaction of (NC5H4HC=NC6H4C≡CC6H4C≡CRu(dppe)2Cl) with copper salts in presence of phen or bipy as a coligand. Our synthetic attempts and successes are discussed in combination with spectroscopic and electronic characterization of the compounds. Comparison between phen and bipy complexes were studied by thermal and electrochemical analysis where, thermally robust complexes demonstrate quasireversible redox behaviour analogous to CuI/II/RuII/III couple. SEM of representative complexes 2 a and 2 b clarify the average size and morphology of the complexes. Room temperature luminescence influenced by varying coordinating ability of counter anions along with π‐acidic character in green‐yellow region was observed. Solvent dependant emission displays positive solvatochromism at ambient temperature. The second harmonic generation (SHG) efficiency of the complexes was measured by Kurtz‐powder technique indicating that all complexes display the second harmonic generation (SHG) property.
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