Photocatalytic processes under visible light have constantly been finding more and more applications in organic synthesis as they allow a wide range of transformations to proceed under mild conditions. The combination of photoredox catalysis with metal complex catalysis gives an opportunity to employ the advantages of these two methodologies. Covalent bonding of photocatalyst and metal complex catalyst using bridging ligands increases the efficiency of the electron and energy transfer between these two parts of the catalyst, leading to more efficient and selective catalytic systems. Up to now, after numerous investigations of the photocatalytic reduction of CO₂ and hydrogen generation, such a strategy was firmly established to substantially increase the catalyst’s activity. This review is aimed at the achievements and perspectives in the field of design and application of heterobinuclear metal complexes as photocatalysts in organic synthesis.

Dinuclear complexes [(bpy)₂Ru(Phen-NPy₂)PdCl₂]²⁺ were used as photoactivated precatalysts in a Cu-free Sonogashira reaction. They provide three times faster product formation than the mixed catalytic system [Ru(bpy)₃]²⁺/(RNPy₂)Cl₂.

We report a one-step synthesis of trifluoromethyl-substituted di(pyridin-2-yl)amine-based ligands. N-(hetero)aryl-substituted bis(5-(trifluoromethyl)pyridin-2-yl)amines were obtained from 2-bromo-5-(trifluoromethyl)pyridine and corresponding aromatic amines via Pd-catalyzed amination reaction in the presence of a Pd(dba)₂/BINAP catalytic system. Four new ligands were prepared in good to high yields and characterized by NMR, IR spectroscopies and mass spectrometry. The structure of one of the products was additionally supported by X-ray analysis.