High-Yielding Syntheses of Multifunctionalized Ru^II Polypyridyl-Type Sensitizer: Experimental and Computational...

Ru^II complexes based on functionalized 2,6-di(quinolin-8-yl)pyridine (dqp) ligands feature excellent photophysical and geometrical properties, thus suggesting dqp ligands as ideal surrogates for 2,2'-bipyridine (bpy) or 2,2':6',2″-terpyridine (tpy). However, the synthesis of multifunctionalized [Ru(dqp)₂]²⁺-based complexes is often low-yielding, which has hampered their practical value to date. In this study, a universal high-yielding route was explored and corroborated by a mechanistic investigation based on ¹H NMR, MS, and density functional theory. With application of high-boiling but less-coordinating solvents (i.e., DMF) during the coordination of dqp by the precursor [Ru(dqp)(MeCN)₃]²⁺, the required reaction temperature is lowered considerably (by 30 °C). In comparison to tpy, the reaction rate for dqp is further reduced which is assigned to the higher steric demand upon the coordination process. Namely, the onset of coordination of a tpy derivative at 60 °C and of dqp at 90 °C is significantly milder than in previous protocols. The versatility of the procedure is demonstrated by the high-yielding syntheses of multifunctionalized Ru^II complexes reaching up to 90%, whereby the presence of hydroxyl groups and losses during purification may lower the isolated yields substantially. In addition, the same strategy of high-boiling but less-coordinating solvents enabled a milder one-pot protocol to prepare [Ru(dqp)₂]²⁺ from a [Ru(MeCN)₆]²⁺ source, i.e., without the need for in situ reduction or halide abstraction as typical for Ru^IIICl₃ hydrate. Hence, the developed protocol benefits from an improved thermal tolerance of sensitive functional groups, which may be applicable also to related polypyridyl-type ligands.