Pure and Applied Chemistry

Abstract: A class of molecular electron transfer cascades—those based on Pt^II complexes of 2-(1-pyrazole)-pyridine (pzpy) ligands—are reported. The synthesis of a new electron-acceptor imide-modified pzpy ligands is reported, and their application to transition-metal chemistry demonstrated by the synthesis of the Pt^II chloride and acetylide complexes. These donor–acceptor assemblies are promising models for investigation of photoinduced charge separation. Accordingly, picosecond time-resolved infrared (TRIR) and femtosecond transient absorption (TA) studies have been undertaken to elucidate the nature and dynamics of the lowest excited states in Pt(NAP-pyr-pyrazole)(–CC–Ph–C₇H₁₅)₂. It has been established that the initial population of an MLL'CT excited state in the chromophoric [Pt(pyridine-pyrazole)(acetylide)] core is followed by an electron transfer to the naphthalimide (NAP) acceptor, forming a charge-separated state. This state is characterized by a large shift in ν(CO) vibrations of the NAP acceptor, as well as by a very intense and broad [×10 times in comparison to ν(CO)] asymmetric acetylide stretch which incorporates –CC–Pt–CC– framework and occurs at approximately 300 cm^–1 lower in energy than its ground-state counterpart. In CH₂Cl₂ at room temperature, the charge-separated state with the lifetime of 150 ps collapses into an almost isoenergetic NAP-localized triplet state; the rate of this transformation changes upon decreasing the temperature to 263 K. This final excited state, ³NAP-(pyr-pyrazole)Pt(–CC–Ph–C₇H₁₅)₂, has an unusually long, for Pt^II complexes, excited-state lifetime of tens of microseconds. The work demonstrates the possibility of tuning excited-state properties in this new class of Pt^II chromophores designed for electron-transfer cascades.