Visible light-harvesting trans bis(alkylphosphine) platinum(ii)-alkynyl complexes showing long-lived triplet excited states as triplet photosensitizers for triplet-triplet annihilation upconversion

摘要

Symmetric and asymmetric linear trans-bis(tributylphosphine) Pt(ii) bis(acetylide) complexes with functionalized aryl alkynyl ligands (coumarin, naphthalimide and phenyl acetylides) were prepared, which show enhanced absorption in the visible region (molar absorption coefficients up to 76,800 M~(-1) cm~(-1) at 459 nm) and long-lived triplet excited states (up to 139.9 μs). At room temperature, the naphthalimide acetylide-phenyl acetylide complex (Pt-4) shows dual emission (fluorescence-phosphorescence), whereas other complexes show only fluorescence emission. The triplet excited states of the complexes were studied with nanosecond time-resolved transient difference absorption spectroscopy and DFT calculations on the spin density surface. The complexes were used as triplet photosensitizers for ratiometric O_2 sensing, as well as triplet-triplet annihilation (TTA) upconversion (upconversion quantum yield up to 27.2%). The TTA upconversion of the complexes requires triplet acceptors with different T_1 state energy levels and was studied with nanosecond time-resolved emission spectroscopy. Our results are useful for designing new Pt(ii) complexes that show strong absorption of visible light and long-lived triplet excited states, as well as for the application of these complexes as triplet photosensitizers for O_2 sensing, photocatalysis and TTA upconversion. This journal is