The dyes (5-(4-carboxylphenyl)-10,15,20-tritolylporphyrinato)zinc(II) (MCP) and (5,15-bis(4-carboxylphenyl)-15,20-ditolylporphyrinato)zinc(II) (DCP), as their sodium salts, were used to form assemblies with the unsaturated cluster Pd3(dppm)3(CO)(2+) ([Pd3(2+)], dppm = (Ph2P)2CH2) via ionic CO2(-)···Pd3(2+) interactions. The photophysical properties in their triplet states were studied. The position of the T1 state of [Pd3(2+)] (∼8190 cm(-1)) has been proposed using DFT computations and was corroborated by the presence of a Tn → S0 delayed emission at 680-700 nm arising from a T1-T1 annihilation process at 77 K. The static quenching of the near-IR phosphorescence of the dyes at 785 nm (T1 → S0) was observed. Thermodynamically poor reductive and oxidative driving forces render the photoinduced electron transfer quenching process either inoperative or very slow in the T1 states. Instead, slow to medium T1-T1 energy transfer ((3)dye*···[Pd3(2+)] → dye···(3)[Pd3(2+)]*) operates through a Förster mechanism exclusively with kET values of ∼1 × 10(5) s(-1) on the basis of transient absorption measurements at 298 K.
This research output has an Altmetric Attention Score of 2. This is our high-level measure of the quality and quantity of online attention that it has received. This Attention Score, as well as the ranking and number of research outputs shown below, was calculated when the research output was last mentioned on 08 April 2016.
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