Tunable Self-Referenced Molecular Thermometers via Manipulation of Dual Emission in Platinum(II) Pyridinedipyrrolide...

Optical temperature sensors based on self-referenced readout schemes such as the emission ratio and the decay time are crucial for a wide range of applications, with the former often preferred due to simplicity of instrumentation. This work describes a new group of dually emitting dyes, platinum(II) pincer complexes, that can be used directly for ratiometric temperature sensing without an additional reference material. They consist of Pt(II) metal center surrounded by a pyridinedipyrrolide ligand (PDP) and a terminal ligand (benzonitrile, pyridine, 1-butylimidazol or carbon monoxide). Upon excitation with blue light, these complexes exhibit green to orange emission, with quantum yields in anoxic toluene at 25 °C ranging from 13% to 86% and decay times spanning from 8.5 to 97 micros. The emission is attributed to simultaneous thermally activated delayed fluorescence (TADF) and phosphorescence processes on the basis of photophysical investigations and DFT calculations. Rather uniquely, simple manipulations in substituents of the PDP ligand and alteration of the terminal ligand allow fine-tuning of the ratio between TADF and phosphorescence from almost 100% TADF emission (Pt(^MesPDP^C6F5(BN)) to over 80% of phosphorescence (Pt(^PhPDP^Ph(BuIm)). Apart from ratiometric capabilities, the complexes also are useful as decay time-based temperature indicators with temperature coefficients exceeding 1.5% K^-1 in most cases. Immobilization of the dyes into oxygen-impermeable polyacrylonitrile produces temperature sensing materials that can be read out with an ordinary RGB camera or a smartphone. In addition, Pt(^PhPDP^Ph)Py can be incorporated into biocompatible RL100 nanoparticles suitable for cellular nanothermometry, as we demonstrate with temperature measurements in multicellular colon cancer spheroids.