Matrix Effects on Photoluminescence and Oxygen Sensitivity of a Molecular Ruby

Abstract

Abstract The molecular ruby analogue [Cr(ddpd) 2 ] 3+ (ddpd= N , N’ ‐dimethyl‐ N , N ’‐dipyridine‐2‐ylpyridine‐2,6‐diamine) exhibits near infrared (NIR) emission with a high photoluminescence (PL) quantum yield Φ PL of 11 % and a lifetime of 898 μs in deaerated water at room temperature. While ligand‐based control of the photophysical properties has received much attention, influences of the counter anions and microenvironment are still underexplored. In this study, the luminescence properties of the molecular ruby were systematically examined for the counter anions Cl − , Br − , [BF 4 ] − , [PF 6 ] − , [BPh 4 ] − , and [BArF 24 ] − in acetonitrile (MeCN) solution, in crystals, and embedded into polystyrene nanoparticles (PSNP). Stern‐Volmer analyses of the oxygen quenching studies in the intensity and lifetime domain showed the highest oxygen sensitivity of the complexes with the counter anions of [BF 4 ] − and [BArF 24 ] − , which also revealed the longest luminescence lifetimes. Embedding [Cr(ddpd) 2 ][PF 6 ] 3 in PSNPs and shielding with poly(vinyl alcohol) yields a strongly NIR‐emissive oxygen‐insensitive material with a record Φ PL of 15.2 % under ambient conditions.