# Solvent-Responsive Luminescence of an 8-Hydroxyquinoline-Modified 1H-Imidazo[4,5-f][1,10]phenanthroline Ligand and Its Cu(I) Complexes: Excited-State Mechanisms and Structural Effects

## TL;DR

This paper explores how different solvents affect the light emission of copper complexes, revealing how their structures influence luminescence behavior for sensor applications.

## Contribution

The study reveals solvent-dependent excited-state mechanisms in Cu(I) complexes modified with an 8-hydroxyquinoline ligand.

## Key findings

- Free ipqH2 shows dual emission via ESPT and tautomerization in alcohol/DMSO mixtures.
- Cu(I) complexes exhibit red-shifted emission in water-rich DMSO due to (IL + ML)CT states.
- Flexible diphosphine ligands enhance DMF sensitivity, while rigid ligands show weaker solvent responses.

## Abstract

Understanding how solvents influence the luminescence behavior of Cu(I) complexes is crucial for designing advanced optical sensors. This study reports the synthesis, structures and photophysical investigation of an 8-hydroxyquinoline-functionalized 1H-imidazo[4,5-f][1,10]phenanthroline ligand, ipqH2, and its four Cu(I) complexes with diphosphine co-ligands. Photoluminescence studies demonstrated distinct solvent-dependent excited-state mechanisms. In DMSO/alcohol mixtures, free ipqH2 exhibited excited-state proton transfer (ESPT) and enol-keto tautomerization, producing dual emission at about 447 and 560 nm, while the complexes resisted ESPT due to hydrogen bond blocking by PF6− anions and Cu(I) coordination. In DMSO/H2O, aggregation-caused quenching (ACQ) and high-energy O–H vibrational quenching dominated, but complexes 1 and 2 showed a significant red-shifted emission (569–574 nm) with high water content due to solvent-stabilized intra-ligand charge transfer and metal-to-ligand charge transfer ((IL+ML)CT) states. In DMSO/DMF, hydrogen bond competition and solvation-shell reorganization led to distinct responses: complexes 1 and 3, with flexible bis[(2-diphenylphosphino)phenyl]ether (POP) ligands, displayed peak splitting and (IL + ML)CT redshift emission (501 ⟶ 530 nm), whereas complexes 2 and 4, with rigid 9,9-dimethyl-4,5-bis(diphenylphosphino)-9H-xanthene (xantphos), showed weaker responses. The flexibility of the diphosphine ligand dictated DMF sensitivity, while the coordination, the hydrogen bonds between PF6− anions and ipqH2, and water solubility governed the alcohol/water responses. This work elucidates the multifaceted solvent-responsive mechanisms in Cu(I) complexes, facilitating the design of solvent-discriminative luminescent sensors.