Improved Photostability of a CuI Complex by Macrocyclization of the Phenanthroline Ligands. Issue 14 (18th February 2020)

• Record Type: Journal Article
• Authors: Brandl, Thomas; Kerzig, Christoph; Le Pleux, Loïc; Prescimone, Alessandro; Wenger, Oliver S.; Mayor, Marcel
• Is Part Of: Chemistry. Volume 26:Issue 14(2020)
• Page Start: 3119
• Page End: 3128
• Publication Date: 2020-02-18
• Subjects: copper complexes -- ligand design -- macrocycles -- photochemistry -- photostability; Chemistry -- Periodicals; 540
• DOI: 10.1002/chem.201904754
• Languages: English
• ISSNs: 0947-6539

Abstract

Abstract: The development of molecular materials for conversion of solar energy into electricity and fuels is one of the most active research areas, in which the light absorber plays a key role. While copper(I)‐bis(diimine) complexes [Cu I (L)2 ] + are considered as potent substitutes for [Ru II (bpy)3 ] 2+, they exhibit limited structural integrity as ligand loss by substitution can occur. In this article, we present a new concept to stabilize copper bis(phenanthroline) complexes by macrocyclization of the ligands which are preorganized around the Cu I ion. Using oxidative Hay acetylene homocoupling conditions, several Cu I complexes with varying bridge length were prepared and analyzed. Absorption and emission properties are assessed; rewardingly, the envisioned approach was successful since the flexible 1, 4‐butadiyl‐bridged complex does show enhanced MLCT absorption and emission, as well as improved photostability upon irradiation with a blue LED compared to a reference complex. Abstract : Rescue Cu I phenanthroline complexes : Like a safety buoy the macrocyclized bisphenanthroline ligand surrounds the Cu I ion and improves the complex's photostability, visible‐light absorptivity, and emission compared to an open analogue (see graphic).