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 [CuI(L)2]+ are considered as potent substitutes for [RuII(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 CuI ion. Using oxidative Hay acetylene homocoupling conditions, several CuI 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.
Highlights
Increasing energy demand leads to the development of new strategies to convert solar energy into electricity
We present a new concept to stabilize copper bis(phenanthroline) complexes by macrocyclization of the ligands which are preorganized around the
Both ligands 6 and 7 expose a trimethylsilyl (TMS)-protected acetylene at their periphery with the intention sketched in Figure 1, namely, to enable macrocyclization of the deprotected acetylenes by oxidative acetylene coupling upon preorganization in a CuI complex
Summary
Increasing energy demand leads to the development of new strategies to convert solar energy into electricity. The loss of one electron results in an uneven number of electrons in the d orbitals leading to a flattening distortion of the ligands due to pseudo-Jahn–Teller effects.[14,15,16] This flattening facilitates the exciplex formation with Lewis bases (e.g. solvent molecules and/or counterions) favoring non-radiative relaxation processes Another drawback of complexes with CuI as a first row d10 transition metal is their limited structural integrity due to ligand loss by substitution.[17,18] not all interesting RuII complexes can be mimicked by CuI analogues. In the case of 3 the strain was further released by subsequent hydrogenation of the diacetylene bridge resulting in the buta-1,4-diyl interlinked bis phenanthroline CuI complex 1 (Scheme 1)
Sign-in/Register to view highlights & summary Sign-in/Register to access full text options 
Talk to us
Join us for a 30 min session where you can share your feedback and ask us any queries you have
Schedule a callDisclaimer: All third-party content on this website/platform is and will remain the property of their respective owners and is provided on "as is" basis without any warranties, express or implied. Use of third-party content does not indicate any affiliation, sponsorship with or endorsement by them. Any references to third-party content is to identify the corresponding services and shall be considered fair use under The CopyrightLaw.
