Steric and Electronic Influence of Excited-State Decay in Cu(I) MLCT Chromophores

For the past 11 years, a dedicated effort in our research group focused on fundamentally advancing the photophysical properties of cuprous bis-phenanthroline-based metal-to-ligand charge transfer (MLCT) excited states. We rationalized that, by gaining control over the numerous factors limiting the more widespread use of CuI MLCT photosensitizers, they would be readily adopted in numerous light-activated applications given the earth-abundance of copper and the extensive library of 1,10-phenanthrolines developed over the last century. Significant progress has been achieved by recognizing valuable structure-property concepts developed by other researchers in tandem with detailed ultrafast and conventional time-scale investigations, in-silico-inspired molecular designs to predict spectroscopic properties, and applying novel synthetic methodologies. Ultimately, we achieved a plateau in exerting cooperative steric influence to control CuI MLCT excited state decay. This led to combining sterics with pi-conjugation and/or inductive electronic effects to further exert control over molecular photophysical properties. The lessons gleaned from our studies of homoleptic complexes were recently extended to heteroleptic bis(phenanthrolines) featuring enhanced visible light absorption properties and long-lived room-temperature photoluminescence. This Account navigates the reader through our intellectual journey of decision-making, molecular and experimental design, and data interpretation in parallel with appropriate background information related to the quantitative characterization of molecular photophysics using CuI MLCT chromophores as prototypical examples. Initially, CuI MLCT excited states, their energetics, and relevant structural conformation changes implicated in their photophysical decay processes are described. This is followed by a discussion of the literature that motivated our research in this area. This led to our first molecular design in 2013, achieving a 7-fold increase in excited state lifetime relative to the current state-of-the-art. The lifetime and photophysical property enhancement resulted from using 2,9-branched alkyl groups in conjunction with flanking 3,8-methyl substituents, a strategy we adapted from the McMillin group, which was initially described in the late 1990s. Applications of this newly conceived chromophore are presented in solar hydrogen-producing photocatalysis, photochemical upconversion, and photosensitization of [4 + 4] anthracene dimerization of potential interest in thermal storage of solar energy in metastable intermediates. Ultrafast transient absorption and fluorescence upconversion spectroscopic characterization of this and related CuI molecules inform the resultant photophysical properties and vice versa, so the most comprehensive structure-property understanding becomes realized when these experimental tools are collectively utilized to investigate the same series of molecules. Computationally guided structural designs generated newly conceived molecules featuring visible light-harvesting and 2,9-cycloalkane substituted complexes. The latter eventually produced record-setting excited state lifetimes in molecules leveraging both cooperative steric influence and electronic inductive effects. Using photoluminescence data from structurally homologous CuI MLCT excited states collected over 44 years, an energy gap correlation successfully modeled the data spanning a 0.3 eV emission energy range. Finally, a new research direction is revealed detailing structure-photophysical property relationships in heteroleptic CuI phenanthroline chromophores that are photoluminescent at room temperature.