期刊名称：Proceedings of the National Academy of Sciences
印刷版ISSN：0027-8424
电子版ISSN：1091-6490
出版年度：2020
卷号：117
期号：34
页码：20430-20437
DOI：10.1073/pnas.2009996117
出版社：The National Academy of Sciences of the United States of America
摘要：Exploiting earth-abundant iron-based metal complexes as high-performance photosensitizers demands long-lived electronically excited metal-to-ligand charge-transfer (MLCT) states, but these species suffer typically from femtosecond timescale charge-transfer (CT)-state quenching by low-lying nonreactive metal-centered (MC) states. Here, we engineer supermolecular Fe(II) chromophores based on the bis(tridentate-ligand)metal(II)-ethyne-(porphinato)zinc(II) conjugated framework, previously shown to give rise to highly delocalized low-lying 3 MLCT states for other Group VIII metal (Ru, Os) complexes. Electronic spectral, potentiometric, and ultrafast pump–probe transient dynamical data demonstrate that a combination of a strong σ-donating tridentate ligand and a (porphinato)zinc(II) moiety with low-lying π*-energy levels, sufficiently destabilize MC states and stabilize supermolecular MLCT states to realize Fe(II) complexes that express 3 MLCT state photophysics reminiscent of their heavy-metal analogs. The resulting Fe(II) chromophore archetype, FeNHCPZn, features a highly polarized CT state having a profoundly extended 3 MLCT lifetime (160 ps), 3 MLCT phosphorescence, and ambient environment stability. Density functional and domain-based local pair natural orbital coupled cluster [DLPNO-CCSD(T)] theory reveal triplet-state wavefunction spatial distributions consistent with electronic spectroscopic and excited-state dynamical data, further underscoring the dramatic Fe metal-to-extended ligand CT character of electronically excited FeNHCPZn. This design further prompts intense panchromatic absorptivity via redistributing high-energy absorptive oscillator strength throughout the visible spectral domain, while maintaining a substantial excited-state oxidation potential for wide-ranging photochemistry––highlighted by the ability of FeNHCPZn to photoinject charges into a SnO 2 /FTO electrode in a dye-sensitized solar cell (DSSC) architecture. Concepts enumerated herein afford opportunities for replacing traditional rare-metal–based emitters for solar-energy conversion and photoluminescence applications.
关键词：photophysics ; iron ; chromophore ; MLCT ; emission
