{"abstract":[{"lang":"eng","text":"Photoactive chromium(III) complexes saw a conceptual breakthrough with the discovery of the prototypical molecular ruby mer-[Cr(ddpd)2]3+ (ddpd = N,N′-dimethyl-N,N′-dipyridin-2-ylpyridine-2,6-diamine), which shows intense long-lived near-infrared (NIR) phosphorescence from metal-centered spin-flip states. In contrast to the numerous studies on chromium(III) photophysics, only 10 luminescent molybdenum(III) complexes have been reported so far. Here, we present the synthesis and characterization of mer-MoX3(ddpd) (1, X = Cl; 2, X = Br) and cisfac-[Mo(ddpd)2]3+ (cisfac-[3]3+), an isomeric heavy homologue of the prototypical molecular ruby. For cisfac-[3]3+, we found strong zero-field splitting using magnetic susceptibility measurements and electron paramagnetic resonance spectroscopy. Electronic spectra covering the spin-forbidden transitions show that the spin-flip states in mer-1, mer-2, and cisfac-[3]3+ are much lower in energy than those in comparable chromium(III) compounds. While all three complexes show weak spin-flip phosphorescence in NIR-II, the emission of cisfac-[3]3+ peaking at 1550 nm is particularly low in energy. Femtosecond transient absorption spectroscopy reveals a short excited-state lifetime of 1.4 ns, 6 orders of magnitude shorter than that of mer-[Cr(ddpd)2]3+. Using density functional theory and ab initio multireference calculations, we break down the reasons for this disparity and derive principles for the design of future stable photoactive molybdenum(III) complexes."}],"page":"15797-15808","title":"Electronic Structure and Excited-State Dynamics of the NIR-II Emissive Molybdenum(III) Analogue to the Molecular Ruby","publication":"Inorganic Chemistry","volume":62,"publication_status":"published","doi":"10.1021/acs.inorgchem.3c02186","citation":{"ieee":"W. R. Kitzmann et al., “Electronic Structure and Excited-State Dynamics of the NIR-II Emissive Molybdenum(III) Analogue to the Molecular Ruby,” Inorganic Chemistry, vol. 62, no. 39, pp. 15797–15808, 2023, doi: 10.1021/acs.inorgchem.3c02186.","bibtex":"@article{Kitzmann_Hunger_Reponen_Förster_Schoch_Bauer_Feldmann_van Slageren_Heinze_2023, title={Electronic Structure and Excited-State Dynamics of the NIR-II Emissive Molybdenum(III) Analogue to the Molecular Ruby}, volume={62}, DOI={10.1021/acs.inorgchem.3c02186}, number={39}, journal={Inorganic Chemistry}, publisher={American Chemical Society (ACS)}, author={Kitzmann, Winald R. and Hunger, David and Reponen, Antti-Pekka M. and Förster, Christoph and Schoch, Roland and Bauer, Matthias and Feldmann, Sascha and van Slageren, Joris and Heinze, Katja}, year={2023}, pages={15797–15808} }","apa":"Kitzmann, W. R., Hunger, D., Reponen, A.-P. M., Förster, C., Schoch, R., Bauer, M., Feldmann, S., van Slageren, J., & Heinze, K. (2023). Electronic Structure and Excited-State Dynamics of the NIR-II Emissive Molybdenum(III) Analogue to the Molecular Ruby. Inorganic Chemistry, 62(39), 15797–15808. https://doi.org/10.1021/acs.inorgchem.3c02186","mla":"Kitzmann, Winald R., et al. “Electronic Structure and Excited-State Dynamics of the NIR-II Emissive Molybdenum(III) Analogue to the Molecular Ruby.” Inorganic Chemistry, vol. 62, no. 39, American Chemical Society (ACS), 2023, pp. 15797–808, doi:10.1021/acs.inorgchem.3c02186.","short":"W.R. Kitzmann, D. Hunger, A.-P.M. Reponen, C. Förster, R. Schoch, M. Bauer, S. Feldmann, J. van Slageren, K. Heinze, Inorganic Chemistry 62 (2023) 15797–15808.","chicago":"Kitzmann, Winald R., David Hunger, Antti-Pekka M. Reponen, Christoph Förster, Roland Schoch, Matthias Bauer, Sascha Feldmann, Joris van Slageren, and Katja Heinze. “Electronic Structure and Excited-State Dynamics of the NIR-II Emissive Molybdenum(III) Analogue to the Molecular Ruby.” Inorganic Chemistry 62, no. 39 (2023): 15797–808. https://doi.org/10.1021/acs.inorgchem.3c02186.","ama":"Kitzmann WR, Hunger D, Reponen A-PM, et al. Electronic Structure and Excited-State Dynamics of the NIR-II Emissive Molybdenum(III) Analogue to the Molecular Ruby. Inorganic Chemistry. 2023;62(39):15797-15808. doi:10.1021/acs.inorgchem.3c02186"},"status":"public","date_created":"2024-03-07T09:57:30Z","user_id":"48467","intvolume":" 62","department":[{"_id":"306"}],"date_updated":"2024-03-07T10:02:58Z","publisher":"American Chemical Society (ACS)","type":"journal_article","_id":"52345","language":[{"iso":"eng"}],"article_type":"original","publication_identifier":{"issn":["0020-1669","1520-510X"]},"year":"2023","author":[{"full_name":"Kitzmann, Winald R.","last_name":"Kitzmann","first_name":"Winald R."},{"first_name":"David","full_name":"Hunger, David","last_name":"Hunger"},{"first_name":"Antti-Pekka M.","last_name":"Reponen","full_name":"Reponen, Antti-Pekka M."},{"last_name":"Förster","full_name":"Förster, Christoph","first_name":"Christoph"},{"id":"48467","full_name":"Schoch, Roland","last_name":"Schoch","first_name":"Roland","orcid":"0000-0003-2061-7289"},{"orcid":"0000-0002-9294-6076","first_name":"Matthias","full_name":"Bauer, Matthias","last_name":"Bauer","id":"47241"},{"first_name":"Sascha","last_name":"Feldmann","full_name":"Feldmann, Sascha"},{"full_name":"van Slageren, Joris","last_name":"van Slageren","first_name":"Joris"},{"first_name":"Katja","full_name":"Heinze, Katja","last_name":"Heinze"}],"issue":"39","keyword":["Inorganic Chemistry","Physical and Theoretical Chemistry"]}