{"citation":{"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. <i>Inorganic Chemistry</i>. 2023;62(39):15797-15808. doi:<a href=\"https://doi.org/10.1021/acs.inorgchem.3c02186\">10.1021/acs.inorgchem.3c02186</a>","ieee":"W. R. Kitzmann <i>et al.</i>, “Electronic Structure and Excited-State Dynamics of the NIR-II Emissive Molybdenum(III) Analogue to the Molecular Ruby,” <i>Inorganic Chemistry</i>, vol. 62, no. 39, pp. 15797–15808, 2023, doi: <a href=\"https://doi.org/10.1021/acs.inorgchem.3c02186\">10.1021/acs.inorgchem.3c02186</a>.","apa":"Kitzmann, W. R., Hunger, D., Reponen, A.-P. M., Förster, C., Schoch, R., Bauer, M., Feldmann, S., van Slageren, J., &#38; Heinze, K. (2023). Electronic Structure and Excited-State Dynamics of the NIR-II Emissive Molybdenum(III) Analogue to the Molecular Ruby. <i>Inorganic Chemistry</i>, <i>62</i>(39), 15797–15808. <a href=\"https://doi.org/10.1021/acs.inorgchem.3c02186\">https://doi.org/10.1021/acs.inorgchem.3c02186</a>","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={<a href=\"https://doi.org/10.1021/acs.inorgchem.3c02186\">10.1021/acs.inorgchem.3c02186</a>}, 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} }","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.” <i>Inorganic Chemistry</i> 62, no. 39 (2023): 15797–808. <a href=\"https://doi.org/10.1021/acs.inorgchem.3c02186\">https://doi.org/10.1021/acs.inorgchem.3c02186</a>.","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.","mla":"Kitzmann, Winald R., et al. “Electronic Structure and Excited-State Dynamics of the NIR-II Emissive Molybdenum(III) Analogue to the Molecular Ruby.” <i>Inorganic Chemistry</i>, vol. 62, no. 39, American Chemical Society (ACS), 2023, pp. 15797–808, doi:<a href=\"https://doi.org/10.1021/acs.inorgchem.3c02186\">10.1021/acs.inorgchem.3c02186</a>."},"publisher":"American Chemical Society (ACS)","keyword":["Inorganic Chemistry","Physical and Theoretical Chemistry"],"type":"journal_article","_id":"52345","status":"public","article_type":"original","year":"2023","user_id":"48467","publication":"Inorganic Chemistry","page":"15797-15808","language":[{"iso":"eng"}],"volume":62,"department":[{"_id":"306"}],"date_created":"2024-03-07T09:57:30Z","doi":"10.1021/acs.inorgchem.3c02186","publication_status":"published","author":[{"last_name":"Kitzmann","full_name":"Kitzmann, Winald R.","first_name":"Winald R."},{"full_name":"Hunger, David","last_name":"Hunger","first_name":"David"},{"first_name":"Antti-Pekka M.","full_name":"Reponen, Antti-Pekka M.","last_name":"Reponen"},{"first_name":"Christoph","full_name":"Förster, Christoph","last_name":"Förster"},{"orcid":"0000-0003-2061-7289","id":"48467","first_name":"Roland","full_name":"Schoch, Roland","last_name":"Schoch"},{"orcid":"0000-0002-9294-6076","id":"47241","first_name":"Matthias","last_name":"Bauer","full_name":"Bauer, Matthias"},{"last_name":"Feldmann","full_name":"Feldmann, Sascha","first_name":"Sascha"},{"first_name":"Joris","full_name":"van Slageren, Joris","last_name":"van Slageren"},{"last_name":"Heinze","full_name":"Heinze, Katja","first_name":"Katja"}],"publication_identifier":{"issn":["0020-1669","1520-510X"]},"title":"Electronic Structure and Excited-State Dynamics of the NIR-II Emissive Molybdenum(III) Analogue to the Molecular Ruby","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."}],"intvolume":"        62","issue":"39","date_updated":"2024-03-07T10:02:58Z"}