Electronic Structure and Excited-State Dynamics of the NIR-II Emissive Molybdenum(III) Analogue to the Molecular Ruby

Publication type:
Journal article
Metadata:
Autoren
  • Winald R Kitzmann
  • David Hunger
  • Antti-Pekka M Reponen
  • Christoph Fo''rster
  • Roland Schoch
  • Matthias Bauer
  • Sascha Feldmann
  • Joris van Slageren
  • Katja Heinze
Autoren-URL
https://www.webofscience.com/api/gateway?GWVersion=2&SrcApp=fis-test-1&SrcAuth=WosAPI&KeyUT=WOS:001122222200001&DestLinkType=FullRecord&DestApp=WOS_CPL
DOI
10.1021/acs.inorgchem.3c02186
eISSN
1520-510X
Externe Identifier
  • Clarivate Analytics Document Solution ID: AZ5X6
  • PubMed Identifier: 37718553
ISSN
0020-1669
Ausgabe der Veröffentlichung
39
Zeitschrift
INORGANIC CHEMISTRY
Paginierung
15797 - 15808
Datum der Veröffentlichung
2023
Status
Published
Titel
Electronic Structure and Excited-State Dynamics of the NIR-II Emissive Molybdenum(III) Analogue to the Molecular Ruby
Sub types
  • Article
Ausgabe der Zeitschrift
62

Data source: Web of Science (Lite)

Other metadata sources:
Autoren
  • Winald R Kitzmann
  • David Hunger
  • Antti-Pekka M Reponen
  • Christoph Förster
  • Roland Schoch
  • Matthias Bauer
  • Sascha Feldmann
  • Joris van Slageren
  • Katja Heinze
DOI
10.1021/acs.inorgchem.3c02186
eISSN
1520-510X
ISSN
0020-1669
Ausgabe der Veröffentlichung
39
Zeitschrift
Inorganic Chemistry
Sprache
en
Online publication date
2023
Paginierung
15797 - 15808
Datum der Veröffentlichung
2023
Status
Published
Herausgeber
American Chemical Society (ACS)
Herausgeber URL
http://dx.doi.org/10.1021/acs.inorgchem.3c02186
Datum der Datenerfassung
2023
Titel
Electronic Structure and Excited-State Dynamics of the NIR-II Emissive Molybdenum(III) Analogue to the Molecular Ruby
Ausgabe der Zeitschrift
62

Data source: Crossref

Abstract
Photoactive chromium(III) complexes saw a conceptual breakthrough with the discovery of the prototypical molecular ruby <i>mer</i>-[Cr(ddpd)<sub>2</sub>]<sup>3+</sup> (ddpd = <i>N</i>,<i>N</i>'-dimethyl-<i>N</i>,<i>N</i>'-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 <i>mer</i>-MoX<sub>3</sub>(ddpd) (<b>1</b>, X = Cl; <b>2</b>, X = Br) and <i>cisfac</i>-[Mo(ddpd)<sub>2</sub>]<sup>3+</sup> (<i>cisfac</i>-<b>[3]</b><sup><b>3+</b></sup>), an isomeric heavy homologue of the prototypical molecular ruby. For <i>cisfac</i>-<b>[3]</b><sup><b>3+</b></sup>, 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 <i>mer</i>-<b>1</b>, <i>mer</i>-<b>2</b>, and <i>cisfac</i>-<b>[3]</b><sup><b>3+</b></sup> 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 <i>cisfac</i>-<b>[3]</b><sup><b>3+</b></sup> 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 <i>mer</i>-[Cr(ddpd)<sub>2</sub>]<sup>3+</sup>. Using density functional theory and <i>ab initio</i> multireference calculations, we break down the reasons for this disparity and derive principles for the design of future stable photoactive molybdenum(III) complexes.
Addresses
  • Department of Chemistry, Johannes Gutenberg University of Mainz, Duesbergweg 10-14, 55128 Mainz, Germany.
Autoren
  • Winald R Kitzmann
  • David Hunger
  • Antti-Pekka M Reponen
  • Christoph Förster
  • Roland Schoch
  • Matthias Bauer
  • Sascha Feldmann
  • Joris van Slageren
  • Katja Heinze
DOI
10.1021/acs.inorgchem.3c02186
eISSN
1520-510X
Externe Identifier
  • PubMed Identifier: 37718553
Funding acknowledgements
  • Deutsche Forschungsgemeinschaft: HE2778/15-1
  • Rowland Institute at Harvard:
  • Studienstiftung des Deutschen Volkes:
  • Deutsche Forschungsgemeinschaft: BA 4467/7-1
  • Fonds der Chemischen Industrie:
  • Deutsche Forschungsgemeinschaft: INST 247/1018-1 FUGG
  • Max Planck Graduate Center:
Open access
false
ISSN
0020-1669
Ausgabe der Veröffentlichung
39
Zeitschrift
Inorganic chemistry
Sprache
eng
Medium
Print-Electronic
Online publication date
2023
Paginierung
15797 - 15808
Datum der Veröffentlichung
2023
Status
Published
Datum der Datenerfassung
2023
Titel
Electronic Structure and Excited-State Dynamics of the NIR-II Emissive Molybdenum(III) Analogue to the Molecular Ruby.
Sub types
  • Journal Article
Ausgabe der Zeitschrift
62

Data source: Europe PubMed Central

Abstract
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.
Autoren
  • Winald R Kitzmann
  • David Hunger
  • Antti-Pekka M Reponen
  • Christoph Förster
  • Roland Schoch
  • Matthias Bauer
  • Sascha Feldmann
  • Joris van Slageren
  • Katja Heinze
Autoren-URL
https://www.ncbi.nlm.nih.gov/pubmed/37718553
DOI
10.1021/acs.inorgchem.3c02186
eISSN
1520-510X
Ausgabe der Veröffentlichung
39
Zeitschrift
Inorg Chem
Sprache
eng
Country
United States
Paginierung
15797 - 15808
Datum der Veröffentlichung
2023
Status
Published
Titel
Electronic Structure and Excited-State Dynamics of the NIR-II Emissive Molybdenum(III) Analogue to the Molecular Ruby.
Sub types
  • Journal Article
Ausgabe der Zeitschrift
62

Data source: PubMed

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