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Multi‐Tier Electronic Structure Analysis of Sita's Mo and W Complexes Capable of Thermal or Photochemical N₂ Splitting

Rupp, Severine ; Plasser, Felix ; Krewald, Vera (2024)
Multi‐Tier Electronic Structure Analysis of Sita's Mo and W Complexes Capable of Thermal or Photochemical N₂ Splitting.
In: European Journal of Inorganic Chemistry, 2020, 2020 (15-16)
doi: 10.26083/tuprints-00015647
Artikel, Zweitveröffentlichung, Verlagsversion

Es ist eine neuere Version dieses Eintrags verfügbar.

URL / URN: https://tuprints.ulb.tu-darmstadt.de/15647

Kurzbeschreibung (Abstract)

An emerging approach for the activation of the nitrogen molecule is the light‐driven splitting of the N–N bond. Less than ten examples for complexes capable of N₂ photoactivation are currently known, and the underlying photophysical and photochemical processes after light absorption are largely unresolved. All complexes have a central [M(µ‐η¹:η¹‐N₂)M] unit with equivalent ligand spheres around each metal. For several of these complexes, small modifications of the ligand sphere result in thermal rather than photochemical activity. Herein, we analyse the electronic structures and computed UV/Vis spectra of four complexes: two thermally and two photochemically active complexes, each either involving molybdenum or tungsten. The analysis of electronic structures and spectra is based on the molecular orbitals, difference densities and the charge‐transfer numbers provided by TheoDORE. We find that the spectra of the photochemically active complexes contain excitations with more ligand‐to‐metal charge‐transfer character and higher intensity, providing a plausible explanation for light‐induced nitrogen splitting.

Typ des Eintrags:

Artikel

Erschienen:

2024

Autor(en):

Rupp, Severine ; Plasser, Felix ; Krewald, Vera

Art des Eintrags:

Zweitveröffentlichung

Titel:

Multi‐Tier Electronic Structure Analysis of Sita's Mo and W Complexes Capable of Thermal or Photochemical N₂ Splitting

Sprache:

Englisch

Publikationsjahr:

9 Januar 2024

Ort:

Darmstadt

Publikationsdatum der Erstveröffentlichung:

2020

Ort der Erstveröffentlichung:

Weinheim

Verlag:

Wiley-VCH

Titel der Zeitschrift, Zeitung oder Schriftenreihe:

European Journal of Inorganic Chemistry

Jahrgang/Volume einer Zeitschrift:

2020

(Heft-)Nummer:

15-16

DOI:

10.26083/tuprints-00015647

URL / URN:

https://tuprints.ulb.tu-darmstadt.de/15647

Zugehörige Links:

Verlags-DOI

Herkunft:

Zweitveröffentlichung DeepGreen

Kurzbeschreibung (Abstract):

Alternatives oder übersetztes Abstract:

Alternatives Abstract	Sprache
The nitrogen molecule cannot only be activated thermally and electrochemically, but also photochemically. A study of the electronic structure of four Mo and W complexes with similar ligand spheres that are either photochemically or thermally active shows that ligand-to-metal charge transfer excitations appear more often and with higher intensity in complexes capable of nitrogen photoactivation.	Englisch

Freie Schlagworte:

Nitrogen activation, Electronic structure, Molybdenum, Tungsten, Density functional theory calculations

Status:

Verlagsversion

URN:

urn:nbn:de:tuda-tuprints-156475

Zusätzliche Informationen:

Special Issue: Nitrogen Fixation

Sachgruppe der Dewey Dezimalklassifikatin (DDC):

500 Naturwissenschaften und Mathematik > 540 Chemie

Fachbereich(e)/-gebiet(e):

07 Fachbereich Chemie
07 Fachbereich Chemie > Theoretische Chemie (am 07.02.2024 umbenannt in Quantenchemie)