Titlebar

Export bibliographic data
Literature by the same author
plus on the publication server
plus at Google Scholar

 

Broadly versus Barely Variable Complex Chromophores of Planar Nickel(II) from κ3-N,N′,C and κ3-N,N′,O Donor Platforms

Title data

Alrefai, Riyadh ; Hörner, Gerald ; Schubert, Hartmut ; Berkefeld, Andreas:
Broadly versus Barely Variable Complex Chromophores of Planar Nickel(II) from κ3-N,N′,C and κ3-N,N′,O Donor Platforms.
In: Organometallics. Vol. 40 (14 April 2021) Issue 8 . - pp. 1163-1177.
ISSN 1520-6041
DOI: https://doi.org/10.1021/acs.organomet.1c00121

Project information

Project financing: Deutsche Forschungsgemeinschaft

Abstract in another language

This work reports on complex chromophores of planar nickel(II) of the general formula [(κ3-N,N′,C/O)Ni–ER], which combines a κ2-N,N′-coordinate aromatic N-heterocycle with a pendant phenyl/phenol donor and the variable coligands ER (= carboxylato, phenolato, amido, and arylthiolato). The absorption properties of the planar complex chromophores vary broadly depending on the interplay of the three constituting components. Increasing the manifold of π*-orbitals at the N-heterocyclic moiety through π-extension along 1,10-phenanthroline, tetrahydrodipyridophenazine, and dipyridophenazine has only a small impact on the energies of charge transfer type transitions across the visible (vis) to near-infrared (NIR) spectral region and is due to an inversion among spatially distinct but energetically close unoccupied molecular orbitals. Substantial absorptivity across the visible spectral region rather associates with the increasing capability among carboxylato, phenolato, amido, and arylthiolato coligands to engage in Ni–O/N/S π-bonding. This adds a mechanism for electronic coupling of coligand RE– and π*-orbitals at the N-heterocycle fragment through occupied d orbitals at nickel, enabling light-induced charge transfer. Aryl-S– performs best in this regard, but {Ni–O/N/S}-to-(N-heterocycle-π*) charge transfer efficacy depends on donor–acceptor orbital alignment and appears to be kinetically hindered except for amido coligands owing to polar effects. Irrespective of the nature of coligand RE–, the choice of the pendant phenyl/phenol side arm rules overall absorptivity by setting the energy of occupied frontier molecular orbitals.

Further data

Item Type: Article in a journal
Refereed: Yes
Institutions of the University: Faculties > Faculty of Biology, Chemistry and Earth Sciences > Department of Chemistry > Chair Inorganic Chemistry IV
Faculties > Faculty of Biology, Chemistry and Earth Sciences > Department of Chemistry > Chair Inorganic Chemistry IV > Chair Inorganic Chemistry IV - Univ.-Prof. Dr. Birgit Weber
Faculties
Faculties > Faculty of Biology, Chemistry and Earth Sciences
Faculties > Faculty of Biology, Chemistry and Earth Sciences > Department of Chemistry
Result of work at the UBT: Yes
DDC Subjects: 500 Science > 540 Chemistry
Date Deposited: 15 Jun 2021 13:01
Last Modified: 15 Jun 2021 13:01
URI: https://eref.uni-bayreuth.de/id/eprint/65902