Buchumschlag

Counter-ligand control of the electronic structure in dinuclear copper-tetrakisguanidine complexes

The redox-active GFA (Guanidino-Functionalized Aromatic compound) 1,4,5,8-tetrakis(tetramethylguanidino)-naphthalene (6) is used to synthesize new dinuclear copper complexes of the formula [6(CuX2)2] with different electronic structures. With X = OAc, a dinuclear CuII complex of the neutral GFA is o...

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Bibliographische Detailangaben
Hauptverfasser: Ziesak, Alexandra Sabrina (VerfasserIn) , Wesp, Tobias (VerfasserIn) , Hübner, Olaf (VerfasserIn) , Kaifer, Elisabeth (VerfasserIn) , Wadepohl, Hubert (VerfasserIn) , Himmel, Hans-Jörg (VerfasserIn)
Dokumenttyp: Article (Journal)
Sprache:Englisch
Veröffentlicht: 19 Oct 2015
In: Dalton transactions
Year: 2015, Jahrgang: 44, Heft: 44, Pages: 19111-19125
ISSN:1477-9234
DOI:10.1039/C5DT03270A
Online-Zugang:Verlag, lizenzpflichtig, Volltext: https://doi.org/10.1039/C5DT03270A
Verlag, lizenzpflichtig, Volltext: https://pubs.rsc.org/en/content/articlelanding/2015/dt/c5dt03270a
Volltext
Verfasserangaben:Alexandra Ziesak, Tobias Wesp, Olaf Hübner, Elisabeth Kaifer, Hubert Wadepohl and Hans-Jörg Himmel
Beschreibung
Zusammenfassung:The redox-active GFA (Guanidino-Functionalized Aromatic compound) 1,4,5,8-tetrakis(tetramethylguanidino)-naphthalene (6) is used to synthesize new dinuclear copper complexes of the formula [6(CuX2)2] with different electronic structures. With X = OAc, a dinuclear CuII complex of the neutral GFA is obtained (electronic structure [CuII-GFA-CuII], two unpaired electrons), and with X = Br a diamagnetic dinuclear CuI complex of the dicationic GFA (electronic structure [CuI-GFA2+-CuI], closed-shell singlet state). The different electronic structures lead to significant differences in the optical, structural and magnetic properties of the complexes. Furthermore, the complex [6(CuI)2]2+ (electronic structure [CuI-GFA2+-CuI], closed-shell singlet state) is synthesized by reaction of 62+ with two equivalents of CuI. Slow decomposition of this complex in solution leads to the fluorescent dye 2,7-bis(dimethylamino)-1,3,6,8-tetraazapyrene. In an improved synthesis of this tetraazapyrene, 6 is reacted with CuBr in the presence of dioxygen. Quantum chemical calculations show that the addition of counter-ligands to the trigonal planar CuI atoms of [6(CuI)2]2+ favors or disfavors one of the electronic structures, depending on the nature of the counter-ligand.
Beschreibung:Gesehen am 15.09.2020
Beschreibung:Online Resource
ISSN:1477-9234
DOI:10.1039/C5DT03270A

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