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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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Bibliographic Details
Main Authors: Ziesak, Alexandra Sabrina (Author) , Wesp, Tobias (Author) , Hübner, Olaf (Author) , Kaifer, Elisabeth (Author) , Wadepohl, Hubert (Author) , Himmel, Hans-Jörg (Author)
Format: Article (Journal)
Language:English
Published: 19 Oct 2015
In: Dalton transactions
Year: 2015, Volume: 44, Issue: 44, Pages: 19111-19125
ISSN:1477-9234
DOI:10.1039/C5DT03270A
Online Access:Verlag, lizenzpflichtig, Volltext: https://doi.org/10.1039/C5DT03270A
Verlag, lizenzpflichtig, Volltext: https://pubs.rsc.org/en/content/articlelanding/2015/dt/c5dt03270a
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Author Notes:Alexandra Ziesak, Tobias Wesp, Olaf Hübner, Elisabeth Kaifer, Hubert Wadepohl and Hans-Jörg Himmel
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Summary: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.
Item Description:Gesehen am 15.09.2020
Physical Description:Online Resource
ISSN:1477-9234
DOI:10.1039/C5DT03270A

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