Hidden Lewis acidity: Studies on the medium and structure dependent fluorescence of zinc(II) complexes

Kurz, Haymo; Hörner, Gerald; Weser, Oskar; Manni, Giovanni Li; Weber, Birgit

doi:10.33774/chemrxiv-2021-grnzt

Cited by 1 publication

(2 citation statements)

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“…The starting structures reflect (i) the known preference of related complexes to form dispersion‐dimers via π‐stacks with minor axial interactions at copper [10] or (ii) the axial expansion of the coordination sphere to CN=4+δ through bonding interaction with the remote carbonyls. The latter mode has been recently suggested for the self‐association of zinc complexes in planar N 2 O 2 fields [16] . While this fragmentary scan of the conformational space cannot be expected to be fully conclusive, some relevant conclusions can be drawn.…”

Section: Resultsmentioning

confidence: 75%

“…The latter mode has been recently suggested for the self-association of zinc complexes in planar N 2 O 2 fields. [16] While this fragmentary scan of the conformational space cannot be expected to be fully conclusive, some relevant conclusions can be drawn. In the previously reported zinc(II)based dimers strong axial interactions have overridden van der Waals interactions.…”

Section: Concentrated Solutions Of [Cul]mentioning

confidence: 98%

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Solvent‐Dependent Self‐Assembly of an Amphiphilic Copper(II) Complex with Bulky Head Groups

et al. 2022

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Dedicated to Prof. Wolfgang Beck on the occasion of his 90th birthday.The aggregation behavior of an amphiphilic copper(II) complex was studied in solution by means of UV-Vis and EPR spectroscopy. While dilute solutions in polar media do not give indication of relevant intermolecular interactions, concentrated solutions in nonpolar media clearly do not reflect the molecular properties of [CuL] (H 2 L: N 2 O 2 ligand of the Jäger-type with bulky head-group and long alkoxy tailing). Massive broadening of EPR-lines is prevalent in non-polar media, such as n-heptane and iso-octane. In combination with DFT-modelling, the solvent-dependence of the EPR response (line widths and Cuhyperfine coupling) could be associated with the formation of oligomers with weak anti-ferromagnetically coupled copper centers. Weak anti-ferromagnetic coupling becomes evident also by SQUID magnetometry at T < 10 K of solid samples of [CuL]. The tendency towards supramolecular aggregation is unequivocally shown by electron microscopy of dried (TEM) and frozen samples (cryo-TEM). While the former approach gives evidence of the formation of extended 2D sheet-like structures with extensions on the micrometer scale, the latter technique identifies the formation of 1D thread-like structures with lengths of several hundred nanometers.

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Section: Resultsmentioning

confidence: 75%

Section: Concentrated Solutions Of [Cul]mentioning

confidence: 98%

Solvent‐Dependent Self‐Assembly of an Amphiphilic Copper(II) Complex with Bulky Head Groups

et al. 2022

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Hidden Lewis acidity: Studies on the medium and structure dependent fluorescence of zinc(II) complexes

Abstract: Supporting information for this article is given via a link at the end of the document.

Cited by 1 publication

References 17 publications

Solvent‐Dependent Self‐Assembly of an Amphiphilic Copper(II) Complex with Bulky Head Groups

Solvent‐Dependent Self‐Assembly of an Amphiphilic Copper(II) Complex with Bulky Head Groups

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