Universität zu Köln

Krest, Alexander, Sandleben, Aaron ORCID: 0000-0002-4141-7406, Valldor, Martin, Werker, Melanie, Ruschewitz, Uwe ORCID: 0000-0002-6511-6894 and Klein, Axel ORCID: 0000-0003-0093-9619 (2017). Heteroleptic Complexes of the Tridentate Pyridine-2,6-di-tetrazolate Ligand. ChemistrySelect, 2 (21). S. 5849 - 5860. WEINHEIM: WILEY-V C H VERLAG GMBH. ISSN 2365-6549

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Abstract

The synthesis and spectroscopic characterisation of a series of heteroleptic complexes of the tridentate pyridine-2,6-di-(5-tetrazolate) (pydtz(2-)) with Co(II), Ni(II), Cu(II) and Zn(II) and pyridine (Py) and H2O as coligands is reported. Single crystal XRD data reveals the formation of octahedrally configured complexes [Co(pydtz)(H2O)(Py)(2)], [Co(pydtz)(H2O)(2)(Py)]2H(2)O, [Ni(pydtz)(Py)(3)]2Py, and [Zn(pydtz)(H2O)(Py)(2)]Py, and a markedly Jahn-Teller distorted octahedral structure for [Cu(pydtz)(H2O)(2)(Py)]. Magnetic measurements reveal a S = 3/2 high-spin configuration for the Co(II) complex [Co(pydtz)(H2O)(Py)(2)], an S = 1 ground state for the Ni(II) derivative and S = 1/2 Cu(II) ions for [Cu(pydtz)(H2O)(2)(Py)], the latter is supported by electron-paramagnetic-resonance spectroscopy. The crystalline materials are subject to severe corrosion as revealed by powder XRD and DSC-TG experiments. H2O and pyridine co-crystallisates and coligands are easily cleaved. At the same time DSC-TG reveal very high stability of the [M(pydtz)] fragments with exothermic decomposition at T > 300 degrees C. As a consequence, in pyridine solution in all cases the species [M(pydtz)(Py)(3)] are observed. Ultraviolet-visible light absorption spectroscopy reveals a strong ligand field procured by the pydtz(2-) ligand and electrochemical measurements suggest very strong sigma-donation but only weak -accepting abilities of pydtz(2-) compared to the isostructural terpy (2,2';6',2''-terpyridine) ligand.

Item Type:	Journal Article
Creators:	Creators Email ORCID ORCID Put Code Krest, Alexander UNSPECIFIED UNSPECIFIED UNSPECIFIED Sandleben, Aaron UNSPECIFIED orcid.org/0000-0002-4141-7406 UNSPECIFIED Valldor, Martin UNSPECIFIED UNSPECIFIED UNSPECIFIED Werker, Melanie UNSPECIFIED UNSPECIFIED UNSPECIFIED Ruschewitz, Uwe UNSPECIFIED orcid.org/0000-0002-6511-6894 UNSPECIFIED Klein, Axel UNSPECIFIED orcid.org/0000-0003-0093-9619 UNSPECIFIED
URN:	urn:nbn:de:hbz:38-224777
DOI:	10.1002/slct.201701124
Journal or Publication Title:	ChemistrySelect
Volume:	2
Number:	21
Page Range:	S. 5849 - 5860
Date:	2017
Publisher:	WILEY-V C H VERLAG GMBH
Place of Publication:	WEINHEIM
ISSN:	2365-6549
Language:	English
Faculty:	Faculty of Mathematics and Natural Sciences
Divisions:	Faculty of Mathematics and Natural Sciences > Department of Chemistry > Institute of Inorganic Chemistry
Subjects:	no entry
Uncontrolled Keywords:	Keywords Language LUMINESCENT LANTHANIDE COMPLEXES; COORDINATION POLYMERS; METAL-COMPLEXES; SPIN-CROSSOVER; PENTAMETHYLENETETRAZOLE COMPLEXES; PT(II) COMPLEXES; TETRAZOLES; COBALT(II); FRAMEWORKS; CHEMISTRY Multiple languages Chemistry, Multidisciplinary Multiple languages
Refereed:	Yes
URI:	http://kups.ub.uni-koeln.de/id/eprint/22477