Universität zu Köln

Haseloer, Alexander ORCID: 0000-0003-0480-7568, Denkler, Luca Mareen ORCID: 0000-0001-9955-9928, Jordan, Rose ORCID: 0000-0003-0764-1639, Reimer, Max, Olthof, Selina ORCID: 0000-0002-8871-1549, Schmidt, Ines, Meerholz, Klaus ORCID: 0000-0001-7450-4672, Hoerner, Gerald ORCID: 0000-0002-3883-2879 and Klein, Axel ORCID: 0000-0003-0093-9619 (2021). Ni, Pd, and Pt complexes of a tetradentate dianionic thiosemicarbazone-based O boolean AND N boolean AND N boolean AND S ligand. Dalton Trans., 50 (12). S. 4311 - 4323. CAMBRIDGE: ROYAL SOC CHEMISTRY. ISSN 1477-9234

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Abstract

New tetradentate phenolate (ONNS)-N-boolean AND-N-boolean AND-S-boolean AND thiosemicarbazone (TSC) ligands and their Ni(ii), Pd(ii) and Pt(ii) complexes were studied. The diamagnetic and square planar configured orange or red complexes show reversible reductive electrochemistry and in part reversible oxidative electrochemistry at very moderate potentials. DFT calculations show essentially pyridyl-imine centred lowest unoccupied molecular orbitals (LUMO) while the highest occupied molecular orbitals (HOMO) receive contributions from the phenolate moiety, the metal d orbitals and the TSC thiolate atom in keeping with UV-vis spectroelectrochemistry. DFT calculations in conjunction with IR spectra showed details of the molecular structures, the UV-vis absorptions were modelled through TD-DFT calculation with very high accuracy. UPS is fully consistent with UV-vis absorption and TD-DFT calculated data and shows decreasing HOMO-LUMO gaps along the series Pd > Pt > Ni.

Item Type:	Journal Article
Creators:	Creators Email ORCID ORCID Put Code Haseloer, Alexander UNSPECIFIED orcid.org/0000-0003-0480-7568 UNSPECIFIED Denkler, Luca Mareen UNSPECIFIED orcid.org/0000-0001-9955-9928 UNSPECIFIED Jordan, Rose UNSPECIFIED orcid.org/0000-0003-0764-1639 UNSPECIFIED Reimer, Max UNSPECIFIED UNSPECIFIED UNSPECIFIED Olthof, Selina UNSPECIFIED orcid.org/0000-0002-8871-1549 UNSPECIFIED Schmidt, Ines UNSPECIFIED UNSPECIFIED UNSPECIFIED Meerholz, Klaus UNSPECIFIED orcid.org/0000-0001-7450-4672 UNSPECIFIED Hoerner, Gerald UNSPECIFIED orcid.org/0000-0002-3883-2879 UNSPECIFIED Klein, Axel UNSPECIFIED orcid.org/0000-0003-0093-9619 UNSPECIFIED
URN:	urn:nbn:de:hbz:38-571704
DOI:	10.1039/d1dt00272d
Journal or Publication Title:	Dalton Trans.
Volume:	50
Number:	12
Page Range:	S. 4311 - 4323
Date:	2021
Publisher:	ROYAL SOC CHEMISTRY
Place of Publication:	CAMBRIDGE
ISSN:	1477-9234
Language:	English
Faculty:	Unspecified
Divisions:	Unspecified
Subjects:	no entry
Uncontrolled Keywords:	Keywords Language TRANSITION-METAL-COMPLEXES; SPECTROPHOTOMETRIC DETERMINATION; ANTIMICROBIAL ACTIVITIES; ELECTRONIC-STRUCTURES; CRYSTAL-STRUCTURES; DERIVATIVES; NICKEL(II); TRIDENTATE; PALLADIUM; SEMICARBAZONES Multiple languages Chemistry, Inorganic & Nuclear Multiple languages
URI:	http://kups.ub.uni-koeln.de/id/eprint/57170