TMPA‐based Cavitary Cobalt (II) Funnel Complexes

Nyssen, Nicolas; Abudayyeh, Abdullah; Zhurkin, Fedor; Aoun, Pamela; Višnjevac, Aleksandar; Colasson, Benoit; Jabin, Ivan; Reinaud, Olivia (2024) TMPA‐based Cavitary Cobalt (II) Funnel Complexes. European Journal of Inorganic Chemistry, 27 (22). ISSN 1434-1948

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Abstract

The synthesis of a series of mononuclear, dicationic CoII funnel complexes is reported herein. Three ligands Calix-TMPAX present a calix[6]arene cone closed at its small rim by a tris(2-pyridylmethyl)amine (TMPA) unit and differ by the nature of three cavity walls, anisole, phenol or quinone. The X-ray diffraction structure of [CoII(MeCN)Calix-TMPAOMe](ClO4)2 displays a trigonal bipyramidal geometry, with Co bound to all 4 nitrogen atoms of the TMPA cap, and to one MeCN guest molecule buried inside the calixarene cavity. All complexes were fully characterized in solution as high spin 5-coordinate species using various techniques, including 1H NMR spectroscopy. For comparison purpose, an analogous CoII complex based on the TMPACH2OH ligand, devoid of a calixarene core, was synthetized. Its X-ray structure shows a dicationic 7-coordinate cobalt(II) center in the N4O3 environment provided by the ligand, leaving no space for exogenous ligand binding. This contrasts with the 5-coordinate complexes obtained with the calix-ligands that allow guest-ligand binding and exchange. A brief overview of the coordination properties of the calix-complexes, compared to those obtained with TMPA ligands, devoid of a cavity, highlights major differences in terms of complexation kinetics, geometry, coordination to the labile site, anion affinity, nuclearity, and stability.

Item Type:	Article
Uncontrolled Keywords:	Cobalt(II); supramolecular; second coordination sphere; host-guest; nitrogen ligand
Subjects:	NATURAL SCIENCES > Chemistry
Divisions:	Division of Physical Chemistry
Projects:	Project title Project leader Project code Project type Biomimetički “funnel” i “bowl” supramolekularni sustavi za selektivno prepoznavanje DNA/RNA-CALIXDNA / CALIXDNA Aleksandar Višnjevac IP-2020-02-3786 HRZZ
Depositing User:	Ema Buhin Šaler
Date Deposited:	21 Apr 2026 12:32
URI:	https://fulir.irb.hr:/id/eprint/11771
DOI:	10.1002/ejic.202400228

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