Structural and magnetic properties of heptacoordinated Mn-II complexes containing a 15-membered pyridine-based macrocycle and halido/pseudohalido axial coligands

Result code in IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F61989592%3A15310%2F16%3A33161061" target="_blank" >RIV/61989592:15310/16:33161061 - isvavai.cz</a>

Result on the web

<a href="http://pubs.rsc.org/en/content/articlepdf/2016/ra/c6ra03754b" target="_blank" >http://pubs.rsc.org/en/content/articlepdf/2016/ra/c6ra03754b</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1039/c6ra03754b" target="_blank" >10.1039/c6ra03754b</a>

Result language

angličtina

Original language name

Structural and magnetic properties of heptacoordinated Mn-II complexes containing a 15-membered pyridine-based macrocycle and halido/pseudohalido axial coligands

Original language description

A series of heptacoordinated Mn-II compounds with a pentadentate 15-membered pyridine-based macrocycle 15-pyN(3)O(2)(3,12,18-triaza-6,9-dioxabicyclo[12.3.1]octadeca-1(18),14,16-triene) and two axially coordinated halido/pseudohalido coligands (X), having a monomeric [Mn(15-pyN(3)O(2))X-2] (X = Br- (1), I- (2), N-3(-) (3), NCS- (4)) or polymeric {[Mn(15-pyN(3)O(2))X](ClO4)}(n) (X = CN- (5)) composition, was prepared and thoroughly characterized. Single crystal X-ray analysis of 2, 3 and 4 determined the distorted pentagonal-bipyramidal geometry of the complexes. The analysis of the magnetic data of complexes 1-4 revealed non-zero values of the axial zero-field splitting parameter D (vertical bar D vertical bar < 0.7 cm(-1)) and weak antiferromagnetic intermolecular interactions (molecular field correction parameter zj approximate to -0.1 cm(-1)). As for the 1D polymeric complex 5, a small antiferromagnetic exchange coupling was found between Mn-II centres, with J = -1.72 cm(-1). The experimentally obtained magnetic parameters (J or zj) were compared with those theoretically calculated at the DFT level in order to reveal the magnetic exchange pathways in 2-4 and to support the polymeric structure of 5 (J(EXP) = -2.79 cm(-1) vs. J(R)/J(Y) = -2.54/-3.06 cm(-1), when the dinuclear spin Hamiltonian was used). It has been also found that extensive systems of hydrogen bonds, non-covalent contacts and pi-pi stacking interactions present in the crystal structures of 2, 3 and 4 have an impact on the formation of supramolecular 1D chains, and as a consequence of this on the magnetic properties of the complexes. Contrary to non-covalent contacts, the influence of the axial ligands on the magnetic nature of the complexes seems to be negligible.

Czech name

—

Czech description

—

Type

J_x - Unclassified - Peer-reviewed scientific article (Jimp, Jsc and Jost)

CEP classification

CA - Inorganic chemistry

OECD FORD branch

—

Project

Result was created during the realization of more than one project. More information in the Projects tab.

Continuities

P - Projekt vyzkumu a vyvoje financovany z verejnych zdroju (s odkazem do CEP)

Publication year

2016

Confidentiality

S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů

Name of the periodical

RSC Advances (online)

ISSN

2046-2069

e-ISSN

—

Volume of the periodical

6

Issue of the periodical within the volume

41

Country of publishing house

GB - UNITED KINGDOM

Number of pages

11

Pages from-to

34674-34684

UT code for WoS article

000374049700069

EID of the result in the Scopus database

—