Tuning of Dimensionality and Nuclearity as a Function of Ligand Field Modulation Resulting in Field-Induced Cobalt(II) Single-Ion Magnet

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F61989592%3A15310%2F23%3A73621969" target="_blank" >RIV/61989592:15310/23:73621969 - isvavai.cz</a>

Výsledek na webu

<a href="https://pubs.acs.org/doi/epdf/10.1021/acs.cgd.2c01255" target="_blank" >https://pubs.acs.org/doi/epdf/10.1021/acs.cgd.2c01255</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1021/acs.cgd.2c01255" target="_blank" >10.1021/acs.cgd.2c01255</a>

Jazyk výsledku

angličtina

Název v původním jazyce

Tuning of Dimensionality and Nuclearity as a Function of Ligand Field Modulation Resulting in Field-Induced Cobalt(II) Single-Ion Magnet

Popis výsledku v původním jazyce

The present study reveals that predetermined diverse topology and desired properties can be achieved by strategically designing the ligand and it confirms that the structural and magnetic features of cobalt(II) complexes have a significant impact of the ligand modulation and proper utilization of a coligand. In this work, tactically, two new Pyclen-based macrocyclic N4 ligands have been designed to demonstrate the effect of the ligand field on structure and magnetic properties. Using these macrocyclic N4 ligands, a series of cobalt complexes, [Co(L1-N-4)(mu-NCS)](2)middot[Co(NCS)(4)] (1), [Co-4(L1-N4)(2){mu-N(CN)(2)}(8)](n)middot2CH(2)Cl(2) (2), and [Co(L2-N4)(NCS)2] (3), have been synthesized and characterized by different physicochemical techniques, including single crystal X-ray diffraction, magnetic, and various spectroscopic methods. The dinuclear plus mononuclear (2 + 1) cobalt complex (1) and 2D cobalt coordination polymer (2) are synthesized using the same macrocyclic N4 ligand: 3,6,9-trimethyl-3,6,9-triaza-1(2,6)pyridinacyclodecaphane (L1-N4) with a variation of coligand from thiocyanato to dicyananamido. A penta-coordinated mononuclear cobalt complex (3) is synthesized by substituting one methyl group of L1-N4 with a carboxaldehyde group, which leads to a [3,9-dimethyl-3,6,9-triaza-1(2,6)-pyridinacyclodecaphane-6-carbaldehyde (L2-N4)] ligand. Single-crystal X-ray diffraction studies reveal the impact of strategic modification of ligands and variation of coligand on the coordination environment, dimensionality, and topology of Co(II) complexes. Whereas, detailed magnetic studies disclose the occurrence of Co(II) ions in a high-spin electronic state for all three complexes, yet, only complex 3 displays exciting slow relaxation of magnetization using an external dc magnetic field and acts as a single-ion magnet, while complexes 1 and 2 display no such property. Detailed theoretical studies have been carried out to better understand and justify the experimentally obtained result.

Název v anglickém jazyce

Tuning of Dimensionality and Nuclearity as a Function of Ligand Field Modulation Resulting in Field-Induced Cobalt(II) Single-Ion Magnet

Popis výsledku anglicky

The present study reveals that predetermined diverse topology and desired properties can be achieved by strategically designing the ligand and it confirms that the structural and magnetic features of cobalt(II) complexes have a significant impact of the ligand modulation and proper utilization of a coligand. In this work, tactically, two new Pyclen-based macrocyclic N4 ligands have been designed to demonstrate the effect of the ligand field on structure and magnetic properties. Using these macrocyclic N4 ligands, a series of cobalt complexes, [Co(L1-N-4)(mu-NCS)](2)middot[Co(NCS)(4)] (1), [Co-4(L1-N4)(2){mu-N(CN)(2)}(8)](n)middot2CH(2)Cl(2) (2), and [Co(L2-N4)(NCS)2] (3), have been synthesized and characterized by different physicochemical techniques, including single crystal X-ray diffraction, magnetic, and various spectroscopic methods. The dinuclear plus mononuclear (2 + 1) cobalt complex (1) and 2D cobalt coordination polymer (2) are synthesized using the same macrocyclic N4 ligand: 3,6,9-trimethyl-3,6,9-triaza-1(2,6)pyridinacyclodecaphane (L1-N4) with a variation of coligand from thiocyanato to dicyananamido. A penta-coordinated mononuclear cobalt complex (3) is synthesized by substituting one methyl group of L1-N4 with a carboxaldehyde group, which leads to a [3,9-dimethyl-3,6,9-triaza-1(2,6)-pyridinacyclodecaphane-6-carbaldehyde (L2-N4)] ligand. Single-crystal X-ray diffraction studies reveal the impact of strategic modification of ligands and variation of coligand on the coordination environment, dimensionality, and topology of Co(II) complexes. Whereas, detailed magnetic studies disclose the occurrence of Co(II) ions in a high-spin electronic state for all three complexes, yet, only complex 3 displays exciting slow relaxation of magnetization using an external dc magnetic field and acts as a single-ion magnet, while complexes 1 and 2 display no such property. Detailed theoretical studies have been carried out to better understand and justify the experimentally obtained result.

Druh

J_imp - Článek v periodiku v databázi Web of Science

CEP obor

—

OECD FORD obor

10402 - Inorganic and nuclear chemistry

Projekt

—

Návaznosti

I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace

Rok uplatnění

2023

Kód důvěrnosti údajů

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

Název periodika

CRYSTAL GROWTH &amp; DESIGN

ISSN

1528-7483

e-ISSN

1528-7505

Svazek periodika

23

Číslo periodika v rámci svazku

3

Stát vydavatele periodika

US - Spojené státy americké

Počet stran výsledku

12

Strana od-do

"1656–1667"

Kód UT WoS článku

000927891900001

EID výsledku v databázi Scopus

2-s2.0-85147223050