Experimental and theoretical investigations on three DyIII4 single molecule magnets: structural and magneto-structural correlations
- Publikationstyp:
- Zeitschriftenaufsatz
- Metadaten:
-
- Autoren
- Shuvankar Mandal
- Abhishek Pramanik
- Sourav Dey
- Luca M Carrella
- Gopalan Rajaraman
- Eva Rentschler
- Sasankasekhar Mohanta
- Autoren-URL
- https://www.webofscience.com/api/gateway?GWVersion=2&SrcApp=fis-test-1&SrcAuth=WosAPI&KeyUT=WOS:000854643500001&DestLinkType=FullRecord&DestApp=WOS_CPL
- DOI
- 10.1039/d2dt02348b
- eISSN
- 1477-9234
- Externe Identifier
- Clarivate Analytics Document Solution ID: 5B6XS
- PubMed Identifier: 36106563
- ISSN
- 1477-9226
- Ausgabe der Veröffentlichung
- 38
- Zeitschrift
- DALTON TRANSACTIONS
- Paginierung
- 14753 - 14766
- Datum der Veröffentlichung
- 2022
- Status
- Published
- Titel
- Experimental and theoretical investigations on three Dy<SUP>III</SUP><sub>4</sub> single molecule magnets: structural and magneto-structural correlations
- Sub types
- Article
- Ausgabe der Zeitschrift
- 51
Datenquelle: Web of Science (Lite)
- Andere Metadatenquellen:
-
- Abstract
- <jats:p>The length of the chain of chelating carboxylate influences the deviation from the ideal geometry which, in turn, influences <jats:italic>U</jats:italic><jats:sub>eff</jats:sub> and <jats:italic>τ</jats:italic><jats:sub>0</jats:sub> values. <jats:italic>Ab initio</jats:italic> and DFT calculations provide an in-depth picture of exchange interactions and SMM properties.</jats:p>
- Autoren
- Shuvankar Mandal
- Abhishek Pramanik
- Sourav Dey
- Luca M Carrella
- Gopalan Rajaraman
- Eva Rentschler
- Sasankasekhar Mohanta
- DOI
- 10.1039/d2dt02348b
- eISSN
- 1477-9234
- ISSN
- 1477-9226
- Ausgabe der Veröffentlichung
- 38
- Zeitschrift
- Dalton Transactions
- Sprache
- en
- Online publication date
- 2022
- Paginierung
- 14753 - 14766
- Status
- Published online
- Herausgeber
- Royal Society of Chemistry (RSC)
- Herausgeber URL
- http://dx.doi.org/10.1039/d2dt02348b
- Datum der Datenerfassung
- 2024
- Titel
- Experimental and theoretical investigations on three Dy<sup>III</sup><sub>4</sub> single molecule magnets: structural and magneto-structural correlations
- Ausgabe der Zeitschrift
- 51
Datenquelle: Crossref
- Abstract
- The work in this report describes the syntheses, crystal structures, dc/ac magnetic behaviour, and theoretical calculations (both <i>ab initio</i> CASSCF and DFT) of three defect dicubane/planar butterfly type tetradysprosium(III) compounds of compositions [Dy<sup>III</sup><sub>4</sub>L<sub>4</sub>(μ<sub>3</sub>-OH)<sub>2</sub>(carboxylate)<sub>2</sub>(dmf)<sub>2</sub>] (carboxylate = formate (1), acetate (2), propionate (3)), where H<sub>2</sub>L = 2-(2-hydroxy-3-ethoxybenzylideneamino)phenol. In the butterfly type structures, two Dy<sup>III</sup> centres (Dy<sub>b</sub>) occupy the body positions while two other (Dy<sub>w</sub>) units occupy the wing positions. SHAPE analyses reveal that the coordination geometries of the Dy<sub>b</sub> and Dy<sub>w</sub> centres, both octacoordinated, are triangular dodecahedron (TDD) and square antiprism (SAPR), respectively. Variable-temperature magnetic susceptibility measurements give an indication of weak antiferromagnetic interactions and variable-field magnetization measurements reveal strong anisotropy in all the three compounds. The variable-temperature/frequency in-phase/out-of-phase AC susceptibility data reveal that all these three compounds are SMMs with two relaxation channels under zero dc field; slow relaxation (SR) and fast relaxation (FR) processes could be assigned to the SAPR (Dy<sub>w</sub>) and TDD (Dy<sub>b</sub>) metal centres, respectively. The simulated <i>U</i><sub>eff</sub> and <i>τ</i><sub>0</sub> values are: 49.0 cm<sup>-1</sup> and 1.76 × 10<sup>-7</sup> s for 1, 30.3 cm<sup>-1</sup> and 1.51 × 10<sup>-8</sup> s for 2 and 23.4 cm<sup>-1</sup> and 9.64 × 10<sup>-7</sup> s for 3. Furthermore, <i>ab initio</i> CASSCF/RASSI-SO/SINGLE_ANISO calculations reveal that the ground state of Dy<sup>III</sup> centres are axial in nature with a dominating contribution from <i>m</i><sub><i>J</i></sub> = |±15/2>. The magnetization relaxation occurs <i>via</i> the first excited KD resulting in the large computed blocking barrier of Dy<sub>w</sub> (SAPR) centres compared to that of the Dy<sub>b</sub> (TDD) centres which corroborates the experimental measurements. The exchange parameters obtained from DFT calculations are generally in line with those obtained from the fitting of <i>χ</i><sub>M</sub><i>T vs. T</i> in POLY_ANISO calculations. Interesting structural and magneto-structural correlations have been found, which are the major outcomes of this investigation.
- Addresses
- Department of Chemistry, University of Calcutta, 92 A. P. C. Road, Kolkata 700 009, India. sm_cu_chem@yahoo.co.in.
- Autoren
- Shuvankar Mandal
- Abhishek Pramanik
- Sourav Dey
- Luca M Carrella
- Gopalan Rajaraman
- Eva Rentschler
- Sasankasekhar Mohanta
- DOI
- 10.1039/d2dt02348b
- eISSN
- 1477-9234
- Externe Identifier
- PubMed Identifier: 36106563
- Funding acknowledgements
- Department of Science and Technology, Ministry of Science and Technology, India: DST/SJF/CSA03/2018-10
- Council of Scientific and Industrial Research, India:
- Department of Science and Technology, Ministry of Science and Technology, India: SB/SJF/2019–20/12
- University of Calcutta: B. I. 75(11) and 76(4)
- Department of Science and Technology, Ministry of Science and Technology, India: SPR/2019/001145
- Indian Institute of Technology Bombay:
- Johannes Gutenberg-Universität Mainz:
- Open access
- false
- ISSN
- 1477-9226
- Ausgabe der Veröffentlichung
- 38
- Zeitschrift
- Dalton transactions (Cambridge, England : 2003)
- Sprache
- eng
- Medium
- Electronic
- Online publication date
- 2022
- Paginierung
- 14753 - 14766
- Datum der Veröffentlichung
- 2022
- Status
- Published
- Datum der Datenerfassung
- 2022
- Titel
- Experimental and theoretical investigations on three Dy<sup>III</sup><sub>4</sub> single molecule magnets: structural and magneto-structural correlations.
- Sub types
- Journal Article
- Ausgabe der Zeitschrift
- 51
Datenquelle: Europe PubMed Central
- Abstract
- The work in this report describes the syntheses, crystal structures, dc/ac magnetic behaviour, and theoretical calculations (both ab initio CASSCF and DFT) of three defect dicubane/planar butterfly type tetradysprosium(III) compounds of compositions [DyIII4L4(μ3-OH)2(carboxylate)2(dmf)2] (carboxylate = formate (1), acetate (2), propionate (3)), where H2L = 2-(2-hydroxy-3-ethoxybenzylideneamino)phenol. In the butterfly type structures, two DyIII centres (Dyb) occupy the body positions while two other (Dyw) units occupy the wing positions. SHAPE analyses reveal that the coordination geometries of the Dyb and Dyw centres, both octacoordinated, are triangular dodecahedron (TDD) and square antiprism (SAPR), respectively. Variable-temperature magnetic susceptibility measurements give an indication of weak antiferromagnetic interactions and variable-field magnetization measurements reveal strong anisotropy in all the three compounds. The variable-temperature/frequency in-phase/out-of-phase AC susceptibility data reveal that all these three compounds are SMMs with two relaxation channels under zero dc field; slow relaxation (SR) and fast relaxation (FR) processes could be assigned to the SAPR (Dyw) and TDD (Dyb) metal centres, respectively. The simulated Ueff and τ0 values are: 49.0 cm-1 and 1.76 × 10-7 s for 1, 30.3 cm-1 and 1.51 × 10-8 s for 2 and 23.4 cm-1 and 9.64 × 10-7 s for 3. Furthermore, ab initio CASSCF/RASSI-SO/SINGLE_ANISO calculations reveal that the ground state of DyIII centres are axial in nature with a dominating contribution from mJ = |±15/2>. The magnetization relaxation occurs via the first excited KD resulting in the large computed blocking barrier of Dyw (SAPR) centres compared to that of the Dyb (TDD) centres which corroborates the experimental measurements. The exchange parameters obtained from DFT calculations are generally in line with those obtained from the fitting of χMT vs. T in POLY_ANISO calculations. Interesting structural and magneto-structural correlations have been found, which are the major outcomes of this investigation.
- Autoren
- Shuvankar Mandal
- Abhishek Pramanik
- Sourav Dey
- Luca M Carrella
- Gopalan Rajaraman
- Eva Rentschler
- Sasankasekhar Mohanta
- Autoren-URL
- https://www.ncbi.nlm.nih.gov/pubmed/36106563
- DOI
- 10.1039/d2dt02348b
- eISSN
- 1477-9234
- Ausgabe der Veröffentlichung
- 38
- Zeitschrift
- Dalton Trans
- Sprache
- eng
- Country
- England
- Paginierung
- 14753 - 14766
- Datum der Veröffentlichung
- 2022
- Status
- Published online
- Titel
- Experimental and theoretical investigations on three DyIII4 single molecule magnets: structural and magneto-structural correlations.
- Sub types
- Journal Article
- Ausgabe der Zeitschrift
- 51
Datenquelle: PubMed
- Beziehungen:
- Eigentum von