Mononuclear Dysprosium(III) Complexes with Triphenylphosphine Oxide Ligands: Controlling the Coordination Environment and Magnetic Anisotropy
We report the synthesis, structural and magnetic characterization of five mononuclear DyIII ion complexes using triphenylphosphine oxide as a monodentate ligand. They have formulae [DyIII(OPPh3)3(NO3)3] (1), [DyIII(OPPh3)4(NO3)2](NO3) (2), [DyIII(OPPh3)3Cl3] (3), [DyIII(OPPh3)4Cl2]Cl (4) and [DyIII(...
| Main Authors: | , , , , , , , , |
|---|---|
| Format: | Article |
| Language: | English |
| Published: |
MDPI AG
2018-06-01
|
| Series: | Inorganics |
| Subjects: | |
| Online Access: | http://www.mdpi.com/2304-6740/6/2/61 |
| _version_ | 1819211097342738432 |
|---|---|
| author | Stuart K. Langley Kuduva R. Vignesh Kerey Holton Sophie Benjamin Gary B. Hix Wasinee Phonsri Boujemaa Moubaraki Keith S. Murray Gopalan Rajaraman |
| author_facet | Stuart K. Langley Kuduva R. Vignesh Kerey Holton Sophie Benjamin Gary B. Hix Wasinee Phonsri Boujemaa Moubaraki Keith S. Murray Gopalan Rajaraman |
| author_sort | Stuart K. Langley |
| collection | DOAJ |
| description | We report the synthesis, structural and magnetic characterization of five mononuclear DyIII ion complexes using triphenylphosphine oxide as a monodentate ligand. They have formulae [DyIII(OPPh3)3(NO3)3] (1), [DyIII(OPPh3)4(NO3)2](NO3) (2), [DyIII(OPPh3)3Cl3] (3), [DyIII(OPPh3)4Cl2]Cl (4) and [DyIII(OPPh3)4Cl2](FeCl4) (5). These complexes are characterized using single crystal X-ray diffraction, which revealed that each complex has a unique coordination environment around the DyIII ion, which results in varying dynamic magnetic behavior. Ab initio calculations are performed to rationalize the observed magnetic behavior and to understand the effect that the ligand and coordination geometry around the DyIII ion has on the single-molecule magnet (SMM) behavior. In recent years, seven coordinate DyIII complexes possessing pseudo ~D5h symmetry are found to yield attractive blocking temperatures for the development of new SMM complexes. However, here we show that the strength of the donor ligand plays a critical role in determining the effective energy barrier and is not simply dependent on the geometry and the symmetry around the DyIII ion. Seven coordinate molecules possessing pseudo D5h symmetry with strong equatorial ligation and weak axial ligation are found to be inferior, exhibiting no SMM characteristics under zero-field conditions. Thus, this comprehensive study offers insight on improving the blocking temperature of mononuclear SMMs. |
| first_indexed | 2024-12-23T06:21:39Z |
| format | Article |
| id | doaj.art-c20f7f1d6ffd4505afd129331f52bcca |
| institution | Directory Open Access Journal |
| issn | 2304-6740 |
| language | English |
| last_indexed | 2024-12-23T06:21:39Z |
| publishDate | 2018-06-01 |
| publisher | MDPI AG |
| record_format | Article |
| series | Inorganics |
| spelling | doaj.art-c20f7f1d6ffd4505afd129331f52bcca2022-12-21T17:57:10ZengMDPI AGInorganics2304-67402018-06-01626110.3390/inorganics6020061inorganics6020061Mononuclear Dysprosium(III) Complexes with Triphenylphosphine Oxide Ligands: Controlling the Coordination Environment and Magnetic AnisotropyStuart K. Langley0Kuduva R. Vignesh1Kerey Holton2Sophie Benjamin3Gary B. Hix4Wasinee Phonsri5Boujemaa Moubaraki6Keith S. Murray7Gopalan Rajaraman8School of Science and the Environment, Division of Chemistry, Manchester Metropolitan University, Manchester M15 6BH, UKDepartment of Chemistry, IIT Bombay, Mumbai 400076, IndiaSchool of Science and the Environment, Division of Chemistry, Manchester Metropolitan University, Manchester M15 6BH, UKSchool of Science and Technology, Nottingham Trent University, Nottingham NG11 8NS, UKSchool of Sciences, University of Wolverhampton, Wolverhampton WV1 1LY, UKSchool of Chemistry, Monash University, Clayton, VIC 3800, AustraliaSchool of Chemistry, Monash University, Clayton, VIC 3800, AustraliaSchool of Chemistry, Monash University, Clayton, VIC 3800, AustraliaDepartment of Chemistry, IIT Bombay, Mumbai 400076, IndiaWe report the synthesis, structural and magnetic characterization of five mononuclear DyIII ion complexes using triphenylphosphine oxide as a monodentate ligand. They have formulae [DyIII(OPPh3)3(NO3)3] (1), [DyIII(OPPh3)4(NO3)2](NO3) (2), [DyIII(OPPh3)3Cl3] (3), [DyIII(OPPh3)4Cl2]Cl (4) and [DyIII(OPPh3)4Cl2](FeCl4) (5). These complexes are characterized using single crystal X-ray diffraction, which revealed that each complex has a unique coordination environment around the DyIII ion, which results in varying dynamic magnetic behavior. Ab initio calculations are performed to rationalize the observed magnetic behavior and to understand the effect that the ligand and coordination geometry around the DyIII ion has on the single-molecule magnet (SMM) behavior. In recent years, seven coordinate DyIII complexes possessing pseudo ~D5h symmetry are found to yield attractive blocking temperatures for the development of new SMM complexes. However, here we show that the strength of the donor ligand plays a critical role in determining the effective energy barrier and is not simply dependent on the geometry and the symmetry around the DyIII ion. Seven coordinate molecules possessing pseudo D5h symmetry with strong equatorial ligation and weak axial ligation are found to be inferior, exhibiting no SMM characteristics under zero-field conditions. Thus, this comprehensive study offers insight on improving the blocking temperature of mononuclear SMMs.http://www.mdpi.com/2304-6740/6/2/61single molecule magnetssingle ion magnetsphosphine oxide complexeslanthanide SMMsmagnetic anisotropyab initio calculations |
| spellingShingle | Stuart K. Langley Kuduva R. Vignesh Kerey Holton Sophie Benjamin Gary B. Hix Wasinee Phonsri Boujemaa Moubaraki Keith S. Murray Gopalan Rajaraman Mononuclear Dysprosium(III) Complexes with Triphenylphosphine Oxide Ligands: Controlling the Coordination Environment and Magnetic Anisotropy Inorganics single molecule magnets single ion magnets phosphine oxide complexes lanthanide SMMs magnetic anisotropy ab initio calculations |
| title | Mononuclear Dysprosium(III) Complexes with Triphenylphosphine Oxide Ligands: Controlling the Coordination Environment and Magnetic Anisotropy |
| title_full | Mononuclear Dysprosium(III) Complexes with Triphenylphosphine Oxide Ligands: Controlling the Coordination Environment and Magnetic Anisotropy |
| title_fullStr | Mononuclear Dysprosium(III) Complexes with Triphenylphosphine Oxide Ligands: Controlling the Coordination Environment and Magnetic Anisotropy |
| title_full_unstemmed | Mononuclear Dysprosium(III) Complexes with Triphenylphosphine Oxide Ligands: Controlling the Coordination Environment and Magnetic Anisotropy |
| title_short | Mononuclear Dysprosium(III) Complexes with Triphenylphosphine Oxide Ligands: Controlling the Coordination Environment and Magnetic Anisotropy |
| title_sort | mononuclear dysprosium iii complexes with triphenylphosphine oxide ligands controlling the coordination environment and magnetic anisotropy |
| topic | single molecule magnets single ion magnets phosphine oxide complexes lanthanide SMMs magnetic anisotropy ab initio calculations |
| url | http://www.mdpi.com/2304-6740/6/2/61 |
| work_keys_str_mv | AT stuartklangley mononucleardysprosiumiiicomplexeswithtriphenylphosphineoxideligandscontrollingthecoordinationenvironmentandmagneticanisotropy AT kuduvarvignesh mononucleardysprosiumiiicomplexeswithtriphenylphosphineoxideligandscontrollingthecoordinationenvironmentandmagneticanisotropy AT kereyholton mononucleardysprosiumiiicomplexeswithtriphenylphosphineoxideligandscontrollingthecoordinationenvironmentandmagneticanisotropy AT sophiebenjamin mononucleardysprosiumiiicomplexeswithtriphenylphosphineoxideligandscontrollingthecoordinationenvironmentandmagneticanisotropy AT garybhix mononucleardysprosiumiiicomplexeswithtriphenylphosphineoxideligandscontrollingthecoordinationenvironmentandmagneticanisotropy AT wasineephonsri mononucleardysprosiumiiicomplexeswithtriphenylphosphineoxideligandscontrollingthecoordinationenvironmentandmagneticanisotropy AT boujemaamoubaraki mononucleardysprosiumiiicomplexeswithtriphenylphosphineoxideligandscontrollingthecoordinationenvironmentandmagneticanisotropy AT keithsmurray mononucleardysprosiumiiicomplexeswithtriphenylphosphineoxideligandscontrollingthecoordinationenvironmentandmagneticanisotropy AT gopalanrajaraman mononucleardysprosiumiiicomplexeswithtriphenylphosphineoxideligandscontrollingthecoordinationenvironmentandmagneticanisotropy |