Influence of anion induced geometry change in Zn(ii) on the magnetization relaxation dynamics of Dy(iii) in Zn–Dy–Zn complexes. Issue 30 (21st July 2020)

• Record Type: Journal Article
• Authors: Shukla, Pragya; Ansari, Kamal Uddin; Gao, Chen; Vaidya, Shefali; Tripathi, Shalini; Kumar, Pardeep; Butcher, Ray J.; Overgaard, Jacob; Shanmugam, Maheswaran
• Is Part Of: Dalton transactions. Volume 49:Issue 30(2020)
• Page Start: 10580
• Page End: 10593
• Publication Date: 2020-07-21
• Subjects: Chemistry, Inorganic -- Periodicals; Chemistry, Physical and theoretical -- Periodicals; Chemistry, Inorganic -- Periodicals; 546.05
• DOI: 10.1039/d0dt00949k
• Languages: English
• ISSNs: 1477-9226

Abstract

Abstract : A series of [Zn2 Dy(L1 )2 (OAc)4 ](X) where X = (NO3 )0.92 (Br)0.08 (1 ), ClO4 (2 ), Cl (3 ) and PF6 (4 ) complexes were synthesized and their dc and ac magnetic data investigated. Experimental results are validated through MOLCAS calculations. Abstract : A family of hetero-trinuclear metal complexes with the general molecular formula [Zn2 Dy(L1 )2 (OAc)4 ] (X) where X = (NO3 )0.92 (Br)0.08 (1 ), ClO4 (2 ), Cl (3 ) and PF6 (4 ) were structurally characterized using a Schiff base ligand (HL1 ). The Dy(iii ) ion in 1–4 exhibits distorted square anti-prism geometry; however, the extent of distortion observed around Dy(iii ) in these complexes differ from each other. Consequently, 1–4 show distinct magnetization relaxation dynamics, with the anisotropic energy barrier of 25.4 cm −1, 12.9 cm −1, 14.08 cm −1 and 55.5 cm −1, respectively. The detailed electronic structure of 1–4 and the experimentally observed magnetization relaxation dynamics trends were rationalized using ab initio calculations. The detailed investigation discloses the non-zero influence of the anion themselves and the anion induced geometry change in Zn(ii ) affects the electronic structure of Dy(iii ), which in turn affects the magnetization relaxation dynamics. Overall, the study unveils an unprecedented methodology i.e. change in geometry of Zn(ii ) by altering the anion in the crystal lattice to modulate the relaxation dynamics of Dy(iii ).