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The First Series of Heterometallic Ln III ‐V IV Complexes Based on Substituted Malonic Acid Anions: Synthesis, Structure and Magnetic Properties
Author(s) -
Bazhina Evgeniya S.,
Aleksandrov Grigory G.,
Kiskin Mikhail A.,
Korlyukov Alexander A.,
Efimov Nikolay N.,
Bogomyakov Artem S.,
Starikova Alyona A.,
Mironov Vladimir S.,
Ugolkova Elena A.,
Minin Vadim V.,
Sidorov Alexey A.,
Eremenko Igor L.
Publication year - 2018
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.201801034
Subject(s) - chemistry , crystallography , antiferromagnetism , lanthanide , malonic acid , stereochemistry , ion , biochemistry , physics , organic chemistry , condensed matter physics
The reaction of VOSO 4 with K 2 cbdc (cbdc 2– is cyclobutane‐1,1‐dicarboxylate anion) and Ln(NO 3 ) 3 (Ln = La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Y, Er, Tm, Yb, Lu) yielded 17 novel heterometallic Ln III ‐V IV compounds comprising stable bis‐chelate units {V IV O(cbdc) 2 (H 2 O)}. Three structural types of compounds are formed depending on the nature of the rare‐earth metal: 1D polymers {[Ln(VO)(cbdc) 2 (H 2 O) 7 ] · 0.5[VO(cbdc) 2 ]} n (structural type I) [Ln = La ( 1 ), Ce ( 2 )], 3D polymers {[KLn(VO) 2 (cbdc) 4 (H 2 O) 9 ] · 3.5H 2 O} n (structural type II) [Ln = La ( 3 ), Ce ( 4 ), Pr ( 5 ), Nd ( 6 ), Sm ( 7 ), Eu ( 8 ), Gd ( 9 ), Tb ( 10 ), Dy ( 11 ), Ho ( 12 )] comprising trinuclear units {LnV 2 }, and octanuclear complexes {[KLn(VO) 2 (cbdc) 4 (H 2 O) 11 ] · 2H 2 O} 2 (structural type III) [Ln = Y ( 13 ), Er ( 14 ), Tm ( 15 ), Yb ( 16 ), Lu ( 17 )] containing dinuclear units {LnV}. Magnetic properties were investigated for all isolated compounds. The Gd III ‐V IV compound has ferromagnetic and antiferromagnetic exchange interactions between isotropic V IV and Gd III ions. Calculations using the DFT method at the UB3LYP/6‐31G(d,p)/SDD level of theory were performed in order to explain the different nature of exchange interactions in two Gd III ‐V IV pairs. The Yb III ‐V IV complex displays single‐molecule magnet properties; the effective energy barrier was estimated at Δ E eff /k B = 26 K. The magnetic properties of Ln III ‐V IV compounds with heavy lanthanide ions (Ln III = Er, Tm, Yb) were rationalized in terms of crystal‐field calculations for Ln III ions.