Heteroleptic chiral bis(phthalocyaninato) terbium double-decker single-ion magnets

Abstract

Chiral binaphthyl and dibutylamino were incorporated onto the periphery of the bis(phthalocyaninato) terbium SIM, confirming the effectiveness of tuning the double-decker SIM peroperties thorugh tuning the molecular magnetic anisotropy.

Single‐Ion Magnet Investigation of ABAB‐Type Tetrachloro‐ and Tetraalkoxy‐Substituted Bis(phthalocyaninato) Terbium Double‐Decker with D2 Symmetrical Ligand Field

“…Interestingly, butterfly‐shaped magnetic hysteresis loops are found at 2 K for 1 with three different sweep rates (100, 200, and 500 Oe/s) of the magnetic field, reconfirming its SIM nature. The hysteresis loop becomes narrower along with decrease of the sweep rate and increase of the temperature, which is in agreement with previously reported SMMs . As can be seen clearly in the bottom of Figure , the magnetic hysteresis loop for 1 could still be observed even at the temperature as high as 15 K with the sweep rate of 500 Oe/s.…”

Bis[1,8,15,22-tetrakis(3-pentyloxy)phthalocyaninato]terbium Double-Decker Single-Ion Magnets

“…As a result, we have tried to pursue the help of theoretical calculation and introduce the term of “the static electronic potential around the lanthanide ion” to evaluate the coordination field strength. Previous investigation has revealed that the greater static electronic potential around the lanthanide ion well explains the enhanced magnetic function of sandwich-type bis­(phthalocyaninato)­lanthanide SIMs. ,, In the present case, DFT calculations were also conducted for TbH­[Pc­(α-OC 5 H 11 ) 4 ] 2 ( 1 ) and Tb­[Pc­(α-OC 5 H 11 ) 4 ] 2 ( 2 ) to further understand their SIM behaviors on the basis of the single-crystal molecular structure of 2 . It is noteworthy that, for the purpose of simplifying the calculation, the substitution of OC 3 H 7 instead of OC 5 H 11 was carried out for the potential calculation.…”

Rare-earth based tetrapyrrolic sandwiches: chemistry, materials and applications

“…In the same manner, erbium(III) complex [(Bu 2 N) 8 Pc]Er(Pc) was also synthesized and its anionic form was a first sandwichtype phthalocyanine-based erbium(III) compound with fieldinduced slow relaxation. 82 Chiral heteroleptic complex was synthesized in a similar manner by the reaction of [(Bu 2 N) 8 Pc]Tb(acac) with H 2 [(BNPO) 4 Pc], 83 and it also revealed excellent SMM characteristics. Such superior SMM behaviour of amino-substituted complexes was explained using DFT calculations in terms of the electrostatic effects of electron-rich ligands.…”

“…Chiral heteroleptic complex was synthesized in a similar manner by the reaction of [(Bu 2 N) 8 Pc]Tb(acac) with H 2 [(BNPO) 4 Pc] , 83 and it also revealed excellent SMM characteristics. Such superior SMM behaviour of amino-substituted complexes was explained using DFT calculations in terms of the electrostatic effects of electron-rich ligands.…”