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CN-122010987-A - Binuclear dysprosium single-molecule magnet with solvent molecule magnetic response and synthesis method and application thereof

CN122010987ACN 122010987 ACN122010987 ACN 122010987ACN-122010987-A

Abstract

The invention relates to a binuclear dysprosium single-molecule magnet with solvent molecular magnetic response, a synthesis method and application thereof, wherein a binuclear system with solvent response sites is directionally constructed by utilizing a nitrogen-oxygen pyridine Schiff base ligand and dysprosium ions for self-assembly. The single crystal of the material can undergo reversible single crystal to single crystal conversion in different solvent atmospheres, accompanied by reversible exchange of coordinating solvent molecules. The structural change directly causes reversible switching of macroscopic magnetic properties, and realizes 'non-invasive' dynamic regulation and control of magnetic relaxation behavior.

Inventors

  • Jiang Zichan
  • MA FANG
  • LIN YUYANG
  • HU BO

Assignees

  • 宁波职业技术大学

Dates

Publication Date
20260512
Application Date
20251215

Claims (10)

  1. 1. A binuclear dysprosium single-molecule magnet, characterized in that the binuclear dysprosium single-molecule magnet has a molecular formula structure of one of: complex 1 { [ Dy (o-pcbs) (CH) 3 OH)(H 2 O) 3 ]·2Br·H 2 O} 2 Complex 2 { [ Dy (o-pcbs) (CH 3 OH) 2 (H 2 O) 2 ]·2Br·CH 3 CN} 2 ; wherein o-pcbs represents a 2-nitroxypyridyl- (2-hydroxy) phenylhydrazone Schiff base.
  2. 2. The binuclear dysprosium single-molecule magnet according to claim 1, wherein the complex 1 is crystallized in the P21/n space group with unit cell parameters of α=90°,β=95.410(3)°,γ=90°, Z=4, μ= 6.833mm -1 , F (000) = 1378.3, the complex 2 is crystallized in the P bca space group, the unit cell parameters are α=90°,β=90°,γ=90°, Z=8,μ=6.261mm -1 ,F(000)=2878.8。
  3. 3. The binuclear dysprosium single-molecule magnet according to claim 1, wherein the Dy-O bond length of complex 1 is as follows Within the Dy-O bond length of the complex 2 Range.
  4. 4. The binuclear dysprosium single-molecule magnet according to claim 1, wherein the complex 1 is a yellow bulk crystal and the complex 2 is a red bulk crystal.
  5. 5. The binuclear dysprosium single molecule magnet of claim 1, wherein complex 1 and complex 2 can undergo reversible interconversions in different solvent environments.
  6. 6. The binuclear dysprosium single molecule magnet of claim 1, wherein complex 1 is convertible to complex 2 in CH 3 OH solvent, and wherein complex 2 is convertible to complex 1 in CH 3 CN solvent.
  7. 7. The method for preparing the binuclear dysprosium single-molecule magnet according to any one of claims 1 to 6, comprising the following steps: Dissolving O-pcbs ligand in CH 3 CN, sequentially adding alkali or alkali solution and DyBr 3 ·6H 2 O, reacting to obtain yellow solution, filtering the yellow solution, and volatilizing at room temperature until yellow massive crystals are separated out, namely the complex 1; Adding CH 3 CN solvent to the solution containing yellow bulk crystal or directly soaking the yellow bulk crystal in CH 3 CN solvent until the yellow crystal bulk is changed into red crystal bulk, namely complex 2.
  8. 8. The method for preparing the binuclear dysprosium single-molecule magnet according to claim 7, wherein the molar ratio of the O-pcbs ligand, dyBr 3 ·6H 2 O and alkali is 1 (1-1.2): 1-1.2.
  9. 9. The method for preparing the binuclear dysprosium single-molecule magnet according to claim 7, wherein the alkali is one or more selected from potassium hydroxide, sodium hydroxide, triethylamine, ammonium hydroxide and the like, and the solvent in the alkali solution is CH 3 OH, diethyl ether or CH 3 CN.
  10. 10. The use of the binuclear dysprosium single-molecule magnet of claims 1-6 for preparing a dynamic smart material with external solvent response.

Description

Binuclear dysprosium single-molecule magnet with solvent molecule magnetic response and synthesis method and application thereof Technical Field The invention relates to the technical field of preparation of molecular-based magnetic materials, in particular to a binuclear dysprosium single-molecule magnet with solvent molecular magnetic response, and a synthesis method and application thereof. Background The single-molecule magnet is a novel molecular magnetic material which presents magnetic bistable state and slow magnetic relaxation phenomenon at molecular scale. Particularly, when dysprosium ions with strong magnetic anisotropy are selected as spin sources, the material not only shows outstanding magnetic properties and rich relaxation dynamics behaviors, but also shows important research potential and practical application prospect in the front fields of high-density information storage, quantum computation and the like. According to the different number of dysprosium spin centers, the dysprosium spin centers can be divided into a mononuclear dysprosium single-ion magnet, a binuclear dysprosium molecular magnet and a polynuclear dysprosium molecular magnet. Among the above classes, the binuclear dysprosium single-molecule magnet has the unique structural advantages that on one hand, single-ion magnetic anisotropy of dysprosium ions can be accurately regulated and controlled through a coordination field, and on the other hand, magnetic exchange effect between two dysprosium ions can be regulated by means of bridging ligands, so that quantum tunneling effect is obviously inhibited, and effective optimization of magnetic relaxation behavior and overall performance is realized. Through the magnetic-structural relation research of a single-molecule magnet system, the coordination environment, coordination configuration and strength of a coordination field around dysprosium ions determine the arrangement of ground state multiple state subenergy levels, and the arrangement is one of the causes of the magnetic anisotropy of dysprosium ions. The regulation and control of the magnetic properties of the single-molecule magnet are one of the core research issues for pushing the single-molecule magnet to practical application. The existing regulation and control methods are various, and comprise functional group modification of ligand structures, replacement of metal ion types and even optimization of the whole molecular crystal stacking mode. Once these methods are implemented, the molecular structure and macroscopic properties of the material are fixed, dynamic tunability is lacking, and the synthesis process often requires redesign and complicated steps. Despite the diversity of regulatory strategies, the use of mild, reversible external stimuli (such as solvent environmental changes) to achieve precise, dynamic regulation of single-molecule magnet structure and magnetic behavior remains a great challenge. This is mainly because in molecular crystals, solvent molecules are often randomly or randomly encapsulated, and it is difficult to achieve ordered, reversible intercalation and deintercalation of solvent molecules, and thus cause significant changes in coordination environment and magnetic anisotropy. Therefore, a novel intelligent molecular magnet capable of generating sensitive and reversible magnetic response to solvent environment is developed, and precious opportunities are provided for understanding the relationship between the structure and the performance at the molecular level. Disclosure of Invention Based on the shortcomings of the prior art, the invention aims to provide a novel intelligent molecular magnet capable of generating sensitive and reversible magnetic response to a solvent environment. The invention solves the technical problems by adopting the following scheme: a binuclear dysprosium single molecule magnet having a molecular formula structure of one of: complex 1 { [ Dy (o-pcbs) (CH) 3OH)(H2O)3]·2Br·H2O}2 Complex 2 { [ Dy (o-pcbs) (CH 3OH)2(H2O)2]·2Br·CH3CN}2; wherein o-pcbs represents a 2-nitroxypyridyl- (2-hydroxy) phenylhydrazone Schiff base. Further, the complex 1 is crystallized in the P21/n space group, and the unit cell parameter isα=90°,β=95.410(3)°,γ=90°,Z=4, μ= 6.833mm -1, F (000) = 1378.3, the complex 2 is crystallized in the P bca space group, the unit cell parameters areα=90°,β=90°,γ=90°,Z=8,μ=6.261mm-1,F(000)=2878.8。 Further, the asymmetric unit of the complex 1 consists of one Dy 3+ ion, one o-pcbs ligand, one coordinated methanol molecule, three coordinated water molecules, and bromide ions in two lattices and one lattice water molecule. Further, dy 3+ ion in the complex 1 is eight coordination, and is coordinated with two coordinated water molecules, one coordinated methanol molecule and imine nitrogen atom, and the phenolic hydroxyl oxygen atom, the carbonyl oxygen atom and one oxygen atom from the water molecules are located in the axial direction at the equatorial p