# US 12,180,231 B2 · Molecular magnetic material and a method for preparation thereof

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- Number: US 12,180,231 B2
- Document ID: US12180231B2
- Status: Granted
- Kind: B2
- Application number: 17/604,819
- Filed: 2020-04-09
- Published: 2022-06-09
- Granted: 2024-12-31
- Earliest claimed: 2019-04-25
- Assignees: Uniwersytet Jagiellonski
- Applicants: Uniwersytet Jagiellonski
- Inventors: Janusz Szklarzewicz; Maciej Hodorowicz
- Web page: https://patentgrep.com/patent/US12180231B2

## CPC

- C07F 11/00: Compounds containing elements of Groups 6 or 16 of the Periodic Table
- H01F 1/42: of organic or organo-metallic materials {, e.g. graphene}(H01F1/44 takes precedence)
- C07F: ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM (metal-containing porphyrins C07D487/22)
- H01F: MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES

## Abstract

A molecular magnetic material comprising salt molecules of a hexsacyanide tungsten anion complex of the formula: [WIV(CN)6(NN)]2-, a hexsacyanide tungsten anion complex of the formula: [WV(CN)6(NN)]—, wherein: W is a tungsten cation, CN is a cyano ligand, and NN is an NN-donating bidentate organic ligand forming a five-membered ring with the tungsten atom; and at least one type of a cation [A]n+¬, where n is an integer in the range of 1 to 4.

## Claims

### Claim 1

A method for preparing a molecular magnetic material, the method comprising the steps of:
providing a mixture of a hexacyanide tungsten anion complex of a formula [WIV(CN)6(NN)]2- and a hexacyanide tungsten anion complex of a formula [WV(CN)6(NN)]−,
wherein:
W is a tungsten cation,
CN is a cyano ligand, and
NN is an NN-donating bidentate organic ligand forming a five-membered ring with the tungsten atom;
adding to said mixture at least one type of a cation [A]n+, where n is an integer equal from 1 to 4, to form salt molecules comprising both anion complexes: [WIV(CN)6(NN)]2− and [WV(CN)6(NN)]− and the added cation [A]n+, wherein the cation [A]n+ is selected from the group consisting of Mn2+, Fe2+, Fe3+, Co2+, Ni2+, Ag+, Zn2+, Cd2+, Hg2+, TI2+, Pb2+, Cu2+, Ce3+, Ce4+, Nd3+, La3+, Pr3+, Sm3+, Gd3+, Tb3+, Dy3+, Er3+, Ho3+, Yb3+, Eu3+, H+, Na+, K+, Rb+, Cs+, Pb(bpy)2+, Pb(bpy)22+, Cd(bpy)2+, Cd(bpy)22+, and Zn(bpy)2+.

### Claim 2 (depends on 1)

The method according to claim 1 wherein the mixture of [WIV(CN)6(NN)]2− and [WV(CN)6(NN)]− is prepared by incomplete oxidation of [WIV(CN)6(NN)]2− to [WV(CN)6(NN)]− with an oxidizing agent.

### Claim 3 (depends on 2)

The method according to claim 2 wherein the oxidation is carried out with an oxidizing agent selected from a group consisting of H2O2, KMnO4 and Ce(NO3)4.

### Claim 4 (depends on 1)

The method according to claim 1 wherein the mixture of [WIV(CN)6(NN)]2− and [WV(CN)6(NN)]− is prepared by mixing an ion complex of a formula [WIV(CN)6(NN)]2− with an ion complex of a formula [WV(CN)6(NN)]−.

### Claim 5 (depends on 1)

The method according to claim 1, wherein the cation [A]n+ is added in a form of its salt selected from the group consisting of Cd(bpy)(NO3)2, Cd(NO3)2, Cd(NO3)2·4H2O, Zn(NO3)2, Zn(bpy)(NO3)2, ZnCl2, Pb(NO3)2, Cu(CH3COO)2, AgNO3, Gd(NO3)3, Tb(NO3)3, ErCl3, and Hg(NO3)2.

### Claim 6 (depends on 1)

The method according to claim 1, wherein the formed salt molecules comprising anion complexes: [WIV(CN)6(NN)]2− and [WV(CN)6(NN)]− and the cations [A]n+ are isolated from the reaction mixture by precipitation of the salt molecules or evaporation of the mixture solvent.