Mechanically interlocked air-stable radicals

Patent metadata

Field	Value
Publication number	US-10867718-B2
Application number	US-201816032212-A
Country	US
Kind code	B2
Filing date	Jul 11, 2018
Priority date	Jul 11, 2017
Publication date	Dec 15, 2020
Grant date	Dec 15, 2020

Abstract

Provided herein are mechanically interlocked air-stable persistent organic radicals. The radical compositions may access a multiplicity of radical, cationic redox states as well as a fully cationic redox state. A composition comprises a first ring mechanically interlocked with a second ring or a salt thereof, wherein the first ring comprises a 4,4′-bipyridinium subunit or a derivative thereof and a diazapyrenium subunit or a derivative thereof and the second ring comprises a 4,4′-bipyridinium subunit or a derivative thereof. In some embodiments, the second ring further comprises a diazapyrenium subunit or a derivative thereof. Methods of preparing the compositions are also provided.

First claim

We claim:

1. A salt comprising a mechanically interlocked molecule characterized by a monoradical heptacationic oxidation state and seven counteranions per mechanically interlocked molecule,
wherein the mechanically interlocked molecule comprises a first ring mechanically interlocked with a second ring,
wherein the first ring comprises (i) a 4,4′-bipyridinium subunit or a derivative thereof and (ii) a diazapyrenium subunit or a derivative thereof;
wherein the second ring comprises (i) a 4,4′-bipyridinium subunit or a derivative thereof and (ii) a diazapyrenium subunit or a derivative thereof or a 4,4′-bipyridinium subunit or a derivative thereof; and
wherein the mechanically interlocked molecule is an air-stable radical characterized by seven nitrogen in a cationic state and one nitrogen having an unpaired electron.

2. The salt of claim 1 , wherein the first ring comprises a compound of Formula III,

or a derivative thereof,
wherein the first ring is characterized as a tetracation and each nitrogen is in the cationic state or the first ring is characterized as a monoradical triscation and three nitrogen are in the cationic state and one nitrogen has the unpaired electron.

3. The salt of claim 1 , wherein the second ring comprises (i) a compound of Formula III,

or a derivative thereof or (ii) a compound of Formula IV,

or a derivative thereof,
wherein the second ring is characterized as a tetracation and each nitrogen is in the cationic state or the second ring is characterized as a monoradical triscation and three nitrogen are in the cationic state and one nitrogen has the unpaired electron.

4. The salt of claim 1 , wherein the mechanically interlocked molecule comprises a composition of Formula V,

or a derivative thereof.

5. The salt of claim 1 , wherein the mechanically interlocked molecule comprises a composition of formula VI,

or a derivative thereof.

6. The salt of claim 1 , wherein the counteranion is PF 6 —.

7. The salt of claim 1 , wherein the salt is prepared by (a) providing a radical cationic inclusion complex and reacting the complex with (i) 2,7-diazapyrene, (ii) 4,4′-bipyridine, or a derivative of either (i) or (ii).

8. A crystalline composition comprising the salt of claim 1 having a molecular packing arrangement defined by triclinic space group P 1 (no. 2).

9. The crystalline composition of claim 8 , wherein the composition has lattice parameters of a=13.5±0.1 Å, b=16.5±0.1 Å, c=22.5±0.1 Å, α=86.1±0.1°, β=88.9±0.1°, γ=82.5±0.1°.

10. The crystalline composition of claim 8 , wherein the composition has lattice parameters of a=13.3±0.1 Å, b=27.9±0.1 Å, c=31.5±0.1 Å, α=73.4±0.1°, β=89.8±0.1°, γ=81.0±0.1°.

11. A memory device comprising the salt of claim 1 .

Assignees

• Univ Northwestern

Inventors

• Liu Zhichang
• Sun Junling
• Stoddart James Fraser

Classifications

• C30B29/54

  Organic compounds · CPC title

• C07D401/14

  containing three or more hetero rings · CPC title

• C30B7/00

  Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions (from molten solvents C30B9/00; by normal or gradient freezing C30B11/00; under a protective fluid C30B27/00) · CPC title

• C07D519/00 Primary

  Heterocyclic compounds containing more than one system of two or more relevant hetero rings condensed among themselves or condensed with a common carbocyclic ring system not provided for in groups C07D453/00 or C07D455/00 · CPC title

• C07D471/06

  Peri-condensed systems · CPC title