Supramolecular tessellation of rigid triangular macrocycles

Patent metadata

Field	Value
Publication number	US-11560644-B2
Application number	US-202017006031-A
Country	US
Kind code	B2
Filing date	Aug 28, 2020
Priority date	Aug 28, 2019
Publication date	Jan 24, 2023
Grant date	Jan 24, 2023

Abstract

Disclosed herein are crystalline compositions comprising tessellated rigid triangular macrocycles in a two-dimensional plane and methods of making the same.

First claim

The invention claimed is:

1. A crystalline composition comprising a plurality of tessellated rigid triangular macrocycles in a two-dimensional plane, wherein the rigid triangular macrocycle is NDI-Δ.

2. The crystalline composition of claim 1 , wherein the crystalline composition has hexagonal symmetry in a plane.

3. The crystalline composition of claim 1 , wherein each rigid triangular macrocycle of the crystalline composition interacts via face-to-face [π . . . π] interactions with three other rigid triangular macrocycles in the two-dimensional plane.

4. The crystalline composition of claim 1 , wherein the crystalline composition has a molecular packing arrangement defined by space group P1 and has a molecular packing arrangement defined by unit cell dimensions a=8.7±0.1 Å, b=18.3±0.1 Å, c=18.9±0.1 Å, α=62.2±0.1°, β=85.0±0.1°, and γ=77.4±0.1°.

5. The crystalline composition of claim 1 , wherein the crystalline composition has a molecular packing arrangement defined by space group P6 2 and has a molecular packing arrangement defined by unit cell dimensions a=34.5±0.1 Å, b=34.5±0.1 Å, c=8.5±0.1 Å, α=90.0±0.1°, β=90.0±0.1°, and γ=90.0±0.1°.

6. The crystalline composition of claim 1 further comprising a plurality of π-electron donors.

7. The crystalline composition of claim 6 , wherein the π-electron donor is tetrathiafulvalene.

8. The crystalline composition of claim 6 , wherein the rigid triangular macrocycle and the π-electron donor form a host-guest inclusion complex.

9. The crystalline composition of claim 8 , wherein the crystalline composition has a molecular packing arrangement defined by space group P-1 and has a molecular packing arrangement defined by unit cell dimensions a=15.9±0.1 Å, b=16.0±0.1 Å, c=16.8±0.1 Å, α=69.4±0.1°, β=69.3±0.1°, and γ=71.0±0.1°.

10. The crystalline composition of claim 6 , wherein the crystalline composition comprises two crystallographically distinct rigid triangular macrocycles.

11. The crystalline composition of claim 10 , wherein crystalline composition has (i) a first layer comprising the rigid triangular macrocycle and the π-electron donor and (ii) a second layer comprising the rigid triangular macrocycle and lacking the π-electron donor.

12. The crystalline composition of claim 10 , wherein the crystalline composition has a molecular packing arrangement defined by space group P32 1 and has a molecular packing arrangement defined by unit cell dimensions a=19.2±0.1 Å, b=19.2±0.1 Å, c=15.5±0.1 Å, α=90.0±0.1°, β=90.0±0.1°, and γ=90.0±0.1°.

13. The crystalline composition of claim 12 , wherein the crystalline composition comprises a supramolecular triangle formed from π-electron donors.

14. The crystalline composition of claim 13 , wherein the three π-electron donors of the supramolecular triangle have mixed-valence character.

15. The crystalline composition of claim 13 , wherein the crystalline composition has a molecular packing arrangement defined by space group P2 1 /n and has a molecular packing arrangement defined by unit cell dimensions a=18.1±0.1 Å, b=15.6±0.1 Å, c=27.3±0.1 Å, α=90.0±0.1°, β=91.2±0.1°, and γ=90.0±0.1°.

16. A method for the preparation of a crystalline composition, the method comprising providing a solution comprising a rigid triangular macrocycle and a solvent;
and diffusing a precipitant or evaporating the solvent under conditions sufficient for the formation a crystalline composition comprising a plurality of tessellated rigid triangular macrocycles in a two-dimensional plane.

17. The method of claim 16 , wherein the rigid triangular macrocycle is NDI-Δ.

18. The method of claim 16 , wherein the solution further comprises a π-electron donor and wherein the crystalline composition comprises the plurality of tessellated rigid triangular macrocycles in a two-dimensional plane and a plurality of π-electron donors.

19. The method of claim 18 , wherein the π-electron donor is tetrathiafulvalene.

Assignees

• Univ Northwestern
• King Abdulaziz City Sci & Tech
• King Abdulaziz City For Science And Tech Kacst

Inventors

• Stoddart James Fraser
• Beldjoudi Yassine

Classifications

• C30B29/66

  Crystals of complex geometrical shape, e.g. tubes, cylinders · CPC title

• C30B29/54

  Organic compounds · CPC title

• C30B7/06

  using non-aqueous solvents · CPC title

• C30B29/68 Primary

  Crystals with laminate structure, e.g. "superlattices" · CPC title

• C30B29/58 Primary

  Macromolecular compounds · CPC title