Chiral π-Conjugated Double Helical Aminyl Diradical with the Triplet Ground State

Abstract

We describe effective development of the highly diastereoselective synthesis of double helical tetraamine 2-H₂-C₂ and propose a mechanism for its formation. The resolution of 2-H₂-C₂ is facilitated by a high racemization barrier of 43 kcal mol^–1 and it is implemented via either a chiral auxiliary or preparative supercritical fluid chromatography. This enables preparation of the first high-spin neutral diradical, with spin density delocalized within an enantiomeric double helical π-system. The presence of two effective 3-electron C–N bonds in the diradical leads to: (1) the triplet (S = 1) high-spin ground state with a singlet-triplet energy gap of 0.4 kcal mol^–1 and (2) the long half-life of up to 6 days in 2-MeTHF at room temperature. The diradical possesses a racemization barrier of at least 26 kcal mol^–1 in 2-MeTHF at 293 K and chiroptical properties, with an absorption anisotropy factor |g| ≈ 0.005 at 548 nm. These unique magnetic and optical properties of our diradical form the basis for the development of next-generation spintronic devices.

1 Introduction

2 Synthesis and Resolution of the C ₂-Symmetric Double Helical Tetraamine 2-H₂-C ₂

3 Synthesis and Characterization of Neutral High-Spin Aminyl Diradical 2^2• -C ₂

4 Conclusion

Key words

helical structures - radicals - chiral resolution - electrophilic aromatic substitution - electron transfer - oxidation - aminyl diradicals

Publication History

Received: 02 July 2024

Accepted: 05 August 2024

Accepted Manuscript online:
05 August 2024

Article published online:
02 September 2024

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