Hetero-Diels–Alder reaction between singlet oxygen and anthracene drives integrative cage self-sorting

DOI: 10.1021/jacs.3c04228

Authors: Yuchong Yang (University of Cambridge) , Tanya K. Ronson (University of Cambridge) , Dingyu Hou (University College London) , Jieyu Zheng (University of Cambridge) , Ilma Jahović (University of Cambridge) , Kai Hong Luo (University of Cambridge) , Jonathan R. Nitschke (University of Cambridge)
Co-authored by industrial partner: No

Type: Journal Paper
Journal: Journal Of The American Chemical Society

State: Published (Approved)
Published: August 2023
Diamond Proposal Number(s): 21497

Abstract: A ZnII8L6 pseudocube containing anthracene-centered ligands, a ZnII4L′4 tetrahedron with a similar side length as the cube, and a trigonal prism ZnII6L3L′2 were formed in equilibrium from a common set of subcomponents. Hetero-Diels–Alder reaction with photogenerated singlet oxygen transformed the anthracene-containing “L” ligands into endoperoxide “LO” ones and ultimately drove the integrative self-sorting to form the trigonal prismatic cage ZnII6LO3L′2 exclusively. This ZnII6LO3L′2 structure lost dioxygen in a retro-Diels–Alder reaction after heating, which resulted in reversion to the initial ZnII8L6 + ZnII4L′4 ⇌ 2 × ZnII6L3L′2 equilibrating system. Whereas the ZnII8L6 pseudocube had a cavity too small for guest encapsulation, the ZnII6L3L′2 and ZnII6LO3L′2 trigonal prisms possessed peanut-shaped internal cavities with two isolated compartments divided by bulky anthracene panels. Guest binding was also observed to drive the equilibrating system toward exclusive formation of the ZnII6L3L′2 structure, even in the absence of reaction with singlet oxygen.

Subject Areas: Chemistry


Instruments: I19-Small Molecule Single Crystal Diffraction

Added On: 24/08/2023 14:36

Documents:
jacs.3c04228.pdf

Discipline Tags:

Molecular Complexes Chemistry Organometallic Chemistry

Technical Tags:

Diffraction Single Crystal X-ray Diffraction (SXRD)