Back to Search Start Over

Single-Crystal-to-Single-Crystal Photosynthesis of Supramolecular Organoboron Polymers with Dynamic Effects

Authors :
Bhandary, Subhrajyoti
Beliš, Marek
Shukla, Rahul
Bourda, Laurens
Kaczmarek, Anna M.
Van Hecke, Kristof
Source :
Journal of the American Chemical Society; 20240101, Issue: Preprints
Publication Year :
2024

Abstract

The solid-state synthesis of single-crystalline organic polymers, having functional properties, remains an attractive and developing research area in polymer chemistry and materials science. However, light-triggered topochemical synthesis of crystalline polymers comprising an organoboron backbone has not yet been reported. Here, we describe an intriguing example of single-crystal-to-single-crystal (SCSC) rapid photosynthesis (occurs on a seconds-scale) of two structurally different linear organoboron polymers, driven by environmentally sustainable visible/sun light, obtained from the same monomer molecule. A newly designed Lewis acid–base type molecular B ← N organoboron adduct (consisting of an organoboron core and naphthylvinylpyridine ligands) crystallizes in two solid-state forms featuring the same chemical structure but different 3D structural topologies, namely, monomers 1and 2. The solvate molecule-free crystals of 1undergo topochemical photopolymerization via an unusual olefin–naphthyl ring [2 + 2] cyclization to yield the single crystalline [3]-ladderane polymer 1Pgrowing along the B ← N linkages, accompanied by instantaneous and violent macroscopic mechanical motions or photosalient effects (such as bending-reshaping and jumping motions). In contrast, visible light-harvesting single crystals of 2quantitatively polymerize to a B ← N bond-stabilized polymer 2Pin a SCSC fashion owing to the rapid [2 + 2] cycloaddition reaction among olefin double bonds. Such olefin bonds in the crystals of 2are suitably preorganized for photoreaction due to the presence of solvate molecules in the crystal packing. Single crystals of 2also show photodynamic jumping motions - in response to visible light but in a relatively slower fashion than the crystals of 1. In addition to SCSC topochemical polymerization and dynamic motions, both monomer crystals and their single-crystalline polymers feature green emissive and short-lived room-temperature phosphorescence properties upon excitation with visible-light wavelength.

Details

Language :
English
ISSN :
00027863 and 15205126
Issue :
Preprints
Database :
Supplemental Index
Journal :
Journal of the American Chemical Society
Publication Type :
Periodical
Accession number :
ejs65594307
Full Text :
https://doi.org/10.1021/jacs.4c00978