@article{01HZKSW4WGP3SSY1R5KXTH6FJF,
  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 1 and 2. The solvate molecule-free crystals of 1 undergo topochemical photopolymerization via an unusual olefin-naphthyl ring [2 + 2] cyclization to yield the single crystalline [3]-ladderane polymer 1P growing 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 2 quantitatively polymerize to a B <- N bond-stabilized polymer 2P in a SCSC fashion owing to the rapid [2 + 2] cycloaddition reaction among olefin double bonds. Such olefin bonds in the crystals of 2 are suitably preorganized for photoreaction due to the presence of solvate molecules in the crystal packing. Single crystals of 2 also 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}},
  author       = {{Bhandary, Subhrajyoti and Beliš, Marek and  Shukla, Rahul and Bourda, Laurens and Kaczmarek, Anna and Van Hecke, Kristof}},
  issn         = {{0002-7863}},
  journal      = {{JOURNAL OF THE AMERICAN CHEMICAL SOCIETY}},
  keywords     = {{X-RAY-DIFFRACTION,SOLID-STATE,TOPOCHEMICAL POLYMERIZATIONS,CYCLOADDITION REACTION,PHOTOPOLYMERIZATION,PHOTODIMERIZATION,COORDINATION}},
  language     = {{eng}},
  number       = {{12}},
  pages        = {{8659--8667}},
  title        = {{Single-crystal-to-single-crystal photosynthesis of supramolecular organoboron polymers with dynamic effects}},
  url          = {{http://doi.org/10.1021/jacs.4c00978}},
  volume       = {{146}},
  year         = {{2024}},
}

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