Journal
PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA
Volume 111, Issue 24, Pages 8717-8722Publisher
NATL ACAD SCIENCES
DOI: 10.1073/pnas.1408620111
Keywords
metal coordination; supramolecular coordination complex; photoirradiation; reversibility; dynamic materials
Categories
Funding
- National Basic Research Program [2013CB834502]
- National Natural Science Foundation of China [21125417, 21222210, 91027041]
- National Science Foundation [1212799]
- Division Of Chemistry
- Direct For Mathematical & Physical Scien [1212799] Funding Source: National Science Foundation
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Control over structural transformations in supramolecular entities by external stimuli is critical for the development of adaptable and functional soft materials. Herein, we have designed and synthesized a dipyridyl donor containing a central Z-configured stiff-stilbene unit that self-assembles in the presence of two 180 degrees di-Pt(II) acceptors to produce size-controllable discrete organoplatinum(II) metallacycles with high efficiency by means of the directional-bonding approach. These discrete metallacycles undergo transformation into extended metallosupramolecular polymers upon the conformational switching of the dipyridyl ligand from Z-configured (0 degrees) to E-configured (180 degrees) when photoirradiated. This transformation is accompanied by interesting morphological changes at nanoscopic length scales. The discrete metallacycles aggregate to spherical nanoparticles that evolve into long nanofibers upon polymer formation. These fibers can be reversibly converted to cyclic oligomers by changing the wavelength of irradiation, which reintroduces Z-configured building blocks owing to the reversible nature of stiff-stilbene photoisomerization. The design strategy defined here represents a novel self-assembly pathway to deliver advanced supramolecular assemblies by means of photocontrol.
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