Self-healing, luminescent metallogelation driven by synergistic metallophilic and fluorine-fluorine interactions

Square planar platinum( ii ) complexes are attractive building blocks for multifunctional soft materials due to their unique optoelectronic properties. However, for soft materials derived from synthetically simple discrete metal complexes, achieving a combination of optical properties, thermorespons...

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Bibliographic Details
Published in:Soft matter 2020-03, Vol.16 (11), p.2795-282
Main Authors: Kolari, Kalle, Bulatov, Evgeny, Tatikonda, Rajendhraprasad, Bertula, Kia, Kalenius, Elina, Nonappa, Haukka, Matti
Format: Article
Language:English
Subjects:
Coordination compounds
Crystallography
Fluorine
Gelation
Gels
Handedness
Ligands
Luminescence
Materials recovery
Mechanical properties
Metal complexes
Nanofibers
NMR
Nuclear magnetic resonance
Optical materials
Optical properties
Optics
Optoelectronics
Perfluoroalkyl & polyfluoroalkyl substances
Photomicrographs
Platinum
Rheological properties
Rheology
Single crystals
Storage modulus
Superstructures
X-ray diffraction
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Summary:Square planar platinum( ii ) complexes are attractive building blocks for multifunctional soft materials due to their unique optoelectronic properties. However, for soft materials derived from synthetically simple discrete metal complexes, achieving a combination of optical properties, thermoresponsiveness and excellent mechanical properties is a major challenge. Here, we report the rapid self-recovery of luminescent metallogels derived from platinum( ii ) complexes of perfluoroalkyl and alkyl derivatives of terpyridine ligands. Using single crystal X-ray diffraction studies, we show that the presence of synergistic platinum-platinum (Pt Pt) metallopolymerization and fluorine-fluorine (F F) interactions are the major driving forces in achieving hierarchical superstructures. The resulting bright red gels showed the presence of highly entangled three-dimensional networks and helical nanofibres with both ( P and M ) handedness. The gels recover up to 87% of their original storage modulus even after several cycles under oscillatory step-strain rheological measurements showing rapid self-healing. The luminescence properties, along with thermo- and mechanoresponsive gelation, provide the potential to utilize synthetically simple discrete complexes in advanced optical materials. Aggregation and self-assembly of terpyridine platinum( ii ) complex with fluorinated alkyl substituent, driven by synergistic metallophilic and fluorophilic interactions, result in formation of a robust, self-healing, and luminescent gel.
ISSN:1744-683X
1744-6848
DOI:10.1039/c9sm02186h