- 标题
- 摘要
- 关键词
- 实验方案
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Fabrication of Large Single Crystals for Pt-Based Linear Polymers with Controlled-Release and Photoactuator Performance
摘要： Preparation of large single crystals for linear polymers that are amenable to X-ray analysis is very challenging in polymer science. Herein, we employed a coordination driven self-assembly strategy to secure appropriate head-to-tail alignment of anthracene moieties, and for the first time obtained large-sized Pt-based linear polymer crystals through a [4+4] cycloaddition of anthracene in a single-crystal to single-crystal fashion. Using X-ray diffraction analysis to precisely determine polymer crystal structure, we revealed that both the polymerisation and depolymerisation steps proceed via a stable intermediate. Taking advantage of the temperature-dependent slow depolymerization, the afforded Pt-based linear polymer showed potential as a sustained release anticancer drug platform. Furthermore, utilizing the reversible contraction effect of unit-cell volume upon irradiation or heating, the stimuli-responsive crystals were hybridized with polyvinylidene fluoride to obtain a ‘smart material’ with outstanding photoactuator performance. This work not only provides a new approach to prepare metal-containing linear polymer crystals, but also broadens their potential applications towards drug controlled-release and actuator functions.
关键词： Actuator,Sustained release,Topochemical polymerization,Polymer crystals,Linear polymer
更新于2025-09-19 17:13:59
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Fabrication of Large Single Crystals for Pt‐Based Linear Polymers with Controlled‐Release and Photoactuator Performance
摘要： Preparation of large single crystals for linear polymers that are amenable to X-ray analysis is very challenging in polymer science. Herein, we employed a coordination driven self-assembly strategy to secure appropriate head-to-tail alignment of anthracene moieties, and for the first time obtained large-sized Pt-based linear polymer crystals through a [4+4] cycloaddition of anthracene in a single-crystal fashion. Using X-ray diffraction analysis to precisely determine polymer crystal structure, we revealed that both the polymerisation and depolymerisation steps proceed via a stable intermediate. Taking advantage of the temperature-dependent slow depolymerization, the afforded Pt-based linear polymer showed potential as a sustained release anticancer drug platform. Furthermore, utilizing the reversible contraction effect of unit-cell volume upon irradiation or heating, the stimuli-responsive crystals were hybridized with polyvinylidene fluoride to obtain a ‘smart material’ with outstanding photoactuator performance. This work not only provides a new approach to prepare metal-containing linear polymer crystals, but also broadens their potential applications towards drug controlled-release and actuator functions.
关键词： Sustained release,Polymer crystals,Linear polymer,Topochemical polymerization,Actuator
更新于2025-09-11 14:15:04
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Competition between Exceptionally Long‐Range Alkyl Sidechain Ordering and Backbone Ordering in Semiconducting Polymers and Its Impact on Electronic and Optoelectronic Properties
摘要： Intra- and intermolecular ordering greatly impacts the electronic and optoelectronic properties of semiconducting polymers. The interrelationship between ordering of alkyl sidechains and conjugated backbones has yet to be fully detailed, despite much prior effort. Here, the discovery of a highly ordered alkyl sidechain phase in six representative semiconducting polymers, determined from distinct spectroscopic and diffraction signatures, is reported. The sidechain ordering exhibits unusually large coherence lengths (≥70 nm), induces torsional/twisting backbone disorder, and results in a vertically multilayered nanostructure with ordered sidechain layers alternating with disordered backbone layers. Calorimetry and in situ variable temperature scattering measurements in a model system poly{4-(5-(4,8-bis(3-butylnonyl)-6-methylbenzo[1,2-b:4,5-b′]dithiophen-2-yl)thiophen-2-yl)-2-(2-butyloctyl)-5,6-difluoro-7-(5-methylthiophen-2-yl)-2H-benzo[d][1,2,3]triazole} (PBnDT-FTAZ) clearly delineate this competition of ordering that prevents simultaneous long-range order of both moieties. The long-range sidechain ordering can be exploited as a transient state to fabricate PBnDT-FTAZ films with an atypical edge-on texture and 2.5× improved field-effect transistor mobility. The observed influence of ordering between the moieties implies that improved molecular design can produce synergistic rather than destructive ordering effects. Given the large sidechain coherence lengths observed, such synergistic ordering should greatly improve the coherence length of backbone ordering and thereby improve electronic and optoelectronic properties such as charge transport and exciton diffusion lengths.
关键词： semiconducting polymers,organic electronics,polymer crystals,molecular design,alkyl sidechains
更新于2025-09-04 15:30:14