Consistent red luminescence in π-conjugated polymers with tuneable elastic moduli over five orders of magnitude

Guo, Zuoxing; Shinohara, Akira; Pan, Chengjun; Stadler, Florian J.; Z, Liu; Yan, Zhi-Chao; Zhao, Jinlai; Wang, Lei; Nakanishi, Takashi

doi:10.1039/d0mh00029a

Cited by 23 publications

(36 citation statements)

References 37 publications

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“…This very much resembles the behavior of Rouse‐chains, i.e., polymer chains which do not have entanglements. [ 17–23 ]…”

Section: Resultsmentioning

confidence: 99%

“…These findings can be explained by the concept of internal plasticizing. [ 22,23 ] It is clear that the stiffness of the material in melt‐state is determined by the aliphatic backbone of the polyMns, while the side chain “dilutes” it, while in the solid‐state, the modulus of glassy polymers is almost independent of the chemical structure of polymers. [ 29,30 ] Thus making the side chain longer leads to a stronger dilution in the melt state, while this does not matter very much in solid‐state.…”

Section: Resultsmentioning

confidence: 99%

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Effect of n‐Alkyl Side Chain Length on the Thermal and Rheological Properties of PolyN‐(3‐(alkylamino)‐N‐(3‐(isopropylamino)‐3‐oxopropyl)acrylamide) Homopolymers

Kumari

Vishwakarma

Mitra

et al. 2021

Macro Chemistry & Physics

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Four new N‐isopropylacrylamide‐ and N‐n‐alkyl amine‐based acrylamide monomers, N‐(3‐(alkylamino)‐N‐(3‐(isopropylamino)‐3‐oxopropyl) acrylamide (Mn) (n = 4, 8, 10, 12) are successfully synthesized and polymerized via reversible addition‐fragmentation chain‐transfer polymerization (polyMn, n = 4, 8, 10, and 12), which are characterized by gel permeation chromatography, 1H NMR, Fourier transform infra red spectroscopy, thermo‐gravimetry‐differential thermal analysis, differential scanning calorimetry (DSC), and rheology. All polymers are thermally stable and undergo a two‐step degradation process at ≈280 and ≈375 °C. Glass transition temperature (Tg)s of these polymers decrease gradually from 99.6 to 52.5 °C with increasing n‐alkyl side chain length. The rheology of these polymers in melt state agrees to a typical Rouse‐melt behavior and allows for confirming the Tg determined from DSC. Benzyl alcohol solution rheology proves a weak structural build‐up, in particular for polyM12. Comparison of the quantum chemical calculations of polyMns with n = 4–8 reveals increase in backbone helicity with increasing n‐alkyl side chain length.

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“…This very much resembles the behavior of Rouse‐chains, i.e., polymer chains which do not have entanglements. [ 17–23 ]…”

Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Effect of n‐Alkyl Side Chain Length on the Thermal and Rheological Properties of PolyN‐(3‐(alkylamino)‐N‐(3‐(isopropylamino)‐3‐oxopropyl)acrylamide) Homopolymers

Kumari

Vishwakarma

Mitra

et al. 2021

Macro Chemistry & Physics

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“…Moduli 63 The intrinsic optical properties of molecules are generally characterized in dilute solutions. Since π-conjugated molecules have strong intermolecular interactions, aggregation occurs in high-concentration solutions.…”

Section: Consistent Luminescence In Wide Range Of Elasticmentioning

confidence: 99%

“…1.4. Effect of side chain length63 Fi gure 5 Linear rheological spectra of40-43 at 25 °C. Reproduced from Ref.…”

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confidence: 99%

Solvent-Free Conjugated Polymer Fluids with Optical Functions

et al. 2021

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Solvent-free fluidic materials possessing optoelectronic functions are expected to be major components in soft electronics applications. Conjugated polymers are promising targets for this purpose and their design approaches are classified into three types with respect to their structure: conjugation breaking (Type I), copolymerization with flexible polymers (Type II), and side chain engineering (Type III). In this short review, we highlight several early attempts to produce Type III conjugated polymers. We also present fully characterized Type III fluids recently developed by our group, with a brief summary of the structure–property relationship and fluidity-oriented functions.Introduction1 Polymer Design1.1 Fluidity of Polymeric Materials1.2 Type III CPs with T g < 25 °C1.3 Fluidification of Polyfluorenes1.4 Effect of Side Chain Length2 Fluidity-Oriented Functions2.1 Mechanofluorochromism2.2 Consistent Luminescence in Wide Range of Elastic Moduli2.3 Prediction of ViscoelasticityConclusions and Outlook

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“…For example, liquid‐state conjugated polymers have been developed in recent years. [ 23,24 ] Here, we use a layered structure with tunable flexibility to induce motion of conjugated polymers in solid state in a low‐temperature range of around 100 K.…”

Section: Figurementioning

confidence: 99%

Solid‐State Low‐Temperature Thermoresponsive and Reversible Color Changes of Conjugated Polymer in Layered Structure: Beyond Infrared Thermography

Watanabe

Imai

Oaki

2020

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Stimuli-responsive color changes have attracted much interest for development of a variety of sensors. [1-3] How to induce the color changes in response to external stimuli, such as heat, light, and force, is a key to design the molecules and materials. [4,5] For example, thermoresponsiveness is achieved by temperature-dependent gradual structure changes including chromophore. Thermochromism requires reversibility of the structure changes. However, in general, it is not easy to induce these dynamic structure changes at lower temperature, such as cryogenic range, because molecular motion becomes suppressed. Therefore, low-temperature thermoresponsive and reversible color changes are challenging targets and interesting phenomena for chemists. Visualization and quantification of cryogenic temperature range are significant for process controls in biological, medical, and food sciences and industries. Previous works showed a couple of the approaches (Figure S1, Emergence of thermoresponsive and reversible color changes at low temperature is a challenging target. In general, it is not easy to induce sufficient dynamic motion of rigid molecules including chromophore at a lower temperature. The present work shows unusually low-temperature color-change properties originating from the dynamic motion of rigid conjugated polymer in solid state. The layered composites of polydiacetylene (PDA) and guest l-arginine (L-Arg) (PDA-(L-Arg)) exhibit temperatureresponsive gradual color changes with reversibility in the range of 123-333 K in solid crystalline state. The dynamic properties are induced by gradual and reversible distortion of the π-conjugated main chain in response to temperature. The tuned flexibility of the layered structure facilitates motion of the rigid π-conjugated molecule at low temperature. The PDA-(L-Arg)-coated substrates are applied to visualization and quantification of 2D and 3D temperature distributions generated by cooling with liquid nitrogen. These thermographic devices afford to image lower temperature range than typical infrared thermography. The present work indicates potentials of layered architectures with tunable flexibility for emergence of dynamic properties. Supporting Information). [6-14] Metalorganic frameworks consisting of lanthanide ions and photo-responsive ligands showed the gradual changes of fluorescent color with reversibility from 4 K. [7-10] The unique color-changing behavior is ascribed to the temperature-dependent energy transfer efficiency. The thermochromic visible color variation around 90 K was reported on salicylideneaniline derivatives. [11-13] The temperaturedependent tautomerization of the two forms proceeds during the color changes in the solid crystalline state. The similar color changes were observed on a solidstate conjugated polymer, namely poly(3dodecylthiophene), in the range of 110-420 K. [14] As the ratio of two conformations varies depending on temperature, the intensity of the two peaks in the absorption spectra shows the ratiometric changes. However, the gradua...

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Consistent red luminescence in π-conjugated polymers with tuneable elastic moduli over five orders of magnitude

Abstract: Bulky but flexible alkyl side chains enable π-conjugated polymers to possess wide-range elastic modulus tuneability, yet consistent red luminescent properties.

Cited by 23 publications

References 37 publications

Effect of n‐Alkyl Side Chain Length on the Thermal and Rheological Properties of PolyN‐(3‐(alkylamino)‐N‐(3‐(isopropylamino)‐3‐oxopropyl)acrylamide) Homopolymers

Effect of n‐Alkyl Side Chain Length on the Thermal and Rheological Properties of PolyN‐(3‐(alkylamino)‐N‐(3‐(isopropylamino)‐3‐oxopropyl)acrylamide) Homopolymers

Solvent-Free Conjugated Polymer Fluids with Optical Functions

Solid‐State Low‐Temperature Thermoresponsive and Reversible Color Changes of Conjugated Polymer in Layered Structure: Beyond Infrared Thermography

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