Molecular engineering of a porphyrin-based hierarchical superstructure: planarity control of a discotic metallomesogen for high thermal conductivity

Park, Minwook; Kang, Dong‐Gue; Ko, Hyeyoon; Rim, Minwoo; Tran, Duy Thanh; Park, Sungjune; Kang, Minji; Kim, Tae-Wook; Kim, Namil; Jeong, Kwang‐Un

doi:10.1039/d0mh00966k

Cited by 14 publications

(9 citation statements)

References 41 publications

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“…As shown in Figures and S1, a tetrathiafulvalene (TTF)-based reactive mesogen with the thiol functional group (abbreviated as TTF-SH) was systematically synthesized for the monomeric building block of the shape-morphing polymer network. Because TTF has a sp 2 hybridized rigid core structure, it plays an important role in improving the thermal conductivity of materials by providing an effective phonon conduction pathway. − The flexible alkyl chains and thiol reactive groups are chemically attached around the periphery of the TTF mesogenic core to realize the mesophase and to construct the three-dimensional (3D) disulfide polymer network (Figure a). More specifically, the introduction of four alkyl chains on the side of the TTF mesogenic core allows TTF-SH to form a thermotropic mesophase.…”

Section: Resultsmentioning

confidence: 99%

Shape-Morphing Thermoactuators: Tetrathiafulvalene-Based Polymer Networks with an Effective Phonon Conduction Pathway

Rim

Kang

et al. 2021

Chem. Mater.

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The development of a shape memory polymer (SMP) with high thermal conductivity should precede the fabrication of fast-responsive soft thermoactuators because the effective heat transfer in thermoactuators expedites the shape-morphing process. A tetrathiafulvalene (TTF)-based monomer (TTF-SH) containing four flexible chains and thiol reactive functions is newly designed and synthesized for the development of SMP with excellent thermal conductivity. Thanks to the thermally induced chemical bond formation of TTF-SH from thiol to disulfide, TTF-based SMP is simply prepared without the addition of any catalyst or initiator. The TTF SMP exhibits not only high thermal conductivity (1.12 W/(m K)) but also high fixing and recovery ratios (99.42 and 99.98%). The correlation between heat transfer and shape-morphing speed of the TTF SMP is established by examining shape memory characteristics over time. The TTF SMP shows a fast shape-morphing response due to its excellent thermal conductivity. With the newly developed TTF SMP thermoactuator, we demonstrate a warning sensor to alarm the device overheating as well as a smart sunshade to automatically cut off solar energy.

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Section: Resultsmentioning

confidence: 99%

Shape-Morphing Thermoactuators: Tetrathiafulvalene-Based Polymer Networks with an Effective Phonon Conduction Pathway

Rim

Kang

et al. 2021

Chem. Mater.

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“…For a variety of 2D (dimension) covalent organic frameworks (COFs) or metal organic framework (MOF) [25] like porphyrin‐based reactive metallomesogen (PorV‐x), as displayed in Figure 2, TC can be significantly enhanced by adjusting the substituted metal ions' size in the centre of the MOF and the molecular planarity via metal core substitution. For instance, the Zn‐substituted PorV‐Zn film with the flattest planarity shows the largest TC of 1.2 W/(m·K) compared with other metals like Cu and Ni [26].…”

Section: Advances In Thermally Conductive Intrinsic Polymer Dielectricsmentioning

confidence: 99%

Research progress of intrinsic polymer dielectrics with high thermal conductivity

Zhou

Yao

Yuan

et al. 2023

IET Nanodielectrics

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Heat dissipation has become an important challenge and technical bottleneck for the rapid development of high‐frequency microelectronic devices and high‐voltage electrical equipment. Thus, there is a great urgent need for high‐performance intrinsically thermally conductive polymer (ITCP) to realise effective heat dissipation. In recent year, the ITCP has received extensive attention due to excellent overall performances and clear advantages over conventional heat conductive polymer composites. The thermal transport physics and its relation with the multiscale chain conformations in polymers with diverse morphologies are reviewed. Then, the current understanding of how the chemistry of polymers, multiscale chain morphologies and conformations would affect phonon transport and the resulting thermal conductivity (TC) in both amorphous and crystalline polymers to unveil the important chemistry‐structure‐property relationships is discussed and anaysed. The latest advances in engineering ITCP from oriented fibre to bulk amorphous states for a high TC are summarised. Lastly, the challenges, prospects and outlook of ITCP have been proposed. The authors anticipate that the present paper will spire more fundamental and applied research in the intrinsic polymer dielectrics field to advance scientific understanding and industrial applications.

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“…Controlling the polarization of light as well as the absorption wavelength of light can be a breakthrough for the fabrication of an advanced EC device. − In order to realize this, the implementation of liquid crystal (LC) materials capable of macroscopic orientation through simple coating techniques has demonstrated promising outcomes. It should be noted that LC materials can not only form uniaxially oriented hierarchical nanostructures by external stimuli such as electric/magnetic fields, surface anchoring, and mechanical shear forces but also stabilize the nanostructures through the three-dimensional (3D) polymer networks. − Therefore, prior to achieving a comprehensive understanding of uniaxially oriented LC materials, a thorough analysis of the hierarchical nanostructure resulting from oriented self-assembly is necessary. ,,− The optical anisotropy of oriented EC LCs can be fabricated into a new type of EC optical device with polarizers.…”

Section: Introductionmentioning

confidence: 99%

Encryptable Electrochromic Smart Windows: Uniaxially Oriented and Polymerized Hierarchical Nanostructures Constructed by Self-Assembly of Tetrathiafulvalene-Based Reactive Mesogens

et al. 2023

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Tetrathiafulvalene (TTF)-based reactive mesogens (TTF-E and TTF-T) are synthesized, self-assembled, uniaxially oriented, and polymerized for the development of encryptable electrochromic smart windows. Electrochemical and spectroscopic experiments prove that the self-assembled TTF mixture (TTFM, TTF-E:TTF-T = 1:1) can reversibly switch the absorption wavelength of the TTF chromophore according to the redox reactions. Based on the identification of the phase transition and crystallographic structure, uniaxially oriented hierarchical nanostructures are easily constructed on the macroscopic area by simple coating and a self-assembly process. Subsequent polymerization of hierarchical nanostructures of TTFM significantly enhances thermal and mechanical stabilities and makes it possible for them to be fabricated as an electrochromic device. The angularly dependent correlation between the anisotropy of mesogens and the linearly polarized light allow us to demonstrate TTFM as smart windows capable of various optical security applications, including privacy protection and information encryption.

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Molecular engineering of a porphyrin-based hierarchical superstructure: planarity control of a discotic metallomesogen for high thermal conductivity

Abstract: With the significance of heat management, recently, high thermal conducting polymers have attracted attention as promising polymeric matrix materials in miniaturized and flexible devices. Porphyrin-based reactive metallomesogens (PorV-x; x =...

Cited by 14 publications

References 41 publications

Shape-Morphing Thermoactuators: Tetrathiafulvalene-Based Polymer Networks with an Effective Phonon Conduction Pathway

Shape-Morphing Thermoactuators: Tetrathiafulvalene-Based Polymer Networks with an Effective Phonon Conduction Pathway

Research progress of intrinsic polymer dielectrics with high thermal conductivity

Encryptable Electrochromic Smart Windows: Uniaxially Oriented and Polymerized Hierarchical Nanostructures Constructed by Self-Assembly of Tetrathiafulvalene-Based Reactive Mesogens

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