A thiazolo[5,4-<i>d</i>]thiazole-bridged porphyrin organic framework as a promising nonlinear optical material

Samal, Mahalaxmi; Valligatla, Sreeramulu; Saad, Nabil A.; Rao, Mandava V; Rao, D. Narayana; Sahu, Rojalin; Biswal, Bishnu P.

doi:10.1039/c9cc05415d

Cited by 68 publications

(29 citation statements)

References 31 publications

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“…Sulfur‐containing thiazole, thiophene, and tetrathiafulvalene are a new class of moieties embedded into COFs and show excellent charge mobility and conductivity [34–37] . Thus, they have extended the applications of COFs to molecular electronics, and energy conversion and storage electrodes [38–43] . However, there is still a lack of study that proves true chemical and electrochemical stability of thiazole‐linked COF under the battery operating conditions.…”

Section: Introductionmentioning

confidence: 99%

“…[34][35][36][37] Thus, they have extended the applications of COFs to molecular electronics, and energy conversion and storage electrodes. [38][39][40][41][42][43] However, there is still a lack of study that proves true chemical and electrochemical stability of thiazole-linked COF under the battery operating conditions.Covalent organic frameworks (COFs) have been considered a potentially versatile electrode structure if they are made highly conductive and flexible to stabilize the redox functionality. Although conceptually plausible, COF-based electrodes have rarely satisfied high capacity, cyclability, and rate capability thus far.…”

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confidence: 99%

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Thiazole‐Linked Covalent Organic Framework Promoting Fast Two‐Electron Transfer for Lithium‐Organic Batteries

Singh

Kim

Kang

et al. 2021

Advanced Energy Materials

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constitutes an untapped resource. [5][6][7] In addition, tailoring molecules by adding redox-active functional groups can modulate both redox potentials and electrontransfer rates. [8,9] Thus, the vast array of organic molecules can construct a new class of electrodes, [10,11] if the main problems, such as excessive solubility, poor electronic conductivity, and vulnerability to chemical side reactions, can be solved. [5][6][7][8][9] A promising answer to these problems is the integration of small molecules into a crystalline network scaffold. [12,13] Covalent organic frameworks (COF) are well suited to form stable molecular crystals [14,15] ; Integration of organic building blocks via strong covalent bonds creates 2D structures, which are layered upon one another and held in place by π-π interactions. The resulting 3D structures inhibit the dissolution of the organic layers. Moreover, periodic mesopores are formed across the entire structure, providing effective ion-transport channels. [16][17][18] Typically, COF electrodes comprise redox functionality and linkage molecules, where the latter is responsible for the shape, mesopore size, π-conjugation, and stability of the COF. [13,19] Heteroatom-containing molecular linkers have been widely utilized to improve the wettability of COFs in electrolyte solutions. [20][21][22][23] β-Ketoenamine-linked COFs have been extensively used for capacitor and battery electrodes, and solid-state electrolytes. [24][25][26] However, a β-ketoenamine unit typically forms a nonconjugated in-plane structure of the COF, [26,27] the effect of which during electrochemical conditions has not yet been studied in depth. Imine linkage comprises partial π-conjugation over the 2D COF layer. [28,29] However, chemical instability of imine has been widely known, for example, hydrolysis in an acidic solution. [30] Therefore, the role of imine linkage remains to be explored in the nonaqueous solution-based electrochemical cells. Thiazole linkage has been recently developed to satisfy both chemical stability and the π-conjugated system. [31][32][33] Sulfur-containing thiazole, thiophene, and tetrathiafulvalene are a new class of moieties embedded into COFs and show excellent charge mobility and conductivity. [34][35][36][37] Thus, they have extended the applications of COFs to molecular electronics, and energy conversion and storage electrodes. [38][39][40][41][42][43] However, there is still a lack of study that proves true chemical and electrochemical stability of thiazole-linked COF under the battery operating conditions.Covalent organic frameworks (COFs) have been considered a potentially versatile electrode structure if they are made highly conductive and flexible to stabilize the redox functionality. Although conceptually plausible, COF-based electrodes have rarely satisfied high capacity, cyclability, and rate capability thus far. Incorporating thiazole moieties into the organic scaffold, it is able to fabricate π-conjugated and crystalline organic electrodes and demonstrate the fast two-elec...

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Section: Introductionmentioning

confidence: 99%

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confidence: 99%

Thiazole‐Linked Covalent Organic Framework Promoting Fast Two‐Electron Transfer for Lithium‐Organic Batteries

Singh

Kim

Kang

et al. 2021

Advanced Energy Materials

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“…Porphyrin has a similar molecular structure, distribution of π-electron cloud, and coordination effect to corrole. Despite the porphyrin-based COFs been extensively investigated into the field of catalysis, [90][91][92] organic optical, [93,94] and biological detection, [95] it remains a challenge to build crystalline one because of the nonplanar configuration and strong electrostatic interactions. Yaghi constructed a series of porphyrin-Co based frameworks (COF-366-X-Co, X = none, OMe 2 , F, and F 4 ) with different electronegative atoms and electrophilic functional groups to regulate their the electronic structures.…”

Section: Nitrogen-rich Building Blocksmentioning

confidence: 99%

Controllable Synthesis and Performance Modulation of 2D Covalent–Organic Frameworks

2021

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Covalent–organic frameworks (COFs) are especially interesting and unique as their highly ordered topological structures entirely built from plentiful π‐conjugated units through covalent bonds. Arranging tailorable organic building blocks into periodically reticular skeleton bestows predictable lattices and various properties upon COFs in respect of topology diagrams, pore size, properties of channel wall interfaces, etc. Indeed, these peculiar features in terms of crystallinity, conjugation degree, and topology diagrams fundamentally decide the applications of COFs including heterogeneous catalysis, energy conversion, proton conduction, light emission, and optoelectronic devices. Additionally, this research field has attracted widespread attention and is of importance with a major breakthrough in recent year. However, this research field is running with the lack of summaries about tailorable construction of 2D COFs for targeted functionalities. This review first covers some crucial polymeric strategies of preparing COFs, containing boron ester condensation, amine‐aldehyde condensation, Knoevenagel condensation, trimerization reaction, Suzuki CC coupling reaction, and hybrid polycondensation. Subsequently, a summary is made of some representative building blocks, and then underlines how the electronic and molecular structures of building blocks can strongly influence the functional performance of COFs. Finally, conclusion and perspectives on 2D COFs for further study are proposed.

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“…As a unique and novel crystalline porous material with structural periodicity and inherent porosity of uniform topology, covalent organic frameworks (COFs) ( Côté et al., 2005 ), which were for the first time successfully synthesized by Yaghi et al. through molecular building blocks in 2005, have received considerable attention and inspired numerous people's research enthusiasm due to their great application potential in gas storage and separation, drug delivery, smart sensors, molecular catalysis, energy storage, photonic and optoelectronic devices ( Zeng et al., 2016 ; Ashraf et al., 2020 ; Sun et al., 2018 ; Ghazi et al., 2016 ; Bhunia et al., 2017 ; Keller et al., 2017 ; Dalapati et al., 2013 ; Peng et al., 2017 ; Biswal et al., 2019 ; Samal et al., 2019 ; Chen et al., 2019 ; Lu et al., 2019 ; Zhang et al., 2020 ; Quertinmont et al., 2020 ). In comparison with the three-dimensional (3D) COFs, the two-dimensional (2D) COFs are more promising because of two factors: (1) the degree of lateral conjugation from π orbitals present throughout the individual 2D layer and (2) the inherent π-π stacking between the two adjacent layers ( Bhunia et al., 2017 ).…”

Section: Introductionmentioning

confidence: 99%

Ether-linked porphyrin covalent organic framework with broadband optical switch

et al. 2021

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Summary It is still a challenge to design and synthesize novel switchable optical materials with ultrafast nonlinear optical (NLO) response in a broad spectral range. These materials have exhibited great application potential in many high-technology fields such as biological imaging, chemical sensors, optical data storage, laser protection, and controllable intelligent and optoelectronic devices. By using porphyrins with highly delocalized 18 π-electron conjugated system as functional building blocks, the first ether-linked porphyrin covalent organic framework materials (COF-Pors) with highly ordered lattice structure have been successfully synthesized. In contrast to the starting porphyrins that only exhibit reverse saturable absorption (RSA) response at 532 nm, the as-prepared COF-Pors shows large NLO effect in a broad range from visible to near infrared. Upon laser illumination, COF-Pors exhibits typical saturable absorption (SA) effect at lower incident laser energy, and RSA response at higher pulse energy.

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A thiazolo[5,4-d]thiazole-bridged porphyrin organic framework as a promising nonlinear optical material

Abstract: We report a porous thiazolo[5,4-d]thiazole-bridged porphyrin organic framework, Por-TzTz-POF, with promising nonlinear optical (NLO) activity.

Cited by 68 publications

References 31 publications

Thiazole‐Linked Covalent Organic Framework Promoting Fast Two‐Electron Transfer for Lithium‐Organic Batteries

Thiazole‐Linked Covalent Organic Framework Promoting Fast Two‐Electron Transfer for Lithium‐Organic Batteries

Controllable Synthesis and Performance Modulation of 2D Covalent–Organic Frameworks

Ether-linked porphyrin covalent organic framework with broadband optical switch

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