Amine-Linked Covalent Organic Frameworks as a Platform for Postsynthetic Structure Interconversion and Pore-Wall Modification

Grunenberg, Lars; Savaşçı, Gökçen; Terban, Maxwell W.; Düppel, Viola; Moudrakovski, Igor L.; Etter, Martin; Dinnebiér, Robert E.; Ochsenfeld, Christian; Lotsch, Bettina V.

doi:10.1021/jacs.0c12249

Cited by 117 publications

(126 citation statements)

References 37 publications

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“…This phenomenon has also been observed in other COFs (Table S1) containing the linkages of "-NH-". [8f,g, 16,17] The pore volume of AAm-TPB and AAm-Py were 0.32 and 0.43 cm 3 g À1 (P/P 0 = 0.99), respectively. Pore size distributions (PSDs) based on the nonlocal density functional theory (NLDFT) method showed the dominant pore sizes for AAm-TPB and AAm-Py were 2.99 nm and 1.02 nm, respectively (Figure 1 b and S5), both of which agreed well with the theoretical values (3.01 nm for AAm-TPB and 1.09 nm for AAm-Py, Figure 2 b and d).…”

Section: Methodsmentioning

confidence: 96%

“…[15] This condensation is reversible, and thus is beneficial for COF synthesis. Different from the aliphatic amine linkage (-CH 2 -NH-) reported by Deng, [8f] Lotsch, [16] Ma [17] and Zhao [11] (Scheme 1), the arylamine linkage (-NH-) developed herein not only feature improved stability but also maintain high conjugation degree beneficial for electrical conduction and redox activity. Moreover, the diphenylamine moieties generated by this condensation resemble the repeating units of polyaniline (PANI), which may further confer the unprecedented arylamine-linked COFs with many promising applications.…”

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confidence: 93%

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Arylamine‐Linked 2D Covalent Organic Frameworks for Efficient Pseudocapacitive Energy Storage

et al. 2021

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The development of new linkages is one of the most efficient strategies to enrich the diversity of covalent organic frameworks (COFs). Particularly, functional linkages can endow COFs with additional tailored properties besides the building units, which further diversify COFs with desirable functions. Herein, we have developed a new arylamine linkage for the construction of COFs. Two new arylamine‐linked COFs (AAm‐TPB and AAm‐Py) were prepared by condensing cost‐effective dimethyl succinyl succinate (DMSS) with corresponding multitopic amines (TPB‐NH2 and Py‐NH2). Due to the abundant electroactive diphenylamine moieties in the COF skeletons resembling that of polyaniline (PANI), a state‐of‐the‐art conductive polymer, the pseudocapacitive energy storage performance of AAm‐TPB was further investigated. Remarkably, the AAm‐TPB electrode exhibits a high capacitance of 271 F g−1 with a three‐electrode setup at a discharge rate of 1 A g−1, which represents one of the highest capacitances among the reported COF‐based electrode materials.

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Section: Methodsmentioning

confidence: 96%

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confidence: 93%

Arylamine‐Linked 2D Covalent Organic Frameworks for Efficient Pseudocapacitive Energy Storage

et al. 2021

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“…We employed PDF analysis on X-ray total scattering synchrotron data (Figure 3b COFs, interlayer correlations are not observed, indicating the relationship between the stacked, and even neighboring layers is not coherent, due to a broadened distribution of interatomic distances between neighboring layers. 62,71 Hence, a good qualitative agreement to the simulated pair distribution functions (AA-1_EE model) is obtained by implementing large atomic displacement parameters in the [001] direction (U33), simulating different levels of reduction in interlayer coherence (Figure 3b). This agreement is not noticeably impacted if the motor unit is considered in the structural model, indicating that the motor units cannot be distinctly resolved without long-range ordering, since the bond distances in the motor units are too similar to the backbone of the material (Figure S16).…”

Section: Materials Synthesismentioning

confidence: 53%

Light-Driven Molecular Motors Embedded in Covalent Organic Frameworks

Stähler

Grunenberg

Terban

et al. 2022

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The incorporation of molecular machines into the backbone of porous framework structures will facilitate nano actuation, enhanced molecular transport, and other out-of-equilibrium host-guest phenomena in well-defined 3D solid materials. In this work, we detail the synthesis of a diamine-based light-driven molecular motor and its incorporation into a series of imine-based polymers and covalent organic frameworks (COF). We study structural and dynamic properties of the molecular building blocks and derived self-assembled solids with a series of spectroscopic, diffraction, and theoretical methods. Using an acid-catalyzed synthesis approach, we are able to obtain the first crystalline 2D COF with stacked hexagonal layers that contains 20 mol-% molecular motors. The COF features a specific pore volume and surface area of up to 0.45 cm3 g−1 and 604 m2 g−1, respectively. Given the molecular structure and bulkiness of the diamine motor, we study the supramolecular assembly of the COF layers and detail stacking disorders between adjacent layers. We finally probe the motor dynamics with in situ spectroscopic techniques revealing current limitations in the analysis of the these new materials and derive important analysis and design criteria as well as synthetic access to new generations of motorized porous framework materials.

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“…Early types of COFs, such as boronate ester-linked COFs and boroxine-linked COFs, [62] were sensitive to water, acid/base, alcohols, and atmospheric moisture, leading to limited application potential. Along with the appearance of some new reactions and well-designed strategies (cascade reaction and postsynthetic modification), COFs with representative linkages, such as triazine, [63] imine, [64] hydrazone, [65] borazine, [66] β-ketoenamine, [67] phenazine, [68] squaraine, [69] imide, [70] spiroborate, [71] acrylonitrile, [72] dioxin, [73] benzoxazole, [74] olefin, [75] benzimidazole, [76] quinoline, [77] α-aminonitrile, [77] benzothiazole, [78] ester, [79] and amine, [80] were successfully synthesized in succession and exhibited satisfactory stabilities owing to the increase in the strength of the chemical bonds in these materials as compared with boron-based linkages.…”

Section: Stabilitymentioning

confidence: 99%

Covalent Organic Framework Membranes for Efficient Chemicals Separation

et al. 2021

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Membrane-based separation is an emerging technology to separate different components. [1] Owing to not only the functions of separation, concentration, and purification, but also the properties of energy efficiency, environmental friendliness, high efficiency, simplicity, manufacturing scalability, small footprint, and ease of operation and control, this technology has been widely used in chemical industry, environmental protection, medicine, food, and desalination. [2,3] Membrane is regarded as a significant method to solve the far-reaching issues such as water shortages, environmental pollution, and energy crisis.Along with the rapid industrialization and sharp increase in population, the problems of water shortages, environmental pollution, and energy crisis become more and more severe and complex, leading to the higher technology requirement for membrane separation. Although the frequently used traditional polymer membrane featured with low cost, good mechanical strength, excellent flexibility, and ease of processing, the two key parameters of permeability and selectivity that are generally used to evaluate membrane separation performance are interinhibitive because of the well-known trade-off effect. [4] One of the main reasons for the trade-off effect is the wide distribution of pore size in polymeric membranes. Therefore, materials with uniform and well-ordered pores are considered as perfect candidates for fabricating highperformance separation membranes. Keeping this in perspective, many meaningful studies have been conducted for constructing homoporous membranes [5] with traditional polymers as starting materials. The obtained membranes have a pore size ranging from 5 to 50 nm and possess great potential for ultrafiltration (UF). [6] However, in some practical application systems such as gas separation, dyes removal, protein and drug recovery as well as desalination, the kinetic dimensions of components to be separated usually are less than 5 nm. Therefore, it is very important that a homoporous structure with a pore size of less than 5 nm is constructed to be used in membrane separation.Covalent organic frameworks (COFs) [7][8][9][10][11] are an emerging class of organic porous crystalline materials with pores that range from 0.5 to 5 nm, [12,13] which are entirely composed by light elements, such as C, H, O, N, B, and Si and are connected by strong covalent bonds. Owing to the unique nature of their well-ordered and tailorable pore channels, high and permanent porosity, excellent thermostability and chemical stability, and ease of functionalization, COF materials have been demonstrated promising potential in many applications, including separation, [14] catalysis, [15] sensor, [16] optoelectronics, [17] energy conversion, [18] and semiconductors, [19] among others. Particularly, these characteristics of COF materials perfectly meet the requirements for making advanced separation membrane. For example, the uniform aperture, high porosity, and excellent stability are beneficial

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Amine-Linked Covalent Organic Frameworks as a Platform for Postsynthetic Structure Interconversion and Pore-Wall Modification

Cited by 117 publications

References 37 publications

Arylamine‐Linked 2D Covalent Organic Frameworks for Efficient Pseudocapacitive Energy Storage

Arylamine‐Linked 2D Covalent Organic Frameworks for Efficient Pseudocapacitive Energy Storage

Light-Driven Molecular Motors Embedded in Covalent Organic Frameworks

Covalent Organic Framework Membranes for Efficient Chemicals Separation

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