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Conspectus2D conjugated metal-organic frameworks (2D -MOFs) have emerged as a class of graphene-like materials with fully π-conjugated aromatic structures. Their unique structural characteristics provide abundant physiochemical features, including regular nanochannels, high electrical conductivity, and customizable band gaps. Recent intensive research has significantly advanced this field, yet the exploration of 2D c-MOFs with enhanced features is limited by the availability of organic linkages and topologies. Designing novel ligands is essential for the construction of new 2D c-MOFs with high crystallinity, excellent conductivity, and tailor-made functions.In this Account, we summarize our recent contributions in fine-tuning the topology of 2D c-MOFs through precise ligand design, thereby giving them fantastic structures and tailor-made functions. First, we propose the concept of replacing planar ligands by nonplanar ligands on conductive MOF skeletons. The incorporation of nonplanar ligands improves the solubility of large π-conjugated organic molecules without interfering with the interlayer π-stacking. Our investigation discovered that conjugate polycyclic aromatics-based ligands can be synthesized through in situ Scholl reactions by means of oxidative cyclodehydrogenation of a nonplanar precursor ligand during the solvothermal synthesis process. Hence, fully conjugated 2D c-MOFs can be directly synthesized from nonplanar organic ligands, simplifying and diversifying the preparation of 2D c-MOFs. Accordingly, the design flexibility of the ligands expands the topological structures and pore types. By controlling the synthesis conditions, we can successfully induce either a rhombus or a kagome topology from a nonplanar D2 symmetric ligand. Moreover, by employing a ligand engineering strategy, we incrementally increase the number of coordination functional groups on a twisted hexabenzocoronene core, resulting in the formation of three distinct symmetric hydroxyl ligands. These ligands elicit diverse target topologies and pore sizes, resulting in variances in the coordination node density on the skeletons. This, in turn, leads to differences in electron transfer abilities, ultimately causing variations in the electrical conductivity and mobility. In addition, we employ a straightforward coupling method to incorporate redox components, such as salphen and pyrazine, into nonplanar ligands, facilitating the synthesis of 2D c-MOFs with highly active centers. This strategy confers upon the resulting frameworks substantial capacity for catalysis and energy storage, offering a good platform for elucidating the structure-property relationships at the molecular level. Moreover, the well-defined synthesis of 2D c-MOFs imparts them with specific properties, particularly in the fields of electrical, electrochemical, and spintronic applications. At the end, the primary challenges facing 2D c-MOFs in achieving tailor functions and their practical applications are proposed. This account is expected to evoke new inspirations and innovative research in the field of 2D c-MOFs, especially in emerging interdisciplinary research areas.
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Crystalline porous organic salts (CPOSs), formed by the self-assembly of organic acids and organic bases through ionic bonding, possess definite structures and permanent porosity and have rapidly emerged as an important class of porous organic materials in recent years. By rationally designing and controlling tectons, acidity/basicity (pKa), and topology, stable CPOSs with permanent porosity can be efficiently constructed. The characteristics of ionic bonds, charge-separated highly polar nano-confined channels, and permanent porosity endow CPOSs with unique physicochemical properties, offering extensive research opportunities for exploring their functionalities and application scenarios. In this review, we systematically summarize the latest progress in CPOS research, describe the synthetic strategies for synthesizing CPOSs, delineate their structural characteristics, and highlight the differences between CPOSs and hydrogen-bonded organic frameworks (HOFs). Furthermore, we provide an overview of the potential applications of CPOSs in areas such as negative linear compression (NLC), proton conduction, rapid transport of CO2, selective and rapid transport of K+ ions, atmospheric water harvesting (AWH), gas sorption, molecular rotors, fluorescence modulation, room-temperature phosphorescence (RTP) and catalysis. Finally, the challenges and future perspectives of CPOSs are presented.
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Conductive metal-organic frameworks (c-MOFs) with outstanding electrical conductivities and high charge carrier mobilities are promising candidates for electronics and optoelectronics. However, the poor solubility of planar ligands greatly hinders the synthesis and widespread applications of c-MOFs. Nonplanar ligands with excellent solubility in organic solvents are ideal alternatives to construct c-MOFs. Herein, contorted hexabenzocoronene (c-HBC) derivatives with good solubility are adopted to synthesize c-MOFs. Three c-MOFs (c-HBC-6O-Cu, c-HBC-8O-Cu, and c-HBC-12O-Cu) with substantially different geometries and packing modes have been synthesized using three multitopic catechol-based c-HBC ligands with different symmetries and coordination numbers, respectively. With more metal coordination centers and increased charge transport pathways, c-HBC-12O-Cu exhibits the highest intrinsic electrical conductivity of 3.31 S m-1. Time-resolved terahertz spectroscopy reveals high charge carrier mobilities in c-HBC-based c-MOFs, ranging from 38 to 64 cm2 V-1 s-1. This work provides a systematic and modular approach to fine-tune the structure and enrich the c-MOF family with excellent charge transport properties using nonplanar and highly soluble ligands.
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Two-dimensional conductive metal-organic frameworks (2D c-MOFs) are an emerging class of promising porous materials with high crystallinity, tunable structures, and diverse functions. However, the limited topologies and difficulties in synthesizing suitable organic linkers remain a great challenge for 2D c-MOFs synthesis and applications. Herein, two layered 2D c-MOF polymorphs with either a rhombus structure (sql-TBA-MOF) or kagome structure (kgm-TBA-MOF) were directly constructed via in situ Scholl reaction and coordination chemistry from a flexible and nonplanar tetraphenylbenzene-based ligand (8OH-TPB) in a one-pot manner. Interestingly, the kgm-TBA-MOF comprising hexagonal and triangular dual pores exhibit higher conductivities of 1.65 × 10-3 S/cm at 298 K and 3.33 × 10-2 S/cm at 353 K than that of sql-TBA-MOF (4.48 × 10-4 and 2.90 × 10-3 S/cm, respectively). Moreover, the morphology and topology can be modulated via the addition of ammonium hydroxide as modulator. The present work provides a new pathway for design, synthesis, and topological regulation of 2D c-MOFs.
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White etâ al., in a recent Correspondence, provided additional structural data to illustrate that CPOS-6 undergoes a single-crystal-to-single-crystal transformation during water adsorption/desorption. This finding gave a better understanding of the relevant experimental phenomena from the perspective of structural transformation and is a good complement to our previous results. However, we wish to emphasize that our research focuses on the kinetic behavior of water during ultrafast adsorption/desorption in nano-confined channels. Herein, we further interpret the rapid transport of water molecules in the nano-confined channels from the perspective of superfluidity.
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Two-dimensional (2D) covalent organic frameworks (COFs) are an emerging class of promising 2D materials with high crystallinity and tunable structures. However, the low electrical conductivity impedes their applications in electronics and optoelectronics. Integrating large π-conjugated building blocks into 2D lattices to enhance efficient π-stacking and chemical doping is an effective way to improve the conductivity of 2D COFs. Herein, two nonplanar 2D COFs with kagome (DHP-COF) and rhombus (c-HBC-COF) lattices have been designed and synthesized from distorted aromatics with different π-conjugated structures (flexible and rigid structure, respectively). DHP-COF shows a highly distorted 2D lattice that hampers stacking, consequently limiting its charge carrier transport properties. Conversely, c-HBC-COF, with distorted although concave-convex self-complementary nodes, shows a less distorted 2D lattice that does not interfere with interlayer π-stacking. Employing time- and frequency-resolved terahertz spectroscopy, we unveil a high charge-carrier mobility up to 44 cm2 V-1 s-1, among the highest reported for 2D COFs.
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Porous organic polymers (POPs), as a new category of advanced porous materials, have received broad research interests owing to the advantages of light-weight, robust scaffolds, high specific surface areas and good functional tailorability. According to the long-range ordering of polymer skeletons, POPs can be either crystalline or amorphous. Macrocycles with inherent cavities can serve as receptors for recognizing or capturing specific guest molecules through host-guest interactions. Incorporating macrocycles in POP skeletons affords win-win merits, e.g. hierarchical porosity and novel physicochemical properties. In this review, we focus on the recent progress associated with new architectures of macrocycle-based POPs. Herein, these macrocycles are divided into two subclasses: non-planar (crown ether, calixarene, pillararene, cyclodextrin, cyclotricatechylene, etc.) and planar (arylene-ethynylene macrocycles). We summarize the synthetic methods of each macrocyclic POP in terms of the functions of versatile building blocks. Subsequently, we discuss the performance of macrocyclic POPs in environmental remediation, gas adsorption, heterogeneous catalysis, fluorescence sensing and ionic conduction. Although considerable examples are reported, the development of macrocyclic POPs is still in its infancy. Finally, we propose the underlying challenges and opportunities of macrocycle-based POPs.
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Open 1D channels found in covalent organic frameworks are unique and promising to serve as pathways for proton conduction; how to develop high-rate yet stable transporting systems remains a substantial challenge. Herein, this work reports a strategy for exploring proton-conducting frameworks by engineering pore walls and installing proton-containing polymers into the pores. Amide-linked and sulfonated frameworks were synthesized from imine-linked precursors via sequentially engineering to oxidize into amide linkages and to further anchor sulfonic acid groups onto the pore walls, enabling the creation of sulfonated frameworks with high crystallinity and channel ordering. Integrating sulfonated polyether ether ketone chains into the open channels enables proton hopping to across the channels, greatly increases proton conductivity and enables a stable continuous run. These results suggest a way to explore proton-conducting COFs via systematic engineering of the wall and space of the open nanochannels.
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Covalent organic frameworks (COFs) enable precise reticulation of organic building units into extended 2D and 3D open networks using strong covalent bonds to constitute predesignable topologies and tunable pore structures, presenting an emerging class of crystalline porous polymers. Although rapid progress and substantial achievements in COF chemistry over the past 15 years have been realised, highly efficient strategies and reproducible procedures still play a central role in achieving high-quality COFs and serve as a major driving force for the further advancement of this promising field. In this review, we focused on the key progress in synthesising high-quality COF crystallites and films by highlighting their uniqueness from the viewpoints of synthetic strategies and procedures. We discussed representative synthetic methods including mechanochemical synthesis, microwave synthesis, multicomponent reaction, multistep synthesis and linker exchange strategies to compare their features in producing COFs. We scrutinised the recently developed "two-in-one" molecular design strategy to showcase advantages in optimising synthetic conditions such as catalyst, monomer feeding rate and tolerance to functional groups. We analysed interfacial polymerisation for fabricating various COF films by emphasising their scope and applicability. Moreover, we proposed key underlying challenges to be solved and predicted future frontiers from the perspectives of synthesising high quality crystallites and films that are key to practical applications.
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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 271â F g-1 with a three-electrode setup at a discharge rate of 1â A g-1 , which represents one of the highest capacitances among the reported COF-based electrode materials.
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2D conductive metal-organic frameworks (2D c-MOFs) are promising candidates for efficient electrocatalysts for the CO2 reduction reaction (CO2 RR). A nitrogen-rich tricycloquinazoline (TQ) based multitopic catechol ligand was used to coordinate with transition-metal ions (Cu2+ and Ni2+ ), which formed 2D graphene-like porous sheets: M3 (HHTQ)2 (M=Cu, Ni; HHTQ=2,3,7,8,12,13-Hexahydroxytricycloquinazoline). M3 (HHTQ)2 can be regarded as a single-atom catalyst where Cu or Ni centers are uniformly distributed in the hexagonal lattices. Cu3 (HHTQ)2 exhibited superior catalytic activity towards CO2 RR in which CH3 OH is the sole product. The Faradic efficiency of CH3 OH reached up to 53.6 % at a small over-potential of -0.4â V. Cu3 (HHTQ)2 exhibited larger CO2 adsorption energies and higher activities over the isostructural Ni3 (HHTQ)2 and the reported archetypical Cu3 (HHTP)2 . There is a strong dependence of both metal centers and the N-rich ligands on the electrocatalytic performance.
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We designed and synthesized A2 B2 type tetraphenyl benzene monomers (p-, m-, and o-TetPB) which have the para-, meta, and ortho-substituted isomeric structures, for the direct construction of isomeric frameworks. Interestingly, both kagome (kgm) and monoclinic square (sql) framework isomers are produced from either p-TetPB (C2h symmetry) or m-TetPB (C2v symmetry) by changing reaction solvents, while their isomeric structures are characterized by X-ray diffraction, computational simulation, microscopy, and sorption isotherm measurements. Only sql frameworks was formed for o-TetPB (C2v symmetry), irrespective of reaction solvents. These results disclose a unique feature in the framework structural formation, that is, the geometry of monomers directs and dominates the lattice growth process while the solvent plays a role in the perturbation of chain growth pattern. The isomeric frameworks exhibit highly selective adsorption of vitamin B12 owing to pore shape and size differences.
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Negative linear compressibility (NLC) is a common sense violation (that is, crystal phases expand in one or more directions under hydrostatic compression). The excellent NLC performance of crystal materials is intrinsically related to the geometric structure of its skeleton. Here, we discovered a crystalline porous organic salt (CPOS-1); high-pressure X-ray diffraction experiments reveal that the CPOS-1 shows colossal NLC (Kc = -90.7 T Pa-1) behavior along the c axis. This incredible performance arises from the flexible "supramolecular spring" formed by the charge-enhanced N-H+···-O-S hydrogen bond interaction between the anionic sulfonate and the cationic ammonium ion. Furthermore, we reveal the relationship between this rare NLC behavior and single crystal proton conductivity using high-pressure electrochemical impedance spectroscopy (EIS) method. We believe that NLC behavior research on such inexpensive and readily available porous organic materials is of great significance for accelerating the research and application of NLC materials, especially in organic system.
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Three isostructural covalent organic frameworks (COFs) with either methoxyl, hydroxyl, or both groups on the channel wall, are synthesized and served as metal-free heterogeneous catalysts for chemical fixation of CO2 . Among them, the COF decorated with both hydroxyl and methoxyl groups named OMe-OH-TPBP-COF exhibits the highest catalytic activity and efficiency for CO2 cycloaddition under mild conditions.
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A highly crystalline bicarbazole-based covalent organic framework (BCzP-COF) was synthesized via an upgraded "two-in-one" strategy by the self-polycondensation of A2 B2 monomer with two neopentyl acetal and two amine groups. Such a strategy is propitious to afford higher crystallinity, larger special surface areas and better morphology than that of using unprotected monomer with free aldehydes and amines. Additionally, the off-white powder of BCzP-COF could serve as acidichromism sensor with a significant color change. Intriguingly, the conductivity of the protonated BCzP-COF can improve by six orders of magnitude compared to that of the pristine samples. This work has the potential to lead to bicarbazole-functional materials for chemosensors and electronic devices.
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Two-dimensional (2D) covalent organic frameworks (COFs) feature open and ordered one-dimensional column nanochannels which offer immense possibilities for incorporation of various guests for specific functions. However, the relatively low chemical stability of most COFs originating from the dynamic covalent linkages hinders their practical application. In this work, a highly crystalline and heteroporous dibenzo[g,p]chrysene-based COF (DBC-2P) was synthesized and served as a host material for ionic conduction. DBC-2P exhibits excellent stability both in strong acid and base due to the large conjugated DBC-based knot that reinforces the interlayer interactions. Subsequent encapsulation of linear polyethylene glycol (PEG) and PEG-LiBF4 salt into the nanochannels of DBC-2P affords a hybrid material with a high ionic conductivity of 2.31×10-3 â S cm-1 . This work demonstrates an efficient post-synthetic strategy for the development of new COF-polymer composites with intriguing properties.
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Self-assembled crystalline porous organic salts (CPOSs) formed by an acid-base combination and with one-dimensional polar channels containing water molecules have been synthesized. The water content in the channels of the porous salts plays an important role in the proton conduction performance of the materials. The porous salts described in this study feature high proton conductivity at ambient conditions and can reach as high as 2.2×10-2 â S cm-1 at 333â K and under high humid conditions. This is among the best conductivity values reported to date for porous materials, for example, metal-organic frameworks and hydrogen-bonded organic frameworks. These materials exhibiting permanent porosity represent a group of porous materials and may find interesting applications in proton-exchange membrane fuel cells.
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We report the first organically synthesized sp-sp3 hybridized porous carbon, OSPC-1. This new carbon shows electron conductivity, high porosity, the highest uptake of lithium ions of any carbon material to-date, and the ability to inhibit dangerous lithium dendrite formation. The new carbon exhibits exceptional potential as anode material for lithium-ion batteries (LIBs) with high capacity, excellent rate capability, long cycle life, and potential for improved safety performance.
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The search for new types of membrane materials has been of continuous interest in both academia and industry, given their importance in a plethora of applications, particularly for energy-efficient separation technology. In this contribution, we demonstrate for the first time that a metal-organic framework (MOF) can be grown on the covalent-organic framework (COF) membrane to fabricate COF-MOF composite membranes. The resultant COF-MOF composite membranes demonstrate higher separation selectivity of H2/CO2 gas mixtures than the individual COF and MOF membranes. A sound proof for the synergy between two porous materials is the fact that the COF-MOF composite membranes surpass the Robeson upper bound of polymer membranes for mixture separation of a H2/CO2 gas pair and are among the best gas separation MOF membranes reported thus far.
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Topochemical polymerization is a highly promising and effective method for constructing complex three-dimensional structures and functionalized polymers. Herein, we present for the first time a topochemical reaction of diacetylene within a meticulously designed covalent organic framework (ZNUC-1). Our experimental results revealed that ZNUC-1 underwent a 1,4-addition reaction under thermal induction, forming an ene-yne-conjugated structure.