Strong Supramolecular Interactions Research Articles

Bioinspired "Intermolecular Pocket" in Soft Molecular Crystal of Porous Organic Cage Exhibiting Reversible Guest Recognition.

Porous Organic Cages (POCs) have gathered a lot of attention in sorts of fields. Previous studies often focused on the functionalization of their intrinsic porosity, while the utilization of the extrinsic porosity has been seldom reported. To date, the rational construction of functionalized extrinsic porosity in POCs is a serious challenge, which still relies on trial and error. Inspired by hydrophobic proteins, in the contribution, a POC (namely NKPOC-DS) is obtained with hydrophobic "intermolecular pocket" as extrinsic porosity constructed through the assembly of disulfide bonds with hydrophobic groups, facilitating strong supramolecular interactions as confirmed by Electrostatic Potential (ESP) maps and single-crystal X-ray diffraction analysis. Notably, NKPOC-DS exhibits a unique C2H6-selective "breathing behaviour" due to the presence of softness in its extrinsic porosity, which does not extend to other gases such as C2H4, CH4, CO2, N2, and H2. Such specific recognition of C2H6 thus provides NKPOC-DS with the ability to preferentially adsorb C2H6 from a C2H6/C2H4 mixture. The innovative approach of biomimicry in the design of functional POCs provides new insights into manipulating the packing of cages, paving the way for potential applications in guest recognition and adsorption separations.

Bioinspired “Intermolecular Pocket” in Soft Molecular Crystal of Porous Organic Cage Exhibiting Reversible Guest Recognition

Porous Organic Cages (POCs) have gathered a lot of attention in sorts of fields. Previous studies often focused on the functionalization of their intrinsic porosity, while the utilization of the extrinsic porosity has been seldom reported. To date, the rational construction of functionalized extrinsic porosity in POCs is a serious challenge, which still relies on trial and error. Inspired by hydrophobic proteins, in the contribution, a POC (namely NKPOC‐DS) is obtained with hydrophobic “intermolecular pocket” as extrinsic porosity constructed through the assembly of disulfide bonds with hydrophobic groups, facilitating strong supramolecular interactions as confirmed by Electrostatic Potential (ESP) maps and single‐crystal X‐ray diffraction analysis. Notably, NKPOC‐DS exhibits a unique C2H6‐selective "breathing behaviour" due to the presence of softness in its extrinsic porosity, which does not extend to other gases such as C2H4, CH4, CO2, N2, and H2. Such specific recognition of C2H6 thus provides NKPOC‐DS with the ability to preferentially adsorb C2H6 from a C2H6/C2H4 mixture. The innovative approach of biomimicry in the design of functional POCs provides new insights into manipulating the packing of cages, paving the way for potential applications in guest recognition and adsorption separations.

CO2 Responsive Thin-Film Transistors Using Conjugated Polymer Complexes with Single-Walled Carbon Nanotubes.

Introduction of amidine groups within the side chains of a conjugated polyfluorene was carried out using copper-catalyzed azide-alkyne cycloaddition. The resulting polymer was shown to form strong supramolecular interactions with the sidewalls of single-walled carbon nanotubes (SWNTs), forming polymer-nanotube complexes that exhibited solubility in various organic solvents. It was shown that the polymer-SWNT complexes were responsive to CO2, where the amidine groups formed amidinium bicarbonate salts upon CO2 exposure, causing the polymer-SWNT complexes to precipitate. This reaction could be reversed by bubbling N2 through the solution, which caused the polymer-SWNT complexes to redissolve. Incorporation of the polymer-SWNT complexes within thin-film transistor (TFT) devices as the active layer resulted in a CO2-responsive TFT sensor. It was found that the sensory device underwent a reversible shift in its threshold voltage from 5 to -1 V as well as a 1 order of magnitude decrease in its on-current upon exposure to CO2. This work shows that conjugated polymer-wrapped SWNTs having sensory elements within the polymer side chain can be used as the active layer within functional SWNT-based TFT sensors.

Revealing and reconstructing the 3D Li-ion transportation network for superionic poly(ethylene) oxide conductor.

Understanding the Li-ions conduction network and transport dynamics in polymer electrolyte is crucial for developing reliable all-solid-state batteries. In this work, advanced nano- X-ray computed tomography combined with Raman spectroscopy and solid state nuclear magnetic resonance are used to multi-scale qualitatively and quantitatively reveal ion conduction network of poly(ethylene) oxide (PEO)-based electrolyte (from atomic, nano to macroscopic level). With the clear mapping of the microstructural heterogeneities of the polymer segments, aluminium-oxo molecular clusters (AlOC) are used to reconstruct a high-efficient conducting network with high available Li-ions (76.7%) and continuous amorphous domains via the strong supramolecular interactions. Such superionic PEO conductor (PEO-LiTFSI-AlOC) exhibites a molten-like Li-ion conduction behaviour among the whole temperature range and delivers an ionic conductivity of 1.87 × 10-4 S cm-1 at 35 °Ϲ. This further endows Li electrochemical plating/stripping stability under 50 μA cm-2 and 50 μAh cm-2 over 2000 h. The as-built Li|PEO-LiTFSI-AlOC|LiFePO4 full batteries show a high rate performance and a capacity retention more than 90% over 200 cycling at 250 μA cm-2, even enabling a high-loading LiFePO4 cathode of 16.8 mg cm-2 with a specific capacity of 150 mAh g-1 at 50 °Ϲ.

Luminescent metal–organic frameworks for ultrasensitive detection of pesticide and biomarker: In situ imaging and real field application

Frequent uses of pesticides for agricultural led to the environmental pollution and ultimately threaten the human body. On the other hand, the monitoring of the biomarker at the optimum level is also very imperative for human health. So the investigation of smart materials is very essential for visual and on‐site monitoring of pesticide and biomarker. In this regard, we have synthesized highly fluorescent MOF (ZnATA, 1) oriented with free‐NH2 functionality as a guest functional moiety. Framework 1 showed the selective and sensitive ratiometric detection of biomarker riboflavin (RBF). Further, sensor 1 exhibited the discriminating recognition of pesticide 2,6‐dichloro‐4‐nitroaniline (DCNA). The detection limit for both RBF and DCNA is very excellent, and the values are 0.13 and 0.07 ppm, respectively. The detection of RBF and DCNA is very fast (within 3 s) and has been realized through colorimetric response and by cost‐effective paper strip method. Interestingly, the sensor displayed the visual and on‐site (in situ imaging by using real fruit and vegetable) recognition of “DCNA” within 3 s. Sensor 1 further demonstrated the recognition of DCNA in different real field sample (environmental water sample) and RBF in food samples (milk and vitamin B2 tablet). The mechanism of sensing for DCNA and RBF has been comprehended through the occurrence of photo‐induced electron transfer, forster resonance energy transfer, and inert filter effect. Further, the recognition mechanism is justified by the theoretical study. The presence of free‐NH2 moiety in the linker of MOF is possibly to establish a strong supramolecular interaction with the analytes.

A crown-ether-enabled eutectic electrolyte for ultra-high temperature lithium metal batteries

Lithium metal batteries (LMBs) are generally restricted to operating below 60 °C and not suitable for high-temperature applications due to their thermally susceptible carbonate electrolytes. Deep eutectic electrolytes (DEE) with strong supramolecular interactions are a new emerging type of liquid-state ionic conductors, and here we present a novel DEE—which is composed of 18-crown-6 ether (18C6) and lithium difluoro(oxalate)borate (LiDFOB)—to extend the working temperature up to 150 °C. Via combined physiochemical and theoretical characterizations, it is identified that such high thermotolerance is a result of specific solvation structure of Li(18C6)4DFOB with multiple Li–O interactions. Moreover, our newly developed DEE triggers the formation of a B/F-rich solid electrolyte interphase, contributing to superior thermal stability and enhanced compatibility with Li-metal anodes. Consequently, Li|DEE|LiFePO4 cell exhibits great tolerance to extremely high temperatures with a capacity reversibility of 83 % after 250 cycles at 120 °C. Even at 150 °C, the cell can retain 77 % of the initial capacity (105 mAh g−1) after 100 cycles. To our knowledge, the DEE is the first liquid electrolyte for LMBs working at unprecedented high-temperature. This work opens intriguing perspectives to design novel electrolytes for demanded performance of LMBs across a wide temperature range.

Asymmetric Photoreactions in Supramolecular Assemblies.

ConspectusStereochemical control of excited-state asymmetric photoreactions has been one of the most challenging topics of modern photochemistry. The short-lived character of electronically excited photosubstrates and their low activation energy barriers to form both enantiomers are the major obstacles to achieving significant enantioselectivity in excited-state asymmetric photochemistry. Recent research demonstrated that the supramolecular strategy is promising to control the stereochemical outcome of asymmetric photoreaction through relatively strong and long-lasting noncovalent interaction at both ground and excited states. In this methodology, chiral hosts/assemblies provide the chiral environment for photochemically transferring chirality to the complexed photosubstrate in both the ground and the excited states by virtue of relatively strong supramolecular interactions, such as hydrogen bonding, van der Waals, π-π, electrostatic, and hydrophobic interactions. The orientation and conformation of the photosubstrate can be critically manipulated by the supramolecular complexation to ensure the subsequent effective stereoselective photochemical conversion.This Account describes our recent advance in asymmetric photoreactions in supramolecular assemblies. Several chiral photoreactions, including photoisomerization of cycloolefins and photocyclodimerization of anthracene and naphthalene derivatives, have been mediated by various supramolecular hosts, such as cyclodextrin (CD), cucurbituril, pillararene, and chiral polymer. The following advantages of supramolecular asymmetric photochemistry were evidenced: (1) The improvement of stereoselectivity can be enabled by the careful design and fabrication of chiral host molecules. (2) Supramolecular complexation could effectively regulate the orientation and conformation of photosubstrates, thus resulting in novel reaction pathways which create unusual photoproducts that are not achievable through traditional reaction conditions. (3) Asymmetric photoreactions in supramolecular systems showed strong correlations with the external environmental variants, such as temperature, solvent, irradiation wavelength, and pressure, which therefore provide a powerful tool for the regulation of stereoselectivities of excited-state photoreactions. (4) Utilizing supramolecular complexation can dramatically speed up photoreactions, a combination of appropriate photosensitizers/photocatalysts being able to drive catalyzed chiral photoreactions effectively. (5) Photoisomerization in chiral supramolecular systems has been applied to chiroptical molecular devices, which exhibited multiple stimulus-response functions and advanced switching performances. We believe that these concepts, methods, and principles derived therefrom are instructive in designing chiral supramolecular hosts, elucidating the stereodifferentiation mechanisms in the ground and excited states, and analyzing and improving the stereochemical outcomes of a diverse range of supramolecular chiral photoreactions.

Ultrathin Conductive Bithiazole‐Based Covalent Organic Framework Nanosheets for Highly Efficient Electrochemical Biosensing

AbstractCovalent organic frameworks (COFs) with unique structural merits show substantial potential in the construction of biosensors. However, high‐performance COF‐based biosensors have rarely been reported due to special requirements for electrochemical biosensing. Here, the ultrathin nitrogen and sulfur‐rich bithiazole‐based COF nanosheets (COF‐Bta‐NSs) with the thickness of ≈1.95 nm are developed by using an interfacial perturbation growth strategy, and are further integrated with acetylcholinesterase (AChE) through strong supramolecular interactions to construct a high‐performance biosensor for organophosphorus pesticides (OPs) detection. By virtue of the excellent electrical conductivity and abundant edge unsaturated sites of COF‐Bta‐NSs, such unique biosensors can be used for the detection of various OPs, showing a wide detection range, ultralow detection limit, and high stability. Significantly, the portable biosensing device is further set up based on commercialized screen‐printed electrode (SPE), which is sensitive and reliable with the actual samples collected from river water and leafy vegetables, confirming the practical applicability. This research provides a novel insight into the development of advanced COF‐based biosensors with excellent performance for biological and environmental analysis.

Polythiourea Superionic Conductors for Solid-State Batteries

Polymer electrolytes are considered as solid-state ionic conductors for the next generation of lithium metal batteries. Particularly, poly(ethylene oxide)-based electrolytes have been extensively studied due to their excellent ion conductivity and interfacial compatibility. Since the lithium-ion transport is strongly coupled with segmental motion of polymer chains, there usually exists a dilemma between the ion conductivity and mechanical strength enhancement. Other problems of low ion conductivity at low temperature and low cation transference number further impede their practical applications in batteries. Here, we report a type of polythiourea solid-state electrolyte, which exhibits a superionic ion conducting behavior. The strong supramolecular interaction between the thiourea group and perchlorate anions promotes the dissolution of high concentration lithium salts in polythiourea. The conducting channel composed of high-density thiourea and percolating polar groups enables rapid cation transport along the polymer chain and even working at the glass state. The combined merits of high transference number, good ion conductivity, and excellent mechanical strength are achieved in this class of superionic ionic conductors, shedding light on alternative solutions for solid-state electrolytes in batteries.

Large anion binding in water.

Large water-soluble anions with chaotropic character display surprisingly strong supramolecular interactions in water, for example, with macrocyclic receptors, polymers, biomembranes, and other hydrophobic cavities and interfaces. The high affinity is traced back to a hitherto underestimated driving force, the chaotropic effect, which is orthogonal to the common hydrophobic effect. This review focuses on the binding of large anions with water-soluble macrocyclic hosts, including cyclodextrins, cucurbiturils, bambusurils, biotinurils, and other organic receptors. The high affinity of large anions to molecular receptors has been implemented in several lines of new applications, which are highlighted herein.

Synthesis and high sensitivity Al3+ recognition of fluorescent probe molecule based on pincer bis‐N‐heterocyclic carbene

Two bis-(Nitrogen-Heterocyclic Carbene, NHC) derivatives, 1, 3-bis[1-(quinolin-8-yl)-imidazolium-3-yl)]-benzene bis-hexafluorophosphate (2a), 2, 5-bis[1-(quinolin-8-yl)-imidazolium-3-yl)]-pyridine bis-hexafluorophosphate (2b), were synthesized, and characterized by 1H NMR and 13C NMR spectra and X-ray single crystal diffraction. The bis-NHC 2a was demonstrated as an excellent fluorescence chemo-sensor molecule for selectively recognition of Al3+ ion in aqueous-organic media. Its pyridine analogue molecule 2b haven't selectivity recognition character to metal ions with the fluorescence enhancement for most metal ions. A 1:1 binding ratio and strong supramolecular interaction between Al3+ ion and the carbonic hydrogen and quinoline nitrogen were suggested by Job's plot analysis and 1HNMR spectroscopy titrations of Al3+ ion and 2a. The detection limit for Al3+ ion was calculated to be 0.32 µM. The practical application in tap water samples has been evaluated, which reveals the potential applications of bis-NHC 2a in complicated environments.

Experimental design of 1-dodecanol@methylated melamine-formaldehyde microencapsulated composite phase change material and the application in energy storage field

The purpose of this study is to explore a new clean and environment protecting composite microcapsule material with 1-dodecanol (DD) as the core and modified methylated melamine-formaldehyde (MMF) as the shell, to meet the needs of low temperature heat or energy storage (0–40 °C). The microencapsulated phase change material (MPCM) base with a mass ratio of 14:3 was synthesized by in-situ emulsion polymerization, then two kinds of additives 10 wt% boron nitride (BN) and 5 wt% BN mixed with 5 wt% carbon nanotubes (CNTs) were applied to solve the defects of easy leakage and low thermal conductivity, while the samples were defined and shorted as BPCM and BCPCM, respectively. The experimental results showed that the prepared BCPCM presented good storage stability in the temperature range of 0–40 °C, which was due to its good thermal conductivity of 0.584 W/m·K, latent heat of 163.8 J/g, and strong supramolecular interaction between 1-DD and MMF. Through charging and discharging tests for batteries under low temperature, BCPCM indicated excellent thermal management performance, which proposed its application potential in the cryogenic storage environments and battery thermal management system (BTMS) field.

An Aqueous Alginate‐based Binder Modified with Zn2+ Ions and Prussian Blue Analogues for Enhanced Silicon Anodes

AbstractIn this work, an aqueous three‐dimensional (3D) crosslinked alginate‐Zn‐Prussian blue analogue (Alg−Zn‐PBAs) binder with improved mechanical property has been constructed for Si anodes. The Alg−Zn‐PBAs aqueous binder is fabricated via Zn2+ ion‐induced co‐precipitation reaction of PBAs nanoparticles and ionic crosslinking reaction of Alg−Zn network. The anchored PBAs nanoparticles can be formed around the Zn2+ ions and offer enhanced stability due to their strong supramolecular interactions to the Alg−Zn matrix. Consequently, the Si anodes using Alg−Zn‐PBAs binder exhibits a capacity of 1372.9 mAh g−1 for 200 cycles at 0.84 A g−1 and a higher capacity when compared to electrodes fabricated by using Alg−Zn binder and Alg binder. This work demonstrates that the combination of PBAs and alginate via an one‐step process of Zn2+ ions induced co‐precipitation reaction is a better design of aqueous binders for lithium‐ion batteries system with a green synthetic process.

3D Printable, Biomimetic Adhesive, and Self-healing Acrylic Elastomers for Customized Attachable Strain Sensor

The advances in flexible electronics, soft robotics, and many other fields resulted in increased demands for high-performance self-healing elastomers (SHEs). In this work, novel SHEs were prepared by photo-initiated copolymerization of acrylic acid and alkyl acrylates. The as-obtained SHEs exhibited 100% autonomous self-healing efficiency at ambient temperature due to the formation of hydrogen bonding between the hydroxyl groups of acrylic acid unit and carbonyl groups of alkyl acrylate unit. The strong supramolecular interaction yielded SHEs with 3D printing capability, high stretchability, and remarkable adhesion properties. Meanwhile, biomimetic adhesion was developed by solvent-wetting method to enable convenient adherence of SHEs on various substrates. Furthermore, the introduction of carboxylic ionic liquid led to the formation of a nonleaking and attachable ionogel by 3D printing for strain sensing applications. The as-obtained strain sensor precisely detected various gestures of human fingers, and successfully recognized sign language through a comprehensive analysis of electronic signals. In sum, the high-performance SHEs look promising for future SHE-based intelligent products thanks to their common raw feedstocks, 3D printing capability, and multi-functional characteristics.

Modulating Polymer Dynamics via Supramolecular Interaction with Ultrasmall Nanocages for Recyclable Gas Separation Membranes with Intrinsic Microporosity.

The engineering of mixed-matrix membranes is severely hindered by the trade-off between mechanical performance and effective utilization of inorganic fillers' microporosity. Herein, we report a feasible approach for optimal gas separation membranes through the fabrication of coordination nanocages with poly(4-vinylpyridine) (P4VP) via strong supramolecular interactions, enabling the homogeneous dispersion of nanocages in polymer matrixes with long-term structural stability. Meanwhile, suggested from dynamics studies, the strong attraction between P4VP and nanocages slows down polymer dynamics and rigidifies the polymer chains, leading to frustrated packing and lowered densities of the polymer matrix. This effect allows the micropores of nanocages to be accessible to external gas molecules, contributing to the intrinsic microporosity of the nanocomposites and the simultaneous enhancement of permselectivities. The facile strategy for supramolecular synthesis and polymer dynamics attenuation paves avenues to rational design of functional hybrid membranes for gas separation applications.

Natural Polysaccharides as Multifunctional Components for One‐Step 3D Printing Tough Hydrogels

AbstractNatural polysaccharides (NPS) are regarded as biomolecular and structural components for preparing high‐performance tough hydrogels. But the one‐step fabrication of NPS‐containing hydrogels in seconds and the template‐free design of complicated high‐resolution structures are still significant challenges in this field. To meet these requirements, various NPS‐containing tough hydrogels are fabricated and processed into 2D/3D structures via the combination of Ru(bpy)32+‐mediated photochemistry and extrusion 3D printing technique. The whole fabrication process is one‐step, completed in tens of seconds under visible light irradiation. It is found that the used NPS plays a key role in achieving the fabrication of high‐performance structured tough hydrogels. The high reactivity of functional groups in the used NPS can shorten their gelation times. Long rigid chains of the used NPS, their hierarchical assemblies, and contrasting multinetworks benefit from the efficient dissipation of mechanical energy and enhancement of its operational stability. Strong supramolecular interactions enable hydrogel precursors to have high viscosities, therefore providing good controllability to design high‐resolution and complicated tough hydrogel structures via extrusion 3D printing. It is anticipated that this straightforward fabrication strategy and findings will open new horizons for NPS‐containing materials.

Robust fluorogenic non-porphyrin interaction of Zn(II) and Hg(II) naphthadiaza-crown macrocyclic complexes with C60: Spectroscopic and dispersion-corrected DFT study

A family of Zn(II) complexes with naphthadiaza-crown macrocyclic host molecules (Ln = L1-L4) were prepared and characterized employing mass spectrometry, elemental microanalysis, 1H, 13C NMR, IR, UV–vis, fluorescence spectroscopy. The fluorescence study on [M(II)Ln]2+(M = Zn with n = 1–4, Hg with n = 5) complexes denoted on the presence of a notable selective supramolecular interaction with C60 in two different solvents, namely N-Methyl-2-pyrrolidone (NMP) and chloroform for both [Zn(II)L4]2+ and [Hg(II)L5]2+. Employing both UV–vis and fluorescence spectroscopy, 1:1 mol ratio were determined for [M(II)Ln]2+/C60 by applying the Job's plots. Comparing with their free ligands Ln interactions, the binding constant measurements (Kb) at λem = 380 for [M(II)Ln]2+/C60 indicated remarkable increases as 22 and 30% for [Zn(II)L4]2+ and [Hg(II)L5]2+, respectively. The observed quenching of the fluorescence bands in [M(II)Ln]2+ can be described in terms of a static process mechanism, attributed to a non-fluorescent supramolecular interaction of [M(II)Ln]2+ with C60. DFT calculations alongside with NMR experiments imply remarkable π-π interactions of the naphthalene functional groups on the aza-crown macrocycles of [M(II)Ln]2+ complexes with C60. The aforesaid promotions in Kb values are rare among the reported non-porphyrin and –phthalocyanine metal-ion-complexes as the host molecules for C60. Based on DFT/M06-2X and B97-D3 result, L4 represented the highest binding energy in the series, assignable to appropriate goodness of fit for C60 due to the larger macrocycle ring. Along with more negative binding energies, more than seven times higher deformation energy was calculated by B97-D3 for the [Zn(L4)]2+/C60 dyad, comparing with the parent Ln/C60. Comparisons of NCI and RDG plots of [Zn(L4)]2+/C60 with Ln/C60, predicted strong supramolecular interaction between the metal centre of [Zn(L4)]2+ with C60, confirmed by NBO analysis.

Infiltration of Proteins in Cholesteric Cellulose Structures.

Cellulose nanocrystals (CNCs) can spontaneously self-assemble into chiral nematic (cn) structures, similar to natural cholesteric organizations. The latter display highly dissipative fracture propagation mechanisms given their “brick” (particles) and “mortar” (soft matrix) architecture. Unfortunately, CNCs in liquid media have strong supramolecular interactions with most macromolecules, leading to aggregated suspensions. Herein, we describe a method to prepare nanocomposite materials from chiral nematic CNCs (cn-CNCs) with strongly interacting secondary components. Films of cn-CNCs were infiltrated at various loadings with strongly interacting silk proteins and bovine serum albumin. For comparison and to determine the molecular weight range of macromolecules that can infiltrate cn-CNC films, they were also infiltrated with a range of poly(ethylene glycol) polymers that do not interact strongly with CNCs. The extent and impact of infiltration were evaluated by studying the optical reflection properties of the resulting hybrid materials (UV–vis spectroscopy), while fracture dissipation mechanisms were observed via electron microscopy. We propose that infiltration of cn-CNCs enables the introduction of virtually any secondary phase for nanocomposite formation that is otherwise not possible using simple mixing or other conventional approaches.

Multiple Hydrogen Bond-Induced Structural Distortion for Broadband White-Light Emission in Two-Dimensional Perovskites

Low-dimensional hybrid lead-halide perovskites with broadband white-light emission upon near-UV excitation have attracted immense scientific interest due to their potential application for the next...

Two arsenic capped Dawson-type supramolecular hybrid assemblies induced by benzimidazole for photo-/electro-catalytic performance

Two arsenic capped Dawson arsenomolybdate supramolecular hybrid assemblies, (Cu(biz)2)12[CuI(H2O)2{As0.5IIIAs2MoV2MoVI16O62}2]·2H2O (1) (biz)6(ptz) {AsIII2As2Mo18O62}·H2O (2) (biz ​= ​benzimidazole, ptz ​= ​5-(4-pyridyl)- tetrazole), have been synthesized under hydrothermal condition and fully characterized by routine method. In compound 1, the arsenic-capped {As0.5As2MoV2MoVI16} cluster is bonded to each other by Cu(H2O)2 linker to form a straight chain, which is further extended into 2D waveform layer and 3D supramolecular network with 1D channels via similar supramolecular interaction between O atom of Dawson cluster and N derived from {Cu(biz)2} complex. In compound 2, bi-arsenic capped {AsIII2As2Mo18 O62} cluster is connected to 17 biz and 3 ptz ligands, which are further attracted by 12 Dawson analogues to form a 12-connected 3D supramolecular net with a 324.433.59 topology via strong H-bonds and supramolecular interactions. Compound 2 represents the highest connectivity of bi-arsenic capped Dawson supramolecular assembly. Two compounds show dual-functional electrocatalytic activity for reduction of nitrite and oxidation of dopamine, as well as efficient photocatalytic performances for degradation of intractable dyes under UV irradiation.