Supramolecular Organic Frameworks Research Articles

Sensitively liquid and gaseous detection of formaldehyde based on a supramolecular organic framework

Because of the serious threat to human health, the development of fluorescent sensor for detection of formaldehyde (FA) has attracted great concern. Herein, a 4,4′-(1,2-diphenylethene-1,2-diyl)dibenzoic acid-based SOF (HNU-44), has been assembled, which can be used to detect FA by quite different fluorescent response in liquid and gas. In liquid phase, HNU-44 exhibits fluorescence enhancement with the limit of detection (LOD) 27.41 ppb. On the contrary, fluorescence quenching happens when HNU-44 is exposed in the FA atmosphere with the LOD of 2.61 ppb. The LOD in gas is even lower than the air quality criterion of gaseous FA (80 ppb) recommended by World Health Organization (WHO). Furthermore, sensing tests were performed on fish samples, which means that HNU-44 can be used in actual sample. This work expands promising approach for effective FA detection both in the experiment test and actual application.

Host-guest interaction tailored cucurbit[6]uril-based supramolecular organic frameworks (SOFs) for drug delivery

An approach for the construction of crystalline porous supramolecular organic frameworks (SOFs) via outer-surface interactions of cucurbit[6]uril (Q[6]) with high yield is presented. This approach enables the noncovalent integration of guest molecules into ordered topologies and creates new host–guest-complex-based SOFs; i.e., the topology can be predesigned and constructed by using [ZnCl4]2− anions to induce the formation of solid Q[6]-SOFs, and the pore wall surface can be easily modified by the Q[6]-encapsulated guest molecules. In addition, one of prepared solid Q[6]-SOFs showed a high drug-loading capacity and smart potential release control for drug-delivery applications

Synthesis of microporous hydrogen-bonded supramolecular organic frameworks through guanosine self-assembly

Extending the structural hierarchy and complexity through small-molecular self-assembly is a powerful way to obtain large discrete, functional molecular architecture. A hydrogen-bonded supramolecular organic framework (HSOF) with nanometer-size pores is constructed in a solid state with simple guanosine-monomer self-assembly. To extend the hierarchy of the G-quartet self-assembly to a higher order thanthatofthetraditionalG-quadruplex,H-bondacceptorsontheC-8 position of guanosine are introduced to establish inter-quadruplex linkage via H bonding to N(2)-HB from the neighboring G-quartet. After screening different C-8 substitution groups and various synthesis conditions, HSOF-G1a' is obtained by solvent evaporation under diluted condition. Single-crystal X-ray structure reveals that cubic repeating units formed by G8 are the supermolecule secondary building block (SBU) with large pores (d=34A). To our knowledge, this is the first G-quartet self-assembly with an organized structure beyond cylindrical G-quadruplexes.

Mitochondria-targeting and ROS-sensitive smart nanoscale supramolecular organic framework for combinational amplified photodynamic therapy and chemotherapy

Owing to their reversibly dynamic features, and the regularity of their architectures, supramolecular organic frameworks (SOFs) have attracted attention as new porous materials. Herein, we propose a smart SOF platform for enhanced photodynamic therapy, where the SOF with a superior mitochondria-targeting capability could be cleaved by reactive oxygen species (ROS) produced by itself for highly enhancing PDT. Moreover, it can further work as a platform for carrying chemo-therapeutic drug doxorubicin for synergistic chemo-photodynamic therapy. The SOF is constructed by combining a tetra-β-cyclodextrin-conjugated porphyrin photosensitizer and a ROS-sensitive thioketal linked adamantane dimer utilizing a host-guest supramolecular strategy. The unique supramolecular framework not only completely resolves the aggregation caused quenching of porphyrin photosensitizers but also endows them with significantly enhanced water-solubility. The in vitro and in vivo results demonstrate that the SOF could be targeted onto mitochondria by confocal imaging, and dissociated by ROS generated by itself, leading to autonomous release of porphyrin photosensitizers and DOX for high anti-cancer activity. It is believed that the strategy using a SOF has the potential of being used to construct versatile agents for combined therapies. Statement of significancePhotosensitizers are the essential element in photodynamic therapy. However, typical photosensitizers commonly encounter poor water-solubility, non-specific tumor-targeting, aggregation-caused quenching (ACQ), which seriously reduce PDT efficacy. A mitochondria-targeting and ROS-sensitive supramolecular organic framework (SOF) is designed for photodynamic therapy in cancer treatment, which could completely overcome the bottleneck in the applications of photosensitizers (PSs). The SOF is constructed by combining a tetra-β-cyclodextrin-conjugated porphyrin photosensitizer and a ROS-sensitive thioketal linked adamantane dimer unit utilizing a host-guest supramolecular strategy. The unique supramolecular framework not only completely resolves the aggregation caused quenching of porphyrin photosensitizers but also endows them with significantly enhanced water-solubility. Moreover, the SOF can be readily functionalized to incorporate the anti-cancer agent Doxorubicin and mitochondria targeting molecules through respective physical encapsulation and host-guest interactions.

High adsorption and separation performance of CO2 over N2 in azo-based (N=N) pillar[6]arene supramolecular organic frameworks* *Project supported by Shandong Province Higher Education Science and Technology Program, China (Grant No. J17KA016), State Key Laboratory of Bio- Fibers and Eco-Textiles (Grant No. K2019-12), and the Cultivation Fund of Henan Normal University, China (Grant No. 2020PL15).

Azo-based pillar[6]arene supramolecular organic frameworks are reported for CO2 and N2 adsorption and separation by density functional theory and grand canonical Monte–Carlo simulation. Azo-based pillar[6]arene provides suitable environment for CO2 adsorption and selectivity. The adsorption and selectivity results show that introducing azo groups can effectively improve CO2 adsorption and selectivity over N2, and both CO2 adsorption and CO2 selectivity over N2 follow the sequence pillar[6]arene_N4 > pillar[6]arene_N2 > pillar[6]arene. Pillar[6]arene_N4 exhibits CO2 adsorption capacity of ∼ 1.36 mmol/g, and superior selectivity of CO2 over N2 of ∼ 116.75 with equal molar fraction at 1 bar (1 bar = 105 Pa) and 298 K. Interaction analysis confirms that both the Coulomb and van der Waals interactions between CO2 with pillar[6]arene frameworks are greater than that of N2. The stronger affinity of CO2 with pillar[6]arene_N4 than other structures and the larger isosteric heat differences between CO2 and N2 rendered pillar[6]arene_N4 to present the high CO2 adsorption capacity and high CO2 selectivity over N2. Our results highlight the potential of azo-functionalization as an excellent means to improve pillar[6]arene for CO2 capture and separation.

Highly Fluorinated Trianglimine Macrocycles: A Supramolecular Organic Framework

AbstractA novel highly fluorinated dialdehyde was prepared by a two-stage synthesis. This reactive building block for dynamic imine chemistry was used in a condensation reaction to generate the first extensively fluorinated trianglimine. An analysis of the material properties and, especially, the crystal structure of the [3+3] macrocycle revealed a supramolecular organic framework with tubular porous channels. The use of fluorinated ligands to generate hydrophobic electron-deficient channel-like pores is an important addition to the ever-expanding field of supramolecular networks and to trianglimine chemistry in general.

Toward a Two-Dimensional Supramolecular Organic Framework with High Degree of Internal Order via Amphiphilic Modification

Solution-phase self-assembly of two-dimensional (2D) networks with a high degree of internal order and long-range periodicity is a great challenge. Herein, we report a rational design to improve 2D...

A Single-Component Supramolecular Organic Framework with Efficient Ultralong Phosphorescence

Supramolecular organic frameworks (SOFs), due to the atomically precise integration of the repeated building units, exhibit intriguing properties and consequently potential applications in chemical...

Robust Supramolecular Nano-Tunnels Built from Molecular Bricks*.

Herein we report a linear ionic molecule that assembles into a supramolecular nano-tunnel structure through synergy of trident-type ionic interactions and π-π stacking interactions. The nano-tunnel crystal exhibits anisotropic guest adsorption behavior. The material shows good thermal stability and undergoes multi-stage single-crystal-to-single-crystal phase transformations to a nonporous structure on heating. The material exhibits a remarkable chemical stability under both acidic and basic conditions, which is rarely observed in supramolecular organic frameworks and is often related to structures with designed hydrogen-bonding interactions. Because of the high polarity of the tunnels, this molecular crystal also shows a large CO2 -adsorption capacity while excluding other gases at ambient temperature, leading to high CO2 /CH4 selectivity. Aggregation-induced emission of the molecules gives the bulk crystals vapochromic properties.

Robust Supramolecular Nano‐Tunnels Built from Molecular Bricks**

AbstractHerein we report a linear ionic molecule that assembles into a supramolecular nano‐tunnel structure through synergy of trident‐type ionic interactions and π–π stacking interactions. The nano‐tunnel crystal exhibits anisotropic guest adsorption behavior. The material shows good thermal stability and undergoes multi‐stage single‐crystal‐to‐single‐crystal phase transformations to a nonporous structure on heating. The material exhibits a remarkable chemical stability under both acidic and basic conditions, which is rarely observed in supramolecular organic frameworks and is often related to structures with designed hydrogen‐bonding interactions. Because of the high polarity of the tunnels, this molecular crystal also shows a large CO2‐adsorption capacity while excluding other gases at ambient temperature, leading to high CO2/CH4 selectivity. Aggregation‐induced emission of the molecules gives the bulk crystals vapochromic properties.

Pyridine Detection Using Supramolecular Organic Frameworks Incorporating Cucurbit[10]uril.

A physical impregnation method is presented in this study, providing a facile approach to encapsulating functional guest molecules (GMs) into robust crystalline supramolecular organic frameworks incorporating cucurbit[10]uril (Q[10]-SOF). As Q[10]-SOF has high evaporated pyridine affinity under normal atmospheric pressure, pyridine molecules in this method were successfully encapsulated into the nanospace formed by GMs and Q[10]-SOF while retaining their crystal framework, morphology, and high stability. GMs@Q[10]-SOF solid materials were found to respond to pyridine, being suitable to be used as solid sensors. Notably, Q[10]-SOF loading with pyrene exhibited a unique response to pyridine along with dramatic fluorescence quenching; loading with dansyl chloride exhibited a unique response to pyridine along with significant fluorescence enhancement, having a quick response within 60 s. Our findings represent a critical advancement in the design of pyridine detection and adsorption for commercial gas identification and sensing.

Adaptive Chirality of an Achiral Cucurbit[8]uril‐Based Supramolecular Organic Framework for Chirality Induction in Water

AbstractChiral framework materials have been developed for many applications including chiral recognition, chiral separation, asymmetric catalysis, and chiroptical materials. Herein, we report that an achiral cucurbit[8]uril‐based supramolecular organic framework (SOF‐1) with the dynamic rotational conformation of tetraphenylethene units can exhibit adaptive chirality to produce M‐SOF‐1 or P‐SOF‐1 with mirror‐image circular dichroism (CD) with gabs≈±10−4 and circularly polarized luminescence (CPL) with glum≈±10−4 induced by L‐/D‐phenylalanine in water, respectively. The chirality induction in CD (gabs≈−10−4) and CPL (glum≈−10−4) of P‐SOF‐1 from achiral SOF‐1 can be presented by using a small amount of adenosine‐5′‐triphosphate disodium (ATP) or adenosine‐5′‐diphosphate disodium (ADP) (only 0.4 equiv) in water. Furthermore, the adaptive chirality of SOF‐1 can be used to determine dipeptide sequences (e.g., Phe‐Ala and Ala‐Phe) and distinguish polypeptides/proteins (e.g., somatostatin and human insulin) with characteristic CD spectra. Therefore, achiral SOF‐1 as an ideal chiroptical platform with adaptive chirality may be applied to determine the enantiopurity of amino acids (e.g., L‐/D‐phenylalanine), develop aqueous CPL materials, and distinguish biological chiral macromolecules (e.g., peptides/proteins) via chirality induction in water.

Adaptive Chirality of an Achiral Cucurbit[8]uril-Based Supramolecular Organic Framework for Chirality Induction in Water.

Chiral framework materials have been developed for many applications including chiral recognition, chiral separation, asymmetric catalysis, and chiroptical materials. Herein, we report that an achiral cucurbit[8]uril-based supramolecular organic framework (SOF-1) with the dynamic rotational conformation of tetraphenylethene units can exhibit adaptive chirality to produce M-SOF-1 or P-SOF-1 with mirror-image circular dichroism (CD) with gabs ≈±10-4 and circularly polarized luminescence (CPL) with glum ≈±10-4 induced by L-/D-phenylalanine in water, respectively. The chirality induction in CD (gabs ≈-10-4 ) and CPL (glum ≈-10-4 ) of P-SOF-1 from achiral SOF-1 can be presented by using a small amount of adenosine-5'-triphosphate disodium (ATP) or adenosine-5'-diphosphate disodium (ADP) (only 0.4 equiv) in water. Furthermore, the adaptive chirality of SOF-1 can be used to determine dipeptide sequences (e.g., Phe-Ala and Ala-Phe) and distinguish polypeptides/proteins (e.g., somatostatin and human insulin) with characteristic CD spectra. Therefore, achiral SOF-1 as an ideal chiroptical platform with adaptive chirality may be applied to determine the enantiopurity of amino acids (e.g., L-/D-phenylalanine), develop aqueous CPL materials, and distinguish biological chiral macromolecules (e.g., peptides/proteins) via chirality induction in water.

Cucurbit[n]uril‐Based Supramolecular Frameworks Assembled through Outer‐Surface Interactions

AbstractPorous materials, especially metal–organic frameworks, covalent organic frameworks, and supramolecular organic frameworks, are widely used in heterogeneous catalysis, adsorption, and ion exchange. Cucurbit[n]urils (Q[n]s) suitable building units for porous materials because they possess cavities with neutral electrostatic potential, portal carbonyls with negative electrostatic potential, and outer surfaces with positive electrostatic potential, which may result in the formation of Q[n]‐based supramolecular frameworks (QSFs) assembled through the interaction of guests within Q[n]s, the coordination of Q[n]s with metal ions, and outer‐surface interaction of Q[n]s (OSIQ). This review summarizes the various QSFs assembled via OSIQs. The QSFs can be classified as being assembled by 1) self‐induced OSIQ, 2) anion‐induced OSIQ, and 3) aromatic‐induced OSIQ. The design and construction of QSFs with novel structures and specific functional properties may establish a new research direction in Q[n] chemistry.

Cucurbit[n]uril-Based Supramolecular Frameworks Assembled through Outer-Surface Interactions.

Porous materials, especially metal-organic frameworks, covalent organic frameworks, and supramolecular organic frameworks, are widely used in heterogeneous catalysis, adsorption, and ion exchange. Cucurbit[n]urils (Q[n]s) suitable building units for porous materials because they possess cavities with neutral electrostatic potential, portal carbonyls with negative electrostatic potential, and outer surfaces with positive electrostatic potential, which may result in the formation of Q[n]-based supramolecular frameworks (QSFs) assembled through the interaction of guests within Q[n]s, the coordination of Q[n]s with metal ions, and outer-surface interaction of Q[n]s (OSIQ). This review summarizes the various QSFs assembled via OSIQs. The QSFs can be classified as being assembled by 1) self-induced OSIQ, 2) anion-induced OSIQ, and 3) aromatic-induced OSIQ. The design and construction of QSFs with novel structures and specific functional properties may establish a new research direction in Q[n] chemistry.

Dimension-controllable and photo-responsive supramolecular organic framworks through cucurbit[8]uril-based self-assembly

Dimension-controllable supramolecular organic frameworks (SOFs) with aggregation-enhanced fluorescence are hierarchically fabricated through the host-guest interactions of cucurbit[8]uril (CB[8]) and coumarin-modified tetraphenylethylene derivatives (TPEC). The three-dimensional layered SOFs could be constructed from the further stacking of two-dimensional mono-layered structures via simply regulating the self-assembly conditions including the culturing time and concentration. Upon light irradiation under the wavelength of 365 nm, the photodimerization of coumarin moieties occurred, which resulted in the transformation of the resultant TPECn/CB[8]4n two-dimensional SOFs into robust covalently-connected 2D polymers with molecular thickness. Interestingly, the supramolecular system of TPECn/CB[8]4n exhibited intriguing multicolor fluorescence emission from yellow to blue in the time range of 0−24 h at 365 nm irradiation, possessing potential applicability for photochromic fluorescence ink.

A crystalline covalent organic framework embedded with a crystalline supramolecular organic framework for efficient iodine capture

A bicrystalline composite based on a triazine covalent organic framework (COF) and a bisbenzimidazole supramolecular organic framework (SOF) was prepared for the first time and used for adsorption of gaseous iodine.

Iron(ii) pillared-layer responsive frameworks via “kagomé dual” (kgd) supramolecular tessellations

FeII supramolecular metal organic framework was constructed by supramolecular tessellation. Guest respiration provides dual channel for optical and magnetic sensing based on allosteric effect.

Room-temperature phosphorescence of a water-soluble supramolecular organic framework

A porous water-soluble supramolecular organic framework efficiently exhibiting phosphorescence was developed both in an aqueous phase and in film state at room-temperature.

A facile cucurbit[8]uril-based porous assembly: utilization in the adsorption of drugs and their controlled release

Cucurbit[n]urils (Q[n]s) are essential members of the supramolecular organic framework family owing to their distinct structure.