Observation of “de Vries-like” properties in bent-core molecules

“de Vries” liquid crystals, defined by a maximum layer shrinkage of ≤1% from the smectic A to C phase transition, are an integral component of ferroelectric liquid crystal (FLC) displays. Bona fide de Vries materials described in the literature are primarily perfluorinated, polysiloxane and polysilane-terminated rod-like (or calamitic) LCs. Herein, for the first time, we report a series of newly designed achiral unsymmetrical bent-core molecules with terminal alkoxy chains exhibiting similar properties to “de Vries” LCs. The new molecular structure is based on the systematic distribution of four phenyl rings attached via ester and imine linkers having 3-amino-2-methylbenzoic acid as the central core with a bent angle of 147°. Detailed microscopic investigations in differently aligned (planar as well as homeotropic) cells along with SAXS/WAXS studies revealed that the materials exhibited a SmA–SmC phase sequence along with the appearance of the nematic phase at higher temperatures. SAXS measurements divulged the layer spacings (d-spacings) and hence, the layer shrinkage was calculated ranging from 0.19% to 0.68% just below the SmA–SmC transition. The variation of the calculated molecular tilt angle (α) derived from the temperature-dependent SAXS data, followed the power law with exponent values 0.29 ± 0.01 and 0.25 ± 0.01 for compounds 1/10 and 1/12, respectively. The experimental values obtained were very close to the theoretically predicted values for the materials with de Vries-like properties. The analysis of temperature-dependent birefringence studies based on the prediction of the Landau theory, showed a dip across the SmA–SmC phase transition typical of compounds exhibiting the de Vries characteristics. The collective results obtained suggest “de Vries” SmA as a probable model for this bent-core system which may find applications in displays.

A simple molecular design of unsymmetrical bent-core molecules exhibiting low layer shrinkage and a dip in the birefringence at the SmA–SmC phase transition, typical characteristics of “de Vries” liquid crystals.     

A soft on/off switch based on the electrochemically reversible H–J interconversion of a floating porphyrin membrane

Soft molecular assemblies that respond reversibly to external stimuli are attractive materials as on/off switches, in optoelectronic, memory and sensor technologies. In this Edge Article, we present the reversible structural rearrangement of a soft porphyrin membrane under an electrical potential stimulus in the absence of solid-state architectures. The free-floating porphyrin membrane lies at the interface between immiscible aqueous and organic electrolyte solutions and is formed through interfacial self-assembly of zinc(ii) meso-tetrakis(4-carboxyphenyl)porphyrins (ZnPor). A potential difference between the two immiscible electrolyte solutions induces the intercalation of bis(triphenylphosphoranylidene)ammonium cations from the organic electrolyte that exchange with protons in the porphyrin membrane. In situ UV/vis absorbance spectroscopy shows that this ionic intercalation and exchange induces a structural interconversion of the individual porphyrin molecules in the membrane from an H- to a J-type molecular configuration. These structural rearrangements are reversible over 30 potential cycles. In situ polarisation-modulation fluorescence spectroscopy further provides clear evidence of structural interconversion of the porphyrin membrane, as intercalation of the organic electrolyte cations significantly affects the latter''s emissive properties. By adjusting the pH of the aqueous phase, additional control of the electrochemically reversible structural interconversion can be achieved, with total suppression at pH 3.

The structural rearrangement of a porphyrin membrane self-assembled at a “soft” liquid|liquid interface from a H- to J-molecular configuration is reversibly modulated by externally manipulating the interfacial Galvani potential difference.     

Rational design of an “all-in-one” phototheranostic

We report here porphodilactol derivatives and their corresponding metal complexes. These systems show promise as “all-in-one” phototheranostics and are predicated on a design strategy that involves controlling the relationship between intersystem crossing (ISC) and photothermal conversion efficiency following photoexcitation. The requisite balance was achieved by tuning the aromaticity of these porphyrinoid derivatives and forming complexes with one of two lanthanide cations, namely Gd³⁺ and Lu³⁺. The net result led to a metalloporphodilactol system, Gd-trans-2, with seemingly optimal ISC efficiency, photothermal conversion efficiency and fluorescence properties, as well as good chemical stability. Encapsulation of Gd-trans-2 within mesoporous silica nanoparticles (MSN) allowed its evaluation for tumour diagnosis and therapy. It was found to be effective as an “all-in-one” phototheranostic that allowed for NIR fluorescence/photoacoustic dual-modal imaging while providing an excellent combined PTT/PDT therapeutic efficacy in vitro and in vivo in 4T1-tumour-bearing mice.

We report here porphodilactol derivatives and their corresponding metal complexes as “all-in-one” phototheranostics by controlling the relationship between intersystem crossing (ISC) and photothermal conversion efficiency following photoexcitation.     

Vibrational Stark shift spectroscopy of catalysts under the influence of electric fields at electrode–solution interfaces

External control of chemical processes is a subject of widespread interest in chemical research, including control of electrocatalytic processes with significant promise in energy research. The electrochemical double-layer is the nanoscale region next to the electrode/electrolyte interface where chemical reactions typically occur. Understanding the effects of electric fields within the electrochemical double layer requires a combination of synthesis, electrochemistry, spectroscopy, and theory. In particular, vibrational sum frequency generation (VSFG) spectroscopy is a powerful technique to probe the response of molecular catalysts at the electrode interface under bias. Fundamental understanding can be obtained via synthetic tuning of the adsorbed molecular catalysts on the electrode surface and by combining experimental VSFG data with theoretical modelling of the Stark shift response. The resulting insights at the molecular level are particularly valuable for the development of new methodologies to control and characterize catalysts confined to electrode surfaces. This Perspective article is focused on how systematic modifications of molecules anchored to surfaces report information concerning the geometric, energetic, and electronic parameters of catalysts under bias attached to electrode surfaces.

Heterogeneous electrocatalysis: characterization of interfacial electric field within the electrochemical double layer.     

Kinetics and mechanistic details of bulk ZnO dissolution using a thiol–imidazole system

Oxide dissolution is important for metal extraction from ores and has become an attractive route for the preparation of inks for thin film solution deposition; however, oxide dissolution is often kinetically challenging. While binary “alkahest” systems comprised of thiols and N-donor species, such as amines, are known to dissolve a wide range of oxides, the mechanism of dissolution and identity of the resulting solute(s) remain unstudied. Here, we demonstrate facile dissolution of both bulk synthetic and natural mineral ZnO samples using an “alkahest” that operates via reaction with thiophenol and 1-methylimidazole (MeIm) to give a single, pseudotetrahedral Zn(SPh)₂(MeIm)₂ molecular solute identified by X-ray crystallography. The kinetics of ZnO dissolution were measured using solution ¹H NMR, and the reaction was found to be zero-order in the presence of excess ligands, with more electron withdrawing para-substituted thiophenols resulting in faster dissolution. A negative entropy of activation was measured by Eyring analysis, indicating associative ligand binding in, or prior to, the rate determining step. Combined experimental and computational surface binding studies on ZnO reveal stronger, irreversible thiophenol binding compared to MeIm, leading to a proposed dissolution mechanism initiated by thiol binding to the ZnO surface with the liberation of water, followed by alternating MeIm and thiolate ligand additions, and ultimately cleavage of the ligated zinc complex from the ZnO surface. Design rules garnered from the mechanistic insight provided by this study should inform the dissolution of other bulk oxides into inks for solution processed thin films.

Oxide dissolution is important for metal extraction from ores and has become an attractive route for the preparation of inks for thin film solution deposition; however, oxide dissolution is often kinetically challenging.     

“Eggs in egg cartons”: co-crystallization to embed molecular cages into crystalline lattices

Discrete (M₃L₂)_n cages assembled from a tripodal ligand (L) and metal ions (M: Cu(i) or Ag(i)) are embedded in networked coordination hosts formed by partial dissociation of the same discrete cages during the crystallization process. The resulting “eggs-in-an-egg-carton” structures provide unique examples of the co-crystallization of discrete and infinite coordination frameworks.

Discrete coordination cages were connected into the infinite lattices via shape-complementary co-crystallization with networked coordination hosts in the “eggs-in-an-egg-carton” styles.     

Density functionals with asymptotic-potential corrections are required for the simulation of spectroscopic properties of materials

Five effects of correction of the asymptotic potential error in density functionals are identified that significantly improve calculated properties of molecular excited states involving charge-transfer character. Newly developed materials-science computational methods are used to demonstrate how these effects manifest in materials spectroscopy. Connection is made considering chlorophyll-a as a paradigm for molecular spectroscopy, 22 iconic materials as paradigms for 3D materials spectroscopy, and the V_N⁻ defect in hexagonal boron nitride as an example of the spectroscopy of defects in 2D materials pertaining to nanophotonics. Defects can equally be thought of as being “molecular” and “materials” in nature and hence bridge the relms of molecular and materials spectroscopies. It is concluded that the density functional HSE06, currently considered as the standard for accurate calculations of materials spectroscopy, should be replaced, in most instances, by the computationally similar but asymptotically corrected CAM-B3LYP functional, with some specific functionals for materials-use only providing further improvements.

Spectroscopic transitions in materials that involve charge transfer require asymptotically corrected density functionals. As most transitions do have some charge transfer character, use of such methods are generally warranted.     

Towards photoswitchable quadruple hydrogen bonds via a reversible “photolocking” strategy for photocontrolled self-assembly

Developing new photoswitchable noncovalent interaction motifs with controllable bonding affinity is crucial for the construction of photoresponsive supramolecular systems and materials. Here we describe a unique “photolocking” strategy for realizing photoswitchable control of quadruple hydrogen-bonding interactions on the basis of modifying the ureidopyrimidinone (UPy) module with an ortho-ester substituted azobenzene unit as the “photo-lock”. Upon light irradiation, the obtained Azo-UPy motif is capable of unlocking/locking the partial H-bonding sites of the UPy unit, leading to photoswitching between homo- and heteroquadruple hydrogen-bonded dimers, which has been further applied for the fabrication of novel tunable hydrogen bonded supramolecular systems. This “photolocking” strategy appears to be broadly applicable in the rational design and construction of other H-bonding motifs with sufficiently photoswitchable noncovalent interactions.

A photolocking strategy is described to achieve the construction of effectively photoswitchable quadruple hydrogen bonds featuring with photoregulable H-bonding affinities, which is further applied in the photocontrollable H-bonded self-assemblies.     

[Ni30S16(PEt3)11]: an open-shell nickel sulfide nanocluster with a “metal-like” core

Reaction of [Ni(1,5-cod)₂] (30 equiv.) with PEt₃ (46 equiv.) and S₈ (1.9 equiv.) in toluene, followed by heating at 115 °C for 16 h, results in the formation of the atomically precise nanocluster (APNC), [Ni₃₀S₁₆(PEt₃)₁₁] (1), in 14% isolated yield. Complex 1 represents the largest open-shell Ni APNC yet isolated. In the solid state, 1 features a compact “metal-like” core indicative of a high degree of Ni–Ni bonding. Additionally, SQUID magnetometry suggests that 1 possesses a manifold of closely-spaced electronic states near the HOMO–LUMO gap. In situ monitoring by ESI-MS and ³¹P{¹H} NMR spectroscopy reveal that 1 forms via the intermediacy of smaller APNCs, including [Ni₈S₅(PEt₃)₇] and [Ni₂₆S₁₄(PEt₃)₁₀] (2). The latter APNC was also characterized by X-ray crystallography and features a nearly identical core structure to that found in 1. This work demonstrates that large APNCs with a high degree of metal–metal bonding are isolable for nickel, and not just the noble metals.

The atomically-precise nanocluster, [Ni₃₀S₁₆(PEt₃)₁₁], features a compact “metal-like” core indicative of a high degree of Ni–Ni bonding, along with an open-shell ground state.     

“Click-switch” – one-step conversion of organic azides into photochromic diarylethenes for the generation of light-controlled systems

Diarylethenes (DAEs) are an established class of photochromic molecules, but their effective incorporation into pre-existing targets is synthetically difficult. Here we describe a new class of DAEs in which one of the aryl rings is a 1,2,3-triazole that is formed by “click” chemistry between an azide on the target and a matching alkyne–cyclopentene–thiophene component. This late-stage zero-length linking allows for tight integration of the DAE with the target, thereby increasing the chances for photomodulation of target functions. Nineteen different DAEs were synthesized and their properties investigated. All showed photochromism. Electron-withdrawing groups, and in particular −M-substituents at the triazole and/or thiophene moiety resulted in DAEs with high photo- and thermostability. Further, the chemical nature of the cyclopentene bridge had a strong influence on the behaviour upon UV light irradiation. Incorporation of perfluorinated cyclopentene led to compounds with high photo- and thermostability, but the reversible photochromic reaction was restricted to halogenated solvents. Compounds containing the perhydrogenated cyclopentene bridge, on the other hand, allowed the reversible photochromic reaction in a wide range of solvents, but had on average lower photo- and thermostabilities. The combination of the perhydrocyclopentene bridge and electron-withdrawing groups resulted in a DAE with improved photostability and no solvent restriction. Quantum chemical calculations helped to identify the photoproducts formed in halogenated as well as non-halogenated solvents. For two optimized DAE photoswitches, photostationary state composition and reaction quantum yields were determined. These data revealed efficient photochemical ring closure and opening. We envision applications of these new photochromic diarylethenes in photonics, nanotechnology, photobiology, photopharmacology and materials science.

New photochromic diarylethenes are reported in which one aryl ring is a 1,2,3-triazole that is formed by “click” chemistry between an azide on the target and a matching alkyne–cyclopentene–thiophene component.     

A homogeneous high-DAR antibody–drug conjugate platform combining THIOMAB antibodies and XTEN polypeptides

The antibody–drug conjugate (ADC) is a well-validated modality for the cell-specific delivery of small molecules with impact expanding rapidly beyond their originally-intended purpose of treating cancer. However, antibody-mediated delivery (AMD) remains inefficient, limiting its applicability to targeting highly potent payloads to cells with high antigen expression. Maximizing the number of payloads delivered per antibody is one key way in which delivery efficiency can be improved, although this has been challenging to carry out; with few exceptions, increasing the drug-to-antibody ratio (DAR) above ∼4 typically destroys the biophysical properties and in vivo efficacy for ADCs. Herein, we describe the development of a novel bioconjugation platform combining cysteine-engineered (THIOMAB) antibodies and recombinant XTEN polypeptides for the unprecedented generation of homogeneous, stable “TXCs” with DAR of up to 18. Across three different bioactive payloads, we demonstrated improved AMD to tumors and Staphylococcus aureus bacteria for high-DAR TXCs relative to conventional low-DAR ADCs.

Efficiency of targeted cell delivery of small molecules was enhanced in cells and animals via a novel well-defined bioconjugation platform combining site-specific antibody conjugation and XTEN polypeptides to enable high payload loading.     

Experimental and Theoretical Study of the Ultrafast Dynamics of a Ni2Dy2‐Compound in DMF After UV/Vis Photoexcitation

Invited for this month''s cover picture are the groups of Wolfgang Hübner (TU Kaiserslautern, Germany), Annie Powell (Karlsruhe Institut of Technology, Germany), and Andreas‐Neil Unterreiner (Karlsruhe Institut of Technology, Germany). The cover picture shows the Dy₂Ni₂‐molecular magnet being excited with a UV/Vis laser pulse, together with its time‐resolved spectrum after the pulse. The comparison of the theoretical and the experimental spectra together with both the observed and the calculated relaxation times reveal, among others, three key points: the intermediate states participating in the laser‐induced dynamics, the partial metal‐to‐oxygen charge‐transfer excitations, and the order of magnitude of the coupling of the molecular magnet to the thermal bath of the environment. Read the full text of their Full Paper at 10.1002/open.202100153.

“… The comparison of the theoretical and the experimental spectra together with both the observed and the calculated relaxation times reveals three key points…” Find out more about the story behind the front cover research at 10.1002/open.202100153.     

Single-chain magnet behavior in a finite linear hexanuclear molecule

The careful monitoring of crystallization conditions of a mixture made of a Tb^III building block and a substituted nitronyl-nitroxide that typically provides infinite coordination polymers (chains), affords a remarkably stable linear hexanuclear molecule made of six Tb^III ions and five NIT radicals. The hexanuclear units are double-bridged by water molecules but ab initio calculations demonstrate that this bridge is inefficient in mediating any magnetic interaction other than a small dipolar antiferromagnetic coupling. Surprisingly the hexanuclears, despite being finite molecules, show a single-chain magnet (SCM) behavior. This results in a magnetic hysteresis at low temperature whose coercive field is almost doubled when compared to the chains. We thus demonstrate that finite linear molecules can display SCM magnetic relaxation, which is a strong asset for molecular data storage purposes because 1D magnetic relaxation is more robust than the relaxation mechanisms observed in single-molecule magnets (SMMs) where under-barrier magnetic relaxation can operate.

A stable hexanuclear molecule made of a Tb^III building block and a substituted nitronyl-nitroxide radical show a single-chain magnet behavior despite being a finite molecule.     

Expanding organofluorine chemical space: the design of chiral fluorinated isosteres enabled by I(i)/I(iii) catalysis

Short aliphatic groups are prevalent in bioactive small molecules and play an essential role in regulating physicochemistry and molecular recognition phenomena. Delineating their biological origins and significance have resulted in landmark developments in synthetic organic chemistry: Arigoni''s venerable synthesis of the chiral methyl group is a personal favourite. Whilst radioisotopes allow the steric footprint of the native group to be preserved, this strategy was never intended for therapeutic chemotype development. In contrast, leveraging H → F bioisosterism provides scope to complement the chiral, radioactive bioisostere portfolio and to reach unexplored areas of chiral chemical space for small molecule drug discovery. Accelerated by advances in I(i)/I(iii) catalysis, the current arsenal of achiral 2D and 3D drug discovery modules is rapidly expanding to include chiral units with unprecedented topologies and van der Waals volumes. This Perspective surveys key developments in the design and synthesis of short multivicinal fluoroalkanes under the auspices of main group catalysis paradigms.

Short aliphatic groups are prevalent in bioactive small molecules and play an essential role in regulating physicochemistry and molecular recognition phenomena.     

Enhancement of Chiroptical Responses of trans‐Bis[(β‐iminomethyl)naphthoxy]platinum(II) Complexes with Distorted Square Planar Coordination Geometry

Invited for this month''s cover picture are the groups of Masahiro Ikeshita and Takashi Tsuno at Nihon University and Yoshitane Imai at Kindai University (Japan). The cover picture shows the comparison of circularly polarized luminescence (CPL) properties of square planar platinum(II) complexes with different coordination geometry. Computational studies have been carried out to investigate these structure‐dependencies, and revealed that the distortion of the coordination geometry results into an enhancement the chiroptical responses of these compounds. Read the full text of their Research Article at 10.1002/open.202100277.

“… How does the stereochemistry of transition metal complexes affect their photophysical properties…” Find out more about the story behind the front cover research at 10.1002/open.202100277.     

An “OFF–ON–OFF” fluorescence protein-labeling probe for real-time visualization of the degradation of short-lived proteins in cellular systems

The ability to monitor proteolytic pathways that remove unwanted and damaged proteins from cells is essential for understanding the multiple processes used to maintain cellular homeostasis. In this study, we have developed a new protein-labeling probe that employs an ‘OFF–ON–OFF’ fluorescence switch to enable real-time imaging of the expression (fluorescence ON) and degradation (fluorescence OFF) of PYP-tagged protein constructs in living cells. Fluorescence switching is modulated by intramolecular contact quenching interactions in the unbound probe (fluorescence OFF) being disrupted upon binding to the PYP-tag protein, which turns fluorescence ON. Quenching is then restored when the PYP-tag–probe complex undergoes proteolytic degradation, which results in fluorescence being turned OFF. Optimization of probe structures and PYP-tag mutants has enabled this fast reacting ‘OFF–ON–OFF’ probe to be used to fluorescently image the expression and degradation of short-lived proteins.

An “OFF–ON–OFF” fluorescence probe for real-time imaging of the expression (fluorescence ‘OFF’) and degradation (fluorescence ‘ON’) of short lived PYP-tag proteins in cellular systems.     

Surface-controlled spatially heterogeneous physical properties of a supramolecular gel with homogeneous chemical composition

Controlling supramolecular self-assembly across multiple length scales to prepare gels with localised properties is challenging. Most strategies concentrate on fabricating gels with heterogeneous components, where localised properties are generated by the stimuli-responsive component. Here, as an alternative approach, we use a spiropyran-modified surface that can be patterned with light. We show that light-induced differences in surface chemistry can direct the bulk assembly of a low molecular weight gelator, 2-NapAV, meaning that mechanical gel properties can be controlled by the surface on which the gel is grown. Using grazing incidence X-ray diffraction and grazing incidence small angle X-ray scattering, we demonstrate that the origin of the different gel properties relates to differences in the architectures of the gels. This provides a new method to prepare a single domain (i.e., chemically homogeneous) hydrogel with locally controlled (i.e., mechanically heterogeneous) properties.

A mechanical pattern is created in a hydrogel film by pre-patterning the underlying surface chemistry. This allows spatial variation of the viscous component of the gel, controlling dissipative forces in the gel film without altering gel chemistry.     

Rational design of a “dual lock-and-key” supramolecular photosensitizer based on aromatic nucleophilic substitution for specific and enhanced photodynamic therapy

Photosensitizing agents are essential for precise and efficient photodynamic therapy (PDT). However, most of the conventional photosensitizers still suffer from limitations such as aggregation-caused quenching (ACQ) in physiological environments and toxic side-effects on normal tissues during treatment, leading to reduced therapeutic efficacy. Thus, integrating excellent photophysical properties and accurate carcinoma selectivity in a photosensitizer system remains highly desired. Herein, a “dual lock-and-key” supramolecular photosensitizer BIBCl–PAE NPs for specific and enhanced cancer therapy is reported. BIBCl–PAE NPs are constructed by encapsulating a rationally designed glutathione (GSH)-activatable photosensitizer BIBCl in a pH-responsive diblock copolymer. In normal tissues, BIBCl is “locked” in the hydrophobic core of the polymeric micelles due to ACQ. Under the “dual key” activation of low pH and high levels of GSH in a tumor microenvironment, the disassembly of micelles facilitates the reaction of BIBCl with GSH to release water-soluble BIBSG with ideal biocompatibility, enabling the highly efficient PDT. Moreover, benefiting from the Förster resonance energy transfer effect of BIBSG, improved light harvesting ability and ¹O₂ production are achieved. In vitro and vivo experiments have demonstrated that BIBCl–PAE NPs are effective in targeting and inhibiting carcinoma. BIBCl–PAE NPs show superior anticancer efficiency relative to non-activatable controls.

The “dual lock-and-key” supramolecular photosensitizers enable specific and enhanced photodynamic therapy (PDT).     

De novo generation of a bright blue fluorophore from 2-oxoglutarate in biological samples

We discovered the generation of a new bright blue fluorophore from a particular type of amine and 2-oxoglutarate (2-OG) under mild conditions without any chemical additives. Two β-aminoethylamine molecules and three 2-OG molecules form an unprecedented 2-pyridone structure with a fused γ-lactam ring (DTPP) via complex reactions including double decarboxylation and quintuple dehydration. The DTPP fluorophore shows a high quantum yield (80%) and photostability. The great potential of the present DTPP generation in the quantitative analysis of 2-OG in biosamples is demonstrated.

DTPP, a bright fluorophore with 2-pyridone and γ-lactam, is generated in a de novo manner from non-fluorogenic 2-oxoglutarate and specific amines. The DTPP-based fluorometry is applied to the analysis of 2-oxoglutarate in a biological sample.     

The inorganic cation-tailored “trapdoor” effect of silicoaluminophosphate zeolite for highly selective CO2 separation

Functional nanoporous materials are widely explored for CO₂ separation, in particular, small-pore aluminosilicate zeolites having a “trapdoor” effect. Such an effect allows the specific adsorbate to push away the sited cations inside the window followed by exclusive admission to the zeolite pores, which is more advantageous for highly selective CO₂ separation. Herein, we demonstrated that the protonated organic structure-directing agent in the small-pore silicoaluminophosphate (SAPO) RHO zeolite can be directly exchanged with Na⁺, K⁺, or Cs⁺ and that the Na⁺ form of SAPO-RHO exhibited unprecedented separation for CO₂/CH₄, superior to all of the nanoporous materials reported to date. Rietveld refinement revealed that Na⁺ is sited in the center of the single eight-membered ring (s8r), while K⁺ and Cs⁺ are sited in the center of the double 8-rings (d8rs). Theoretical calculations showed that the interaction between Na⁺ and the s8r in SAPO-RHO was stronger than that in aluminosilicate RHO, giving an enhanced “trapdoor” effect and record high selectivity for CO₂ with the separation factor of 2196 for CO₂/CH₄ (0.02/0.98 bar). The separation factor of Na-SAPO-RHO for CO₂/N₂ was 196, which was the top level among zeolitic materials. This work opens a new avenue for gas separation by using diverse silicoaluminophosphate zeolites in terms of the cation-tailored “trapdoor” effect.

The sodium form of silicoaluminophosphate RHO zeolite exhibits a pronounced cation-tailored “trapdoor” effect, showing an unprecedented selectivity adsorption separation performance for CO₂/CH₄ and CO₂/N₂.