Anionic Guests Research Articles

Structural features and dynamic behaviour of the interlayer space of layered double hydroxide coatings

Layered double hydroxide (LDH) offer great potentialities to design functional coatings with customizable properties by exploiting their anion exchange properties. We investigated the anion exchange properties and expansion capacity of the interlayer space relating to the starting film morphology. ZnAl LDH coatings of different thicknesses and morphologies were first obtained by an in situ method using Al-based substrates. When the anion to intercalate is relatively bigger than the starting nitrates, the intercalation may be constrained by the initial LDH particle size and density composing the film. After optimising the morphology, the intercalation of three functional anions with potential antimicrobial properties was successfully achieved with an expansion of the interlayer space up to 150 % while holding the coating integrity. The release of the guest anion was studied by immersion in physiological saline solution. Finally, the possibility to regenerate the coating was demonstrated supporting the potential of these hybrid coatings for applications.

Recent Progress of Remediating Heavy Metal Contaminated Soil Using Layered Double Hydroxides as Super-Stable Mineralizer.

Heavy metal contamination in soil, which is harmful to both ecosystem and mankind, has attracted worldwide attention from the academic and industrial communities. However, the most-widely used remediation technologies such as electrochemistry, elution, and phytoremediation. suffer from either secondary pollution, long cycle time or high cost. In contrast, in situ mineralization technology shows great potential due to its universality, durability and economical efficiency. As such, the development of mineralizers with both high efficiency and low-cost is the core of in situmineralization. In 2021, the concept of 'Super-Stable Mineralization' was proposed for the first time by Kong et al.[1] The layered double hydroxides (denoted as LDHs), with the unique host-guest intercalated structure and multiple interactions between the host laminate and the guest anions, are considered as an ideal class of materials for super-stable mineralization. In this review, we systematically summarize the application of LDHs in the treatment of heavy metal contaminated soil from the view of: 1) the structure-activity relationship of LDHs in in situ mineralization, 2) the advantages of LDHs in mineralizing heavy metals, 3) the scale-up preparation of LDHs-based mineralizers and 4) the practical application of LDHs in treating contaminated soil. At last, we highlight the challenges and opportunities for the rational design of LDH-based mineralizer in the future.

Effect of Guest Solvents on the Ionic Conductivity and Electrochemical Performance of Metal-Organic Framework-Based Magnesium Semi-Solid Electrolytes.

Developing suitable electrolytes is crucial for the advancement of rechargeable magnesium batteries. Recently, metal-organic frameworks (MOFs) have shown a great interest in the field of solid electrolytes for metal ion batteries. However, the ionic conductivity as well as the electrolyte stability in the presence of Mg electrodes are shown to be strongly dependent on the guest solvent used to solvate Mg salts in MOFsSEs. Our measurements showed that full evacuation of the MOF structure before semi-solid electrolytes (sSEs) preparation is crucial for achieving relatively low Mg overpotentials regardless of the ionic conductivity values. Moreover, the behavior of the anode/MOFsSEs interfaces (MOF: α-Mg3 [HCOO]6 ; Mg salt : MgCl2 -Mg[TFSI]2 (1 : 1 wt %); guest solvent: acetone, DMF, DEG, DME and tetraglyme) was investigated by EIS, CV and galvanostatic measurements. The current comparative study of the electrochemical deposition processes of magnesium from MOFsSEs revealed that magnesium deposition/dissolution reactions vary depending on the MOF structure, the guest anion species as well as the nature of the guest solvents.

Halogen Bonding Tripodal Metallo-Receptors for Phosphate Recognition and Sensing in Aqueous-Containing Organic Media.

The anion recognition and electrochemical anion-sensing properties of halogen-bonding (XB) tripodal zinc(II) receptors strategically designed and constructed for tetrahedral anion guest binding are described. The XB tris(iodotriazole)-containing hosts exhibit high affinities and selectivities for inorganic phosphate over other more basic, mono-charged oxoanions such as acetate and the halides in a competitive CD3 CN/D2 O (9 : 1 v/v) aqueous solvent mixture. 1 H NMR anion binding and electrochemical voltammetric anion sensing studies with redox-active ferrocene functionalised metallo-tripodal receptor analogues, reveal each of the XB tripods as superior anion complexants when compared to their tris(prototriazole)-containing, hydrogen bonding (HB) counterparts, not only exemplifying the halogen bond as a strong alternative interaction to the traditional hydrogen bond for molecular recognition but also providing rare evidence of the ability of XB receptors to preferentially bind the "harder" phosphate oxoanion over the "softer" and less hydrated halides in aqueous containing media.

Ein bidentates Antimon‐Pniktogenbrücken‐Wirtsystem

AbstractEin zweizähniges Pniktogenbrücken‐Wirtsystem auf der Basis von 1,8‐Diethinylanthracen wurde mittels einer selektiven Zinn‐Antimon‐Austauschreaktion hergestellt und auf seine Fähigkeit untersucht, als Lewis‐saure Wirtskomponente für die Komplexierung von Lewis‐basischen oder anionischen Gästen zu fungieren. In dieser Arbeit wurde mit der C≡C−Sb(C2F5)2‐Gruppe eine neuartige Akzeptorfunktion etabliert, mit der das Potenzial von Antimon(III)‐Funktionen als Vertreter der kaum erforschten Pniktogenbrücken‐Donatoren untersucht werden kann. Die Akzeptorfähigkeit dieses teilfluorierten Wirtsystems wurde gegenüber Halogenidanionen (Cl−, Br−, I−), Dimethylchalkogeniden Me2Y (Y = O, S, Se, Te) und Stickstoffheterozyklen (Pyridin, Pyrimidin) untersucht. Einblicke in das Adduktbildungsverhalten sowie die Bindungssituation solcher E⋅⋅⋅Sb−CF‐Einheiten wurden in Lösung mittels NMR‐Spektroskopie, im festen Zustand durch Röntgenbeugung, durch Elementaranalysen sowie durch rechnerische Methoden (DFT, QTAIM, IQA) gewonnen.

A Bidentate Antimony Pnictogen Bonding Host System.

A bidentate pnictogen bonding host-system based on 1,8-diethynylanthracene was synthesized by a selective tin-antimony exchange reaction and investigated regarding its ability to act as a Lewis acidic host component for the complexation of Lewis basic or anionic guests. In this work, the novel C≡C-Sb(C2 F5 )2 unit was established to study the potential of antimony(III) sites as representatives for the scarcely explored pnictogen bonding donors. The capability of this partly fluorinated host system was investigated towards halide anions (Cl- , Br- , I- ), dimethyl chalcogenides Me2 Y (Y=O, S, Se, Te), and nitrogen heterocycles (pyridine, pyrimidine). Insights into the adduct formation behavior as well as the bonding situation of such E⋅⋅⋅Sb-CF moieties were obtained in solution by means of NMR spectroscopy, in the solid state by X-ray diffraction, by elemental analyses, and by computational methods (DFT, QTAIM, IQA), respectively.

Zn-Salphen Acrylic Films Powered by Aggregation-Induced Enhanced Emission for Sensing Applications

Zn(II) complexes possess attractive characteristics for supramolecular chemistry, catalysis, and optoelectronic applications, while Zn-Salphen counterparts are also suitable as chemical sensors, although limited by solution-based to date. In this study, we report the synthesis of new polymers from methyl methacrylate, n-butyl acrylate, and a non-symmetrical Zn-Salphen complex. We show that this low-fluorescent complex exhibits aggregation-induced emission enhancement (AIEE) properties and that, the incorporation of AIEE complexes into a polymeric matrix make it possible to achieve fluorescent films with enhanced fluorescence suitable for sensing applications. As a proof of concept, these films could detect acetic acid, showing a decrease of up to 73% in the original fluorescence. Host/guest studies showed a subtle disruption of the emission in aggregates upon treatment with anion guests. These results indicate that an interaction between the guest and Zn-Salphen complex may occur, stabilizing or destabilizing the complex and causing a concomitant increase or decrease in emission.

Synthesis of Cu (II) and Zn (II) Complexes of a Quinoline Based Flexible Amide Receptor as Fluorescent Probe for Dihydrogen Phosphate and Hydrogen Sulphate and Their Antibacterial Activity.

A novel 8-hydroxy quinoline-derived amide receptor, in conjunction with its Cu (II) and Zn (II) complexes, has been strategically developed to function as remarkably efficient fluorescent receptors with a distinct capability for anion sensing. The comprehensive characterization of the synthesized compounds were achieved through UV-Vis, IR, NMR, and HRMS spectroscopic techniques. Among the Cu (II) and Zn (II) complexes, the latter exhibits superior selectivity for anions, specifically dihydrogen phosphate and hydrogen sulfate, as their tetrabutylammonium salts in a 9:1 acetonitrile-water (v/v) mixture. The Cu (II) complex demonstrates enhanced anion binding compared to the amide ligand, albeit with reduced selectivity. Furthermore, the affinity was evaluated using the Benesi-Hildebrand plot. The binding constants and Limit of Detection (LOD) for both complexes were precisely quantified. The Job plot illustrates a clear 1:1 binding interaction between the metal complexes and the guest anions. Significantly, both metal-complex receptors display a broad spectrum of antibacterial activity, against both gram-positive and gram-negative bacteria. It is worth highlighting that the Zn (II) complexed receptor outperforms the Cu (II) complexed receptor, as evidenced by its considerably lower Minimum Inhibitory Concentration (MIC) value against both bacterial strains.

Fabrication of branch-like Aph@LDH-MgO material through organic-inorganic hybrid conjugation for excellent anti-corrosion performance

Layered double hydroxides (LDH) frameworks have shown significant enhancement in stability and reusability, and their tailorable architecture brings new insight into the development of the next generation of hybrid materials, which attracted considerable attention in many fields over the years. One of the factors contributing to the widespread applicability of layered double hydroxides is their adaptable composition, which can accommodate a wide spectrum of potential anionic guests. This exceptional property makes the LDH system simple to adjust for various applications. However, most LDH systems are synthesized in situ in an autoclave at high temperatures and pressures that severely restrict the industrial use of such coating systems. In this study, LDH was directly synthesized on a magnesium alloy that had undergone plasma electrolytic oxidation (PEO) treatment in the presence of ethylenediaminetetraacetic acid, thereby avoiding the use of hydrothermal autoclave conditions. This LDH system was compared with a hybrid architecture consisting of organic-inorganic self-assembly. An organic layer was fabricated on top of the LDH film using 4-Aminophenol (Aph) compound, resulting in a smart hierarchical structure that can provide a robust Aph@LDH film with excellent anti-corrosion performance. At the molecular level, the conjugation characteristics and adsorption mechanism of Aph molecule were studied using two levels of theory as follows. First, Localized orbit locator (LOL)-π isosurface, electrostatic potential (ESP) distribution, and average local ionization energy (ALIE) on the molecular surface were used to highlight localization region, reveal the favorable electrophilic and nucleophilic attacks, and clearly explore the type of interactions that occurred around interesting regions. Second, first-principles based on density functional theory (DFT) was applied to study the hybrid mechanism of Aph on LDH system and elucidate their mutual interactions. The experimental and computational analyses suggest that the high π-electron density and delocalization characteristics of the functional groups and benzene ring in the Aph molecule played a leading role in the synergistic effects arising from the combination of organic and inorganic coatings. This work provides a promising approach to design advanced hybrid materials with exceptional electrochemical performance.

Synthesis and Application of Zinc Layered Hydroxide: A Short Review

Zinc Layered hydroxide (ZLH) is a layered material easily synthesized with a structure identical to brucite-like material. Due to the exchangeable anions in the interlayer compensating for the positive charge of a brucite-type layer, ZLH provides a wide application in many fields. This review focuses on the properties and method of synthesis of ZLH by giving an overview of intercalated guest anion in the interlayer of ZLH. The further discussion involved the application of intercalated guest anion in zinc layered hydroxide layer and its properties as a sensitizer, controlled release biomedical, and agriculture to provide the scientific community for research and development by giving current findings. This brief review also presents the success of anion intercalation for controlled release along with the kinetic model involved, which increases the bioavailability and effectiveness of the nanocomposite on its target. It shows the development of research on ZLH nanocomposites toward the sustainability of human life and the environment. This study implies that it is a source of knowledge for researchers about zinc-layered hydroxide materials involving synthesis methods and their application to produce more beneficial nanomaterials.

The Structure, Preparation, Characterization, and Intercalation Mechanism of Layered Hydroxides Intercalated with Guest Anions.

Since the intercalation of anions into layered hydroxides (LHs) has a great impact not only on their nucleation and growth but also on their structure, composition, and size, the intercalation chemistry of LHs has aroused the strong interest of researchers. However, the progress in the fundamental understanding of LHs intercalated with guest anions have not been paralleled by a concomitant development of the preparation and performance improvement of such materials. Considering the guidance of a timely in-depth review for scientists in this area, a systematic introduction about the development that is made on the above-mentioned issues is highly needed but yet missing so far. Herein, recent advances in understanding the chemical composition and structure of LHs intercalated with guest anions are systematically summarized. Meanwhile, typical and emerging bottom-up synthesis methods of LHs intercalated with anions are reviewed, and the potential impact of external reaction parameters on the intercalation of anions into LHs are discussed . Besides, different analytical characterization techniques employed in the examination of guest anion-intercalated LHs are deliberated upon. Finally, although progress is slow in exploring the intercalation mechanism, as many examples as possible are included in this review and inferred the possible intercalation mechanism.

Synthesis, and control release properties of Zirconium –AA7075 - beta naphtha oxy acetate nanocomposites

In this research, Beta naphtha oxy acetate (BNOA) was used as the guest anion, and Zirconium-aluminum 7075 layered double hydroxide (Zr-AA7075-LDH) was employed as the inorganic host, to create an organic–inorganic nanohybrid nanocomposite using the co-precipitation process. At a BNOA concentration of 0.08 M and a Zr/AA7075, R = 2 M ratio, a stable nanohybrid nanocomposite was produced. The formation of a Zr-AA7075-BNOA nanocomposite, wherein the nitrate ion interlayer gap in layered double hydroxide grew from 8.8 to 19.6 Å, demonstrates the successful intercalation of Beta naphtha oxy acetate into these spaces. Moreover, it was discovered that the Brunauer-Emmett-Teller surface area for Zr-AA7075-LDH and Zr-AA7075-BNOA nanocomposites rose from 4.23 to 45.84 m2 g−1. The generated nanocomposite is a mesoporous material with a BJH mean pore diameter of199 Å. CHNS analysis of the sample revealed that the Zr-AA7075- Beta naphtha oxy acetate nanocomposite material is 37.4% (w/w) depend on the carbon content. Pseudo-second order kinetics took over after 200 min of BNOA deintercalation from the Zr-AA7075 lamella being driven by zeroth and first order kinetics. It appears that the organic acid herbicide BNOA can be manufactured using layered double hydroxide as a carrier, as shown by the study's findings.

Effects of Zinc-Layered Hydroxide on Controlled Release of Plant Nutrients and Growth Performance of Kelempayan (Neolamarckia cadamba) Seedlings

The loss of nutrients from conventional fertilisers is often encountered by the agricultural industry. Slow-release fertilisers by nanotechnology application can maintain nutrient availability for effective plantgrowth. Zinc-layered hydroxide nanohybrids have been little explored as controlled release systems offunctional anions, unlike the Layered Double Hydroxides (LDH) that belong to the same family ofanionic clays. The objective of the study was to investigate the effectiveness of zinc-layered hydroxidenanohybrid containing plant nutrient anions as a controlled-release formulation. Two nano-deliverymaterials namely zinc-layered hydroxide nitrate (ZLN) and zinc-layered hydroxide phosphate (ZLP) weresuccessfully synthesised through the co-precipitation and anion exchange methods. The PXRD patterns ofthe resulting nanohybrids, ZLN and ZLP recorded basal spacing of 9.57 and 6.78Å, respectively, at alower 2 angles range of 0-60 o . FTIR analyses confirmed the formation of host-guest nanohybrid whichcomprised the characteristic bands of nitrate and phosphate. Thermogravimetric analyses showed thethermal stability of the nanohybrid obtained where the capability of the host material to function as acontrolled release agent was determined through a controlled release study. Controlled release of plantnutrient sources, nitrate and phosphate from their respective nanohybrids were evaluated using variousrelease medium solutions. The accumulated release of guest anion from interlayer zinc layered hydroxide(ZLH) nanohybrid into pH 4 solution was observed to be faster than pH 6.5. A higher concentration ofsodium carbonate solution showed an increase in the percentage release for both nitrate and phosphateanions into the release medium. A plant growth trial using Kelempayan (Neolamarckia cadamba)seedlings showed that treatment with ZLN and ZLP recorded the highest biomass weight compared toapplication with commercial fertiliser and raw chemicals. The content of N, P and Zn in Kelempayanleaves showed the highest readings for similar treatment. The study found that ZLH has acted as a goodhost for inorganic plant nutrients with slow-release properties and thus has improved the growthperformance of Kelempayan seedlings with better nutrient uptake.

Aggregation-induced emission switch showing high contrast mehanofluorochromism and solvatofluorochromism: Specifically detects HSO3− in bioimaging studies

In this work, a novel mechanoresponsive luminescent (MRL) and aggregation induced emission (AIE) switch, 2-(4-((9-butyl-9H-carbazol-3-yl)ethynyl)benzylidene)malononitrile (CABM) has been synthesized by a perfect blending of the carbazole-based triple bond and benzyl malononitrile conjugated derivative via the ‘sonogashira coupling reaction’. The optoelectronic properties of this donor–π–acceptor (D–π–A) framework spontaneously originates a prominent yellow fluorescence which further exhibits a mechanical stimuli induced orange – red emission. Interestingly, just after fumed with dichloromethane (DCM) vapor, the rubbed CABM powder facilely exhibits a restoration in the emission profile as well as fluorescence color. Moreover, this multidimensional switch, CABM shows a prominent solvent dependent sensitivity towards different polarities of organic solvents. CABM also exhibits a typical intramolecular charge transfer (ICT) mechanism along with AIE behaviors with high solid-state efficiency. Importantly, CABM acts as a fluorescence indicator for the qualitative and quantitative detection of low-level water content as impurity in organic solvent. CABM is also found to specifically sense HSO3− anion compared to other guest anions. These promising observations inspire us for the bioimaging studies by using human blood cells which clearly exhibit that CABM can be used to detect HSO3− in human peripheral blood mononuclear cells (PBMCs).

Mechanism of Sodium Dodecyl Diphenyl Ether Disulfonate Filled Hydrotalcite Inhibiting the Photo-Degradation of Polyvinyl Chloride under Different Ranges of Ultraviolet Wavelength Irradiation

This content introduces a novel Ultraviolet (UV)-shielding material, Zn2Al-MADS-LDH (MADS-LDH), which was synthesized through co-precipitation method to insert sodium dodecyl diphenyl ether disulfonate (MADS) into the interlayer of Zn2Al-LDH layered double hydroxide (LDH), to improve the photoaging resistance of polyvinyl chloride (PVC). The characterization results indicated that MADS-LDH had a host-guest interaction between the LDH host layer and MADS guest anion, and it exhibited superior UV absorption capabilities than Zn2Al-CO3-LDH (CO3-LDH) and a broader absorption spectrum compared to MADS. A series of LDHs/PVC film composite materials containing LDHs nanosheets were prepared by incorporating the prepared LDHs into a PVC matrix via a solvent casting method. As expected, the MADS-LDH/PVC film composite materials exhibited enhanced photoaging resistance. The results of photoaging tests indicated that MADS-LDH inhibits the rate of carbonyl generation during photoaging of MADS-LDH/PVC film composite materials, resulting in a decrease in the carbonyl index (ΔCl) and relative degradation rate (RDR) compared to pristine PVC film and CO3-LDH/PVC film composite materials. Furthermore, the study evaluated the influence of different UV light wavelength ranges, such as UVB (280~315 nm), UVC (200~280 nm), and UV (200~400 nm), on the aging performance of PVC film and LDHs/PVC film composite materials. The results demonstrated that UV had the highest aging effect on PVC composite films, followed by UVC and UVB. Therefore, the MADS-LDH is a highly efficient and promising UV-shielding material with excellent potential for wide applications in the field of PVC.

Synthesis and Luminescence Properties of Self-Assembled Lanthanide Complexes with an EDTA-Type Chelating Ligand in Aqueous Ethanol Solution

Abstract A hexadentate chelating ligand based on ethylenediaminetetraacetic acid (EDTA) with four cholesteryl groups (L2) was designed and synthesized. L2 forms stable 1:1 complexes with lanthanide ions, and the resulting L2-lanthanide complexes form stable self-assemblies with an average particle size of ∼50 nm in aqueous ethanol solution (20 wt%). Under these conditions, the L2-lanthanide complexes exhibit amphiphilic properties and long-lived luminescence. Sodium 2-naphthoate was added as a guest anion to form a 1:2 complex (anion:Ln) with a lanthanide complex resulting in exciton-coupled circular dichroism spectra. 4-Alkyl benzoates were also used as guest anions, and the intensity of the sensitized luminescence largely depends in this case on the length of their alkyl chain.

An artificial selective binding pocket for multivalent anions

ABSTRACT In the study, we designed and synthesised a V-shaped quadruple amide receptor R with a pocket of multiple hydrogen-bond network and characterised it through NMR, HRMS and single crystal X-ray diffraction. By the pre-organised hydrogen-bonding interactions, its pocket could accommodate some selected anions such as CF3SO3 −, HSO4 −, H2PO4 −, Cl− and Br−. The binding constants of R to the guest anions span the order of magnitude from the first power of ten to the third power of ten, according to the 1H NMR titration experiments. The recognition of R to the multivalent anions demonstrated high selectivity, reaching up to 258.8 between the complexes of R with H2PO4 − and Br−. The density functional theory calculations of these stable complexes illustrated that the origin of the high selectivity is the self-fitness of the shape of R’s binding pocket to the shape of guest anions.

A Double-Walled Tetrahedron with AgI 4 Vertices Binds Different Guests in Distinct Sites.

A double-walled tetrahedral metal-organic cage assembled in solution from silver(I), 2-formyl-1,8-naphthyridine, halide, and a threefold-symmetric triamine. The AgI 4 X clusters at its vertices each bring together six naphthyridine-imine moieties, leading to a structure in which eight tritopic ligands bridge four clusters in an (AgI 4 X)4 L8 arrangement. Four ligands form an inner set of tetrahedron walls that are surrounded by the outer four. The cage has significant interior volume, and was observed to bind anionic guests. The structure also possesses external binding clefts, located at the edges of the cage, which bound small aromatic guests. Halide ions bound to the silver clusters were observed to exchange in a well-defined hierarchy, allowing modulation of the cavity volume. The principles uncovered here may allow for increasingly more sophisticated cages with silver-cluster vertex architectures, with post-assembly tuning of the interior cavity volume enabling targeted binding behavior.

A Double‐Walled Tetrahedron with AgI4 Vertices Binds Different Guests in Distinct Sites**

AbstractA double‐walled tetrahedral metal‐organic cage assembled in solution from silver(I), 2‐formyl‐1,8‐naphthyridine, halide, and a threefold‐symmetric triamine. The AgI4X clusters at its vertices each bring together six naphthyridine‐imine moieties, leading to a structure in which eight tritopic ligands bridge four clusters in an (AgI4X)4L8 arrangement. Four ligands form an inner set of tetrahedron walls that are surrounded by the outer four. The cage has significant interior volume, and was observed to bind anionic guests. The structure also possesses external binding clefts, located at the edges of the cage, which bound small aromatic guests. Halide ions bound to the silver clusters were observed to exchange in a well‐defined hierarchy, allowing modulation of the cavity volume. The principles uncovered here may allow for increasingly more sophisticated cages with silver‐cluster vertex architectures, with post‐assembly tuning of the interior cavity volume enabling targeted binding behavior.

Ferrocene-Derived Palladium(II)-Based Metallosupramolecular Structures: Synthesis, Guest Interaction, and Stimulus-Responsiveness Studies

Using ferrocene-based ligand systems, a series of heterobimetallic architectures of the general formula [PdmLn]x+ were designed with the aim of installing an opening and closing mechanism that would allow the release and binding of guest molecules. Palladium complex formation was achieved through coordination to pyridyl groups, and using 2-, 3-, and 4-pyridyl derivatives provided access to defined PdL, PdL2, and Pd2L4 structures, respectively. The supramolecular complexes were characterized using nuclear magnetic resonance (NMR) and infrared spectroscopy, mass spectrometry, and elemental analysis, and for some examples density functional theory calculations and single-crystal X-ray diffraction analysis. 1H NMR spectroscopy was used to investigate disassembly and reassembly of the metallosupramolecular structures. The former was induced by cleavage of the relatively labile Pd-Npyridyl bonds with the introduction of the competing ligands N,N'-dimethylaminopyridine (DMAP) and Cl- (using tetrabutylammonium chloride) to yield [Pd(DMAP)4]2+ and [PdCl4]2-, respectively. The process was found to be reversible for several of the heterodimetallic compounds, with the addition of H+ or Ag+ triggering complex reassembly. Guest binding studies with several architectures revealed interactions with the anionic guests p-toluenesulfonate and octyl sulfate, but not with neutral molecules. Furthermore, the release of guests was reversibly induced with Cl- ions as a stimulus.