Cage-To-Cage Transformations in Self-Assembled Coordination Cages Using "Acid/Base" or "Guest Binding-Induced Strain" as Stimuli.

Controlling supramolecular systems between different functional forms by utilizing acids/bases as stimuli is a formidable challenge, especially where labile coordination bonds are involved. A pair of acid/base responsive, interconvertible 1,5-enedione/pyrylium based Pd2L4-type cages are prepared that exhibit differential guest binding abilities towards disulfonates of varied sizes. A three-state switch has been achieved, where (i) a weakly coordinating base induced cage-to-cage transformation in the first step, (ii) a strongly coordinating base triggered cage disassembly as the second step, and (iii) the third step shows acid(strong) promoted generation of initial cage, thereby completing the cycle. To our surprise, binding of a specific disulfonate guest facilitated cage-to-cage transformations by inducing strain on the cage assembly thereby opening the labile pyrylium rings of the cage. Through a competitive guest binding study, we demonstrated the superior guest binding capability of the octacationic pyrylium-based cage over a similar-sized tetracationic cage. These results provide a reliable approach to reversibly modulate the guest binding properties of acid/base-responsive self-assembled coordination cages.

Neighboring Cage Participation for Assisted Construction of Self-Assembled Multicavity Conjoined Cages and Augmented Guest Binding.

A set of Pd2L4, Pd3L4, and Pd4L4-type single-, double-, and triple-cavity cages are prepared by complexation of Pd(NO3)2 with designer bis-monodentate (L1), tris-monodentate (L2), and tetrakis-monodentate (L3) ligands. The Pd2L4 cage exists in equilibrium with a Pd3L6 cage; the equilibrium shifted to Pd2L4 at 70 °C or upon addition of pyrazine-N,N'-dioxide (PZDO). The Pd2L4 cage binds a PZDO molecule using electrostatic, bifurcated H-bonding and overcoordinated H-bonding interactions. The discrete Pd3L4 and Pd4L4 compounds are conjoined cages comprising of unequal sized Pd2L4 cages (bigger and smaller). The bigger unit of Pd3L4 cage selectively binds a PZDO, and the smaller one binds a nitrate, fluoride, chloride, or bromide. The Pd4L4 cage, having a central bigger Pd2L4 cavity and two smaller peripheral Pd2L4 cavities, binds one PZDO and two nitrate, fluoride, chloride, or bromide. The smaller cavity can be prepared individually from Pd(II) and bis-monodentate ligand (L4), however, in the presence of template like a nitrate, fluoride, chloride, or bromide; otherwise, it forms an oligomeric mixture. Notably, the conjoined Pd3L4 and Pd4L4 cages could be prepared with (preferably) or without using a template for smaller cavity, and the bigger Pd2L4 is formed by sacrificing the possibility of the Pd3L6 moiety. Thus, the conjoined cages are formed in a symbiotic manner where the neighboring cages participate in the formation of each other. The binding of PZDO shows that the presence of one neighboring cage (as in Pd3L4) augments the binding affinity and that is further augmented in the presence of two neighboring cages (as in Pd4L4).

A Template-Free Pd2 L4 Cage with up to Nanomolar Affinity for Chloride in Aqueous Solutions.

Invited for the cover of this issue is the group of Dillip Kumar Chand at the Indian Institute of Technology Madras. The image depicts the efficient chloride binding ability of a designer self-assembled coordination cage in water. The binding occurs selectively even in presence of models of biologically abundant anionic systems. Read the full text of the article at 10.1002/chem.202300891.

A Template-Free Pd2 L4 Cage with up to Nanomolar Affinity for Chloride in Aqueous Solutions.

Selective binding of chloride over the other most abundant anions in living organisms is pivotal due to its essential role in physiological functions. Herein, we report a template-free Pd2 L4 cage exhibiting high selectivity for medium-sized halides (i. e., Cl- , Br- ) in water owing to the size-discriminatory nature of the cage cavity. In pure water, this cage displays high selectivity and micromolar affinity for chloride. The cage shows no binding towards other biologically more abundant essential anions such as phosphates, carboxylates, or bicarbonate. This cage shows an unprecedented nanomolar affinity with 1 : 1 binding stoichiometry for chloride in aqueous-DMSO media. This high affinity was achieved with the best use of traditional hydrogen bonding and electrostatic interactions, as confirmed by single-crystal X-ray diffraction analysis. This well-defined cage sequestrates F- by cleaving a B-F bond in BF4 - in a facile manner in a nonpolar solvent or in the presence of excess ligand. This cage also demonstrates capture of the sub-ppm chloride level that is present in commercial D2 O samples.

Conjoined and non-conjoined coordination cages with palladium(II) vertices: structural diversity, solution dynamics, and intermolecular interactions.

Self-assembled coordination complexes prepared from a combination of Pd(II) components with one or more types of high-symmetry or low-symmetry bis/tris/tetrakis-monodentate ligands are considered in this review. The structures of these complexes are viewed in terms of the presence of a metallo-macromonocycle or conjoined metallo-macromonocycles/metallocages in the frameworks. Analysis of the typical molecular structures revealed an open truth that one or more units of metallo-macromonocycles can be conjoined to afford planar or non-planar systems. In the same line, the enveloping surface of a 3D cage can be considered as a multiple number of conjoined metallomacrocycles that embrace a 3D space from all directions. However, two or more units of cages are conjoined in a multi-3D-cavity cage system and such a system is considered as a conjoined cage. Construction of such conjoined cages having a finite but multiple number of 3D-cavities unified in a single molecular architecture is a challenging task when compared to that of single-3D-cavity based compounds. Conjoining of as many as four units of 3D cages is known so far. Single- as well as multi-cavity cages of lower symmetry have become a very recent trend in this regard where low-symmetry ligands or mixed ligand ensembles are crafted in the framework of the cages. Other structural diversities like helicity in cages, and supramolecular isomerism are also included in this assorted literature work. Although isomerism in classical coordination complexes is well known, it is very less studied in self-assembled coordination complexes. Ligand isomerism is one such feature that is reviewed here. The dynamic behavior of the cages results in interesting reactivity aspects. A large variety of dynamic processes are collected under an umbrella, i.e., "ligand exchange reactions" and described with examples. Intermolecular interaction among the already self-assembled molecules is possible in solution, solid, and gel-phases as discussed in the last part of this review. The understanding of intermolecular interaction is likely to influence different areas of research including crystal engineering, and materials chemistry.

Configurational ligand isomerism in conjoined-cages.

Double-decker shaped conjoined-cages of Pd3L4 formulation are prepared via self-assembly of Pd(II) with a set of three regioisomeric tridentate ligands. Alongside the targeted double-decker cage, unprecedented hour-glass shaped conjoined-cages of Pd3L4 formulation are also formed in two cases. The double-decker cage prepared from one ligand system and the hour-glass from another (but with a regioisomeric ligand) are structurally well suited to exemplify configurational ligand isomerism.

Diastereoselectively self-sorted low-symmetry binuclear metallomacrocycle and trinuclear metallocage.

A pyridine/aniline appended unsymmetrical bis-monodentate ligand N-(3-aminophenyl)nicotinamide, Lun is synthesized via condensation of nicotinic acid with excess m-phenylene diamine. A low-symmetry binuclear complex of the Pd2L'2Lun2 type and an extremely rare trinuclear complex of the Pd3Lun6 type are produced by self-assembly of the ligand Lun with cis-protected palladium(II) (i.e., PdL') and palladium(II), respectively. Two isomers (i.e. [(2,0), (2,0)] and [(1,1), (1,1)]-forms) are theoretically possible for the Pd2L'2Lun2-type complex whereas nine isomers can be envisaged in the case of the Pd3Lun6-type arrangement. However, one of the isomers of the Pd2L'2Lun2-type complex as well as the one for the Pd3Lun6-type complex are experimentally obtained. The exclusive formation of specific isomers could be predicted from the 1D/2D NMR study in the solution state and the DFT calculations in the gas phase/implicit solvent media. The formation of the predicted all-(1,1)-[Pd2(en)2Lun2](NO3)4 has been confirmed by a single-crystal XRD study. DFT calculations for the isomers of the Pd3Lun6-type arrangement show that a [cis(2,2), cis(2,2), cis(2,2)] isomer is energetically favourable than the alternatively predicted [trans(2,2), trans(2,2), trans(2,2)] isomer. Conformational changes within the build of the exclusively formed isomers are proposed on the basis of NMR study.

Controlled and Predictably Selective Oxidation of Activated and Unactivated C(sp3)-H Bonds Catalyzed by a Molybdenum-Based Metallomicellar Catalyst in Water.

The synthesis of carbonyl derivatives from renewable feedstocks, by direct oxidation/functionalization of activated and unactivated C(sp3)-H bonds under a controlled and predictably selective fashion, especially in late stages, remains a formidable challenge. Herein, for the first time, cost-effective and widely applicable protocols for controlled and predictably selective oxidation of petroleum waste and feedstock ingredients like methyl-/alkylarenes to corresponding value-added carbonyls have been developed, using a surfactant-based oxodiperoxo molybdenum catalyst in water. The methodologies use hydrogen peroxide (H2O2) as an environmentally benign green oxidant, and the reactions preclude the need of any external base, additive, or cocatalyst and can be operated under mild eco-friendly conditions. The developed protocols show a wide substrate scope and eminent functional group tolerance, especially oxidation-liable and reactive boronic acid groups. Upscaled multigram synthesis of complex steroid molecules by late-stage oxidation proves the robustness and practical utility of the current protocol since it employs an inexpensive recyclable catalyst and an easily available oxidant. A plausible mechanism has been proposed with the help of few controlled experiments and kinetic and computational studies.

Palladium(II)-Based Self-Assembled Heteroleptic Coordination Architectures: A Growing Family.

Metal-driven self-assembly is one of the most effective approaches to lucidly design a large range of discrete 2D and 3D coordination architectures/complexes. Palladium(II)-based self-assembled coordination architectures are usually prepared by using suitable metal components, in either a partially protected form (PdL') or typical form (Pd; charges are not shown), and designed ligand components. The self-assembled molecules prepared by using a metal component and only one type of bi- or polydentate ligand (L) can be classified in the homoleptic series of complexes. On the other hand, the less explored heteroleptic series of complexes are obtained by using a metal component and at least two different types of non-chelating bi- or polydentate ligands (such as La and Lb ). Methods that allow the controlled generation of single, discrete heteroleptic complexes are less understood. A survey of palladium(II)-based self-assembled coordination cages that are heteroleptic has been made. This review article illustrates a systematic collection of such architectures and credible justification of their formation, along with reported functional aspects of the complexes. The collected heteroleptic assemblies are classified here into three sections: 1) [(PdL')m (La )x (Lb )y ]-type complexes, in which the denticity of La and Lb is equal; 2) [(PdL')m (La )x (Lb )y ]-type complexes, in which the denticity of La and Lb is different; and 3) [Pdm (La )x (Lb )y ]-type complexes, in which the denticity of La and Lb is equal. Representative examples of some important homoleptic architectures are also provided, wherever possible, to set a background for a better understanding of the related heteroleptic versions. The purpose of this review is to pave the way for the construction of several unique heteroleptic coordination assemblies that might exhibit emergent supramolecular functions.

Cuprous Oxide- or Copper-Coated Jute Stick Pieces at an Air-Water Interface for Prevention of Aerial Contamination in Potable Water.

Cuprous oxide and copper have been synthesized via the solvothermal process using basic copper carbonate as the source of copper. Pure Cu2O or Cu could be afforded by simply varying the solvent while keeping the temperature and time constant. In this study, copper-based materials were coated on jute stick pieces (JSP) in situ. Cu2O-coated JSP (Cu2O-JSP) and Cu-coated JSP (Cu-JSP) were characterized by powder X-ray diffraction (PXRD) and scanning electron microscopy (SEM). Cu2O-JSP and Cu-JSP were found to be active against Escherichia coli NCIM 2931 (Gram-negative bacteria) and Staphylococcus aureus (Gram-positive bacteria). The antibacterial nature of the material and the buoyant nature of Cu2O-JSP and Cu-JSP were exploited to develop beaded necklace-like strands that could be floated on potable water to effectively prevent aerial contamination. Leaching of copper from both Cu2O-JSP and Cu-JSP into water was found to be below the permissible limit for copper in drinking water.

Ligand Isomerism in Coordination Cages.

Complexation reactions of palladium(II) nitrate with a set of 3-pyridyl appended nonchelating bidentate ligands possessing regioisomeric phenylene-diurea functionalities as spacers were carried out. The ligands utilized in this study are 1,1'-(1,2-phenylene)bis(3-(pyridin-3-yl)urea), L1; 1,1'-(1,3-phenylene)bis(3-(pyridin-3-yl)urea), L2; and 1,1'-(1,4-phenylene)bis(3-(pyridin-3-yl)urea), L3. The complexation reactions of the ligands (L1, L2, and L3) with palladium(II) produced single discrete isomeric cages (1, 2, and 3) of Pd2L4 formulation in each case and thereby illustrated ligand-isomerism in coordination cages. All 16 hydrogen atoms of eight urea moieties present in four ligand strands are delineated completely endohedrally in cage 1 and completely exohedrally in cage 3, whereas cage 2 exhibited half of the urea hydrogens in exohedral locations and the remaining half in endohedral locations. In addition to the variable number of solvent molecules, the cavities of cages 1 and 2 lodged four and two nitrate ions, respectively, using the endohedral (H)urea atoms (i.e., NH groups) as binding sites, whereas the cavity of 3 remained anion free. The abilities of the complexes 1-3 for adsorption of CO2 gas are demonstrated, and their behaviors are compared.

Discrete and Polymeric Self-Assembled Palladium(II) Complexes as Supramolecular Gelators.

Supramolecular gels prepared from low-molecular-weight gelators have been extensively explored. However, the exploitation of discrete or polymeric metal complexes as gelators is a relatively recent trend. The synthesis of self-assembled coordination complexes from palladium(II) and selected ligands is well established, but the potential of these complexes as gelators is a less explored treasure. Herein we focus on the gelation abilities of some self-assembled palladium(II) complexes and the resulting unique properties. First, discrete complexes with PdL, PdL2 , Pd2 L, Pd2 L2 , Pd2 L4 , and Pd3 L6 compositions are discussed. Second, gelation behavior promoted by coordination-polymer-like gelators formed in situ is explored. These gel samples have been employed in catalysis and the uptake of organic and dye molecules from the solution and gas phases. It is concluded that untapped unique properties can be realized by further exploration of designer palladium(II) complexes.

Polyaromatic molecular peanuts.

Mimicking biological structures such as fruits and seeds using molecules and molecular assemblies is a great synthetic challenge. Here we report peanut-shaped nanostructures comprising two fullerene molecules fully surrounded by a dumbbell-like polyaromatic shell. The shell derives from a molecular double capsule composed of four W-shaped polyaromatic ligands and three metal ions. Mixing the double capsule with various fullerenes (that is, C60, C70 and Sc3N@C80) gives rise to the artificial peanuts with lengths of ∼3 nm in quantitative yields through the release of the single metal ion. The rational use of both metal-ligand coordination bonds and aromatic-aromatic π-stacking interactions as orthogonal chemical glue is essential for the facile preparation of the multicomponent, biomimetic nanoarchitectures.

A Truncated Molecular Star.

A pentanuclear coordination complex assembled from any palladium(II) component and non-chelating ligands is hitherto unreported. The pentanuclear complex [Pd5 (L1)5 (L2)5 ](BF4 )10 , 1 reported here was prepared by the spontaneous complexation of [Pd(DMSO)4 ](BF4 )2 with the non-chelating bidentate ligands 1,4-phenylenebis(methylene) diisonicotinate, L1 and 4,4'-bipyridine, L2 in a one-pot method at room temperature. The planar polycyclic complex 1 with outer diameters of ≈3 nm is termed as a "molecular star" owing to its resemblance with a pentagram shape. Interim paths leading to the star were also probed to decipher related dynamics of the system.

Synthesis and characterization of curcumin loaded PLA-Hyperbranched polyglycerol electrospun blend for wound dressing applications.

This study is aimed to develop curcumin (Cur) incorporated electrospun nanofibers of a blend of poly (lactic acid) (PLA) and hyperbranched polyglycerol (HPG) for wound healing applications. Both the polymers are synthesized and fabricated by electrospinning technique. The produced nanofibers were characterized by Scanning Electron Microscopy (SEM), X-Ray Diffraction (XRD), Fourier Transform Infrared Spectroscopy (FT-IR), Differential Scanning Colorimetry (DSC) and Thermogravimetric Analysis (TGA). Electrospun scaffolds (PLA/HPG/Cur) exhibits very high hydrophilicity, high swelling and drug uptake and promotes better cell viability, adhesion and proliferation when compared to PLA/Cur electrospun nanofibers. Biodegradation study revealed that the morphology of the nanofibers were unaffected even after 14days immersion in Phosphate Buffered Saline. In vitro scratch assay indicates that migration of the cells in the scratch treated with PLA/HPG/Cur is complete within 36h. These results suggest that PLA/HPG/Cur nanofibers can be a potential wound patch dressing for acute and chronic wound applications.

Cage-to-Cage Cascade Transformations.

A series of Pd2 L4 -type binuclear self-assembled coordination cages (1-4), where L stands for a nonchelating bidentate ligand, were prepared. The strategies adopted for the synthesis of the cages were: combination of Pd(II) with 1) a selected ligand or 2) subcomponents of the ligand. Highly efficient cage-to-cage transformation reactions are demonstrated by suitable covalent modification (from 1 to 2 or 3 or 4) or ligand-exchange reactions (from 1 to 2 or 3 or 4; from 2 to 3 or 4). Thus, new cascade transformations (from 1 to 2 to 3; from 1 to 2 to 4) are achieved beautifully.

Reversible Mechanical Interlocking of D-Shaped Molecular Karabiners bearing Coordination-Bond Loaded Gates: Route to Self-Assembled [2]Catenanes.

Complexation of 1,4-phenylenebis(methylene) diisonicotinate, L1, with cis-protected Pd(II) components, [Pd(L')(NO3 )2 ], in an equimolar ratio yielded binuclear complexes, 1 a-d of [Pd2 (L')2 (L1)2 ](NO3 )4 formulation where L' stands for ethylenediamine (en), tetramethylethylenediamine (tmeda), 2,2'-bipyridine (bpy), and phenanthroline (phen). The combination of 4,4'-bipyridine, L2, with the cis-protected Pd(II) units is known to yield molecular squares, 2 a-d. However, 2 b-d coexist with the corresponding molecular triangles, 3 b-d. Combination of an equivalent each of the ligands L1 and L2 with two equivalents of cis-protected Pd(II) components in DMSO resulted in the D-shaped heteroligated complexes [Pd2 (L')2 (L1)(L2)](NO3 )4 , 4 a-d. Two units of the D-shaped complexes interlock, in a concentration dependent fashion, to form the corresponding [2]catenanes [Pd2 (L')2 (L1)(L2)]2 (NO3 )8 , 5 a-d under aqueous conditions. Crystal structures of the macrocycle [Pd2 (tmeda)2 (L1)(L2)](PF6 )4 , 4 b'', and the catenane [Pd2 (bpy)2 (L1)(L2)]2 (NO3 )8 , 5 c, provide unequivocal support for the proposed molecular architectures.

Nanoscale metallogel via self-assembly of self-assembled trinuclear coordination rings: multi-stimuli-responsive soft materials.

A rare variety of coordination rings having the M3L6 composition are prepared by the combination of Pd(NO3)2 with an imidazolyl or benzimidazolyl appended bidentate non-chelating ligand (i.e.L1 or L2). The variable concentration 1H NMR spectra of the trinuclear complexes [Pd3(L1)6](NO3)6, 1a and [Pd3(L2)6](NO3)6, 2a in DMSO-d6 provided valuable information on the self-assembly phenomenon of the already self-assembled complexes. Interestingly, the signals of 2a are broadened upon increasing the concentration. The solution of 2a in DMSO formed a supramolecular metallogel above a certain concentration (i.e. 2% w/v), however, complex 1a could not form any gel. This phenomenon is attributed to the presence of an auxiliary π-surface in the benzimidazole moiety in L2, in contrast to the imidazole moiety of L1. The influence of anions in gel formation was studied by preparing several samples using a variety of palladium(II) salts and L2 in DMSO. It was found that oxoanions like nitrate, perchlorate, triflate and tosylate are amicable for gel formation, probably due to their capabilities of forming H-bonds. The counter anions like tetrafluoroborate, hexafluorophosphate, or hexafluoroantimonate could not assist in the formation of gel. The stimuli-responsive nature of the gel and the reversible gel­sol conversion were demonstrated by dis-assembly and re-assembly processes of 2a as controlled by a pair of stimuli such as halide-nitrate, DMAP-HNO3, and ethylenediamine-Pd(NO3)2. No gel could be prepared by the combination of Ni(NO3)2 or Pt(NO3)2 with ligand L2. Thus, a subtle change in the ligand design, metal ion and counter anion is demonstrated as the responsible parameter for the construction of the three component multi-stimuli-responsive supramolecular gel.

Octadecanuclear gear wheels by self-assembly of self-assembled "double saddle"-type coordination entities: molecular "rangoli".

A series of self-assembled "double saddle"-type trinuclear complexes of [Pd3L'3L2] formulation have been synthesized by complexation of a series of cis-protected palladium(II) components with a slightly divergent "E-shaped" non-chelating tridentate ligand, 1,1'-(pyridine-3,5-diyl)bis(3-(pyridin-3-yl)urea (L). The cis-protecting agents L' employed in the study are ethylenediamine (en), tetramethylethylenediamine (tmeda), 2,2'-bipyridine (bpy), and 1,10-phenanthroline (phen), for 1, 2, 3, and 4, respectively. The crystal structures of [Pd3(tmeda)3(L)2](NO3)6 (2), [Pd3(bpy)3(L)2](NO3)6 (3), and [Pd3(phen)3(L)2](NO3)6 (4) unequivocally support the new architecture. Two of the "double saddle"-type complexes (3 and 4) are suitably crafted with π surfaces at the strategically located cis-protecting sites to facilitate intermolecular π-π interactions in the solid state. As a consequence, six units of the 3 (or 4) are assembled, by means of six-pairs of π-π stacking interactions, in a circular geometry to form an octadecanuclear molecular ring of [(Pd3L'3L2)6] composition. The overall arrangement of the rings in the crystal packing is equated with the traditional Indian art form rangoli.

Stoichiometrically controlled revocable self-assembled "spiro" versus quadruple-stranded "double-decker" type coordination cages.

The simple combination of Pd(II) with the tris-monodentate ligand bis(pyridin-3-ylmethyl) pyridine-3,5-dicarboxylate, L, at ratios of 1:2 and 3:4 demonstrated the stoichiometrically controlled exclusive formation of the "spiro-type" Pd1L2 macrocycle, 1, and the quadruple-stranded Pd3L4 cage, 2, respectively. The architecture of 2 is elaborated with two compartments that can accommodate two units of fluoride, chloride, or bromide ions, one in each of the enclosures. However, the entry of iodide is altogether restricted. Complexes 1 and 2 are interconvertible under suitable conditions.