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Pd(II) Coordination Sphere Engineering: Pyridine Cages, Quinoline Bowls, and Heteroleptic Pills Binding One or Two Fullerenes.

ABSTRACT: Fullerenes and their derivatives are of tremendous technological relevance. Synthetic access and application are still hampered by tedious purification protocols, peculiar solubility, and limited control over regioselective derivatization. We present a modular self-assembly system based on a new low-molecular-weight binding motif, appended by two palladium(II)-coordinating units of different steric demands, to either form a [Pd₂L¹₄]⁴⁺ cage or an unprecedented [Pd₂L²₃(MeCN)₂]⁴⁺ bowl (with L¹ = pyridyl, L² = quinolinyl donors). The former was used as a selective induced-fit receptor for C₆₀. The latter, owing to its more open structure, also allows binding of C₇₀ and fullerene derivatives. By exposing only a fraction of the bound guests' surface, the bowl acts as fullerene protecting group to control functionalization, as demonstrated by exclusive monoaddition of anthracene. In a hierarchical manner, sterically low-demanding dicarboxylates were found to bridge pairs of bowls into pill-shaped dimers, able to host two fullerenes. The hosts allow transferring bound fullerenes into a variety of organic solvents, extending the scope of possible derivatization and processing methodologies.

SUBMITTER: Chen B

PROVIDER: S-EPMC6609009 | biostudies-literature |

REPOSITORIES: biostudies-literature

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Cooperativity of steric bulk and H-bonding in coordination sphere engineering: heteroleptic PdII cages and bowls by design.

Project description:Recently developed self-assembly strategies allow to rationally reduce the symmetry of metallosupramolecular architectures. In addition, the combination of multiple ligand types without creating compound mixtures has become possible. Among several approaches to realize non-statistical heteroleptic assembly, Coordination Sphere Engineering (CSE) makes use of secondary repulsive or attractive interactions in direct vicinity of the metal nodes. Previously, we used steric congestion to turn dinuclear [Pd2L4] cages with fourfold symmetry into [Pd2L3X2] (X = solvent, halide) bowl structures. Here, we introduce a new subtype of this strategy based on balancing hydrogen bonding and repulsive interactions between ligands carrying quinoline (LQu) and 1,8-naphthyridine (LNa) donors to generate trans-[Pd2L2] and [Pd2L3L'] cages, assisted by templation of encapsulated fullerenes. Combined with steric congestion caused by acridine (LAc) donors, we further report the first example of a heteroleptic [Pd2L2L'X2] bowl. Formation, structure and fullerene binding ability of these metallo-supramolecular hosts were studied by NMR, mass spectrometry and single crystal X-ray diffraction.

| S-EPMC8826863 | biostudies-literature

Tunable Fullerene Affinity of Cages, Bowls and Rings Assembled by PdII Coordination Sphere Engineering.

Project description:For metal-mediated host compounds, the development of strategies to reduce symmetry and introduce multiple functionalities in a non-statistical way is a challenging task. We show that the introduction of steric stress around the coordination environment of square-planar PdII cations and bis-monodentate nitrogen donor ligands allows to control the size and shape of the assembled product, from [Pd2 L4 ] cages over [Pd2 L3 ] bowl-shaped structures to [Pd2 L2 ] rings. Therefore, banana-shaped ligand backbones were equipped with pyridines, two different quinoline isomers and acridine, the latter three introducing steric congestion through hydrogen substituents on annelated benzene rings. Differing behavior of the four resulting hosts towards the binding of C60 and C70 fullerenes was studied and related to structural differences by NMR spectroscopy, mass spectrometry and single crystal X-ray diffraction. The three cages based on pyridine, 6-quinoline or 3-quinoline donors were found to either bind C60 , C70 or no fullerene at all.

| S-EPMC6899814 | biostudies-literature

Donor-Site-Directed Rational Assembly of Heteroleptic cis-[Pd2 L2 L'2 ] Coordination Cages from Picolyl Ligands.

Project description:A donor-site engineering approach facilitates the formation of heteroleptic [Pd2 L2 L'2 ]4+ cage structures through a favored cis-'in2 /out2 ' spatial configuration of the methyl groups of 5- and 3-substituted bis-monodentate picolyl ligands with flat acridone and bent phenothiazine backbones. The heteroleptic cages were confirmed by ESI-MS and 2D NMR experiments as well as DFT calculations, which pointed toward a cis-configuration being energetically favored. This was further supported by the synthesis and X-ray structure of a previously unreported cis-[Pd(2-picoline)4 ]2+ complex. The formation of homoleptic structures, however, was met with considerable steric hindrance at the PdII centers, as observed by the formation of [Pd2 L3 (solvent)2 ]4+ and [Pd2 L2 (solvent)4 ]4+ species when only one type of acridone-based ligand was offered. In contrast, bent phenothiazine ligands with outside-pointing methyl groups showed the ability to form interpenetrated double-cages, as revealed by X-ray crystallography. The general route presented herein enables the assembly of uniform cis-[Pd2 L2 L'2 ]4+ coordination cages, thus furthering the possibility to increase structural and functional complexity in supramolecular systems.

| S-EPMC6174927 | biostudies-literature

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Project description:The combination of shape-complementary bis-monodentate ligands LA and LB with PdII cations yields heteroleptic cages cis-[Pd2 LA 2 LB 2 ] by self-sorting. Herein, we report how such assemblies can be diversified by introduction of covalent backbone bridges between two LA units. Together with solvent and guest effects, the flexibility of these linkers can modulate nuclearity, topology, and number of cavities in a family of four structurally diverse assemblies. Ligand LA1 , with flexible linker, reacts in CH3 CN with its LB counterpart to a tetranuclear dimer D1. In DMSO, however, a trinuclear pseudo-tetrahedron T1 is formed. The product of LA2 , with rigid linker, looks similar to D1, but with a rotated ligand arrangement. In presence of an anionic guest, this dimer D2 transforms and a hexanuclear prismatic barrel P2 crystallizes. We demonstrate how controlling a ligand's coordination mode can trigger structural differentiation and increase complexity in metallo-supramolecular assembly.

| S-EPMC7986237 | biostudies-literature

Morphological Control of Heteroleptic cis- and trans-Pd2 L2 L'2 Cages.

Project description:Control over the integrative self-sorting of metallo-supramolecular assemblies opens up possibilities for introducing increased complexity and function into a single self-assembled architecture. Herein, the relationship between the geometry of three ligand components and morphology of three self-sorted heteroleptic [Pd2 L2 L'2 ]4+ cages is examined. Pd-mediated assembly of two bis-monodentate pyridyl ligands with native bite angles of 75° and 120° affords a cis-[Pd2 L2 L'2 ]4+ cage while the same reaction with two ligands with bite angles of 75° and 60° gives an unprecedented, self-penetrating structural motif; a trans-[Pd2 (anti-L)2 L'2 ]4+ heteroleptic cage with a "doubly bridged figure eight" topology. Each heteroleptic assembly can be formed by cage-to-cage conversion of the homoleptic precursors and morphological control of [Pd2 L2 L'2 ] cages is achieved by selective ligand displacement transformations in a system of three ligands and at least six possible cage products.

| S-EPMC5499718 | biostudies-literature

Topological prediction of palladium coordination cages.

Project description:The preparation of functionalized, heteroleptic Pd x L2x coordination cages is desirable for catalytic and optoelectronic applications. Current rational design of these cages uses the angle between metal-binding (∠B) sites of the di(pyridyl)arene linker to predict the topology of homoleptic cages obtained via non-covalent chemistry. However, this model neglects the contributions of steric bulk between the pyridyl residues-a prerequisite for endohedrally functionalized cages, and fails to rationalize heteroleptic cages. We describe a classical mechanics (CM) approach to predict the topological outcomes of Pd x L2x coordination cage formation with arbitrary linker combinations, accounting for the electronic effects of coordination and steric effects of linker structure. Initial validation of our CM method with reported homoleptic Pd12 LFu 24 (LFu = 2,5-bis(pyridyl)furan) assembly suggested the formation of a minor topology Pd15 LFu 30, identified experimentally by mass spectrometry. Application to heteroleptic cage systems employing mixtures of LFu (∠B = 127°) and its thiophene congener LTh (∠B = 149° ∠B exp = 152.4°) enabled prediction of Pd12L24 and Pd24L48 coordination cages formation, reliably emulating experimental data. Finally, the topological outcome for exohedrally (LEx) and endohedrally (LEn) functionalized heteroleptic Pd x L2x coordination cages were predicted to assess the effect of steric bulk on both topological outcomes and coordination cage yields, with comparisons drawn to experimental data.

| S-EPMC8162455 | biostudies-literature

Heteroleptic LaIII Anilate/Dicarboxylate Based Neutral 3D-Coordination Polymers.

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| S-EPMC8123117 | biostudies-literature

Heteroleptic Coordination Environments in Metal-Mediated DNA G-Quadruplexes.

Project description:The presence of metal centers with often highly conserved coordination environments is crucial for roughly half of all proteins, having structural, regulatory, or enzymatic function. To understand and mimic the function of metallo-enzymes, bioinorganic chemists pursue the challenge of synthesizing model compounds with well-defined, often heteroleptic metal sites. Recently, we reported the design of tailored homoleptic coordination environments for various transition metal cations based on unimolecular DNA G-quadruplex structures, templating the regioselective positioning of imidazole ligandosides L I . Here, we expand this modular system to more complex, heteroleptic coordination environments by combining L I with a new benzoate ligandoside L B within the same oligonucleotide. The modifications still allow the correct folding of parallel tetramolecular and antiparallel unimolecular G-quadruplexes. Interestingly, the incorporation of L B results in strong destabilization expressed in lower thermal denaturation temperatures T m . While no transition metal cations could be bound by G-quadruplexes containing only L B , heteroleptic derivatives containing both L I and L B were found to complex CuII, NiII, and ZnII. Especially in case of CuII we found strong stabilizations of up to ΔT m = +34°C. The here shown system represents an important step toward the design of more complex coordination environments inside DNA scaffolds, promising to culminate in the preparation of functional metallo-DNAzymes.

| S-EPMC7000376 | biostudies-literature

Methane Storage in Paddlewheel-Based Porous Coordination Cages.

Project description:Although gas adsorption properties of extended three-dimensional metal-organic materials have been widely studied, they remain relatively unexplored in porous molecular systems. This is particularly the case for porous coordination cages for which surface areas are typically not reported. Herein, we report the synthesis, characterization, activation, and gas adsorption properties of a family of carbazole-based cages. The chromium analog displays a coordination cage record BET (Brunauer-Emmett-Teller) surface area of 1235 m2/g. With precise synthesis and activation procedures, two previously reported cages similarly display high surface areas. The materials exhibit high methane adsorption capacities at 65 bar with the chromium(II) cage displaying CH4 capacities of 194 cm3/g and 148 cm3/cm3. This high uptake is a result of optimal pore design, which was confirmed via powder neutron diffraction experiments.

| S-EPMC6207189 | biostudies-literature

Understanding Gas Storage in Cuboctahedral Porous Coordination Cages.

Project description:Porous molecular solids are promising materials for gas storage and gas separation applications. However, given the relative dearth of structural information concerning these materials, additional studies are vital for further understanding their properties and developing design parameters for their optimization. Here, we examine a series of isostructural cuboctahedral, paddlewheel-based coordination cages, M24(tBu-bdc)24 (M = Cr, Mo, Ru; tBu-bdc2- = 5-tert-butylisophthalate), for high-pressure methane storage. As the decrease in crystallinity upon activation of these porous molecular materials precludes diffraction studies, we turn to a related class of pillared coordination cage-based metal-organic frameworks, M24(Me-bdc)24(dabco)6 (M = Fe, Co; Me-bdc2- = 5-methylisophthalate; dabco = 1,4-diazabicyclo[2.2.2]octane) for neutron diffraction studies. The five porous materials display BET surface areas from 1057-1937 m2/g and total methane uptake capacities of up to 143 cm3(STP)/cm3. Both the porous cages and cage-based frameworks display methane adsorption enthalpies of -15 to -22 kJ/mol. Also supported by molecular modeling, neutron diffraction studies indicate that the triangular windows of the cage are favorable methane adsorption sites with CD4-arene interactions between 3.7 and 4.1 Å. At both low and high loadings, two additional methane adsorption sites on the exterior surface of the cage are apparent for a total of 56 adsorption sites per cage. These results show that M24L24 cages are competent gas storage materials and further adsorption sites may be optimized by judicious ligand functionalization to control extracage pore space.

| S-EPMC6746114 | biostudies-literature

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