Dipyridyl Ligands Research Articles

A Reduced-Symmetry Pd2L4 Cage from a Heterotopic Dipyridyl Ligand.

Two dipyridyl ligands, L3,3 and L3,4, have been used in combination with palladium(II) in the construction of metallosupramolecular species that show anion-dependent behavior in solution. A rare example of a low-symmetry (C2h) lantern-type cage is formed in one instance, [Pd2(L3,3)4]4+, while the isomeric ligand yields a larger double-walled square complex, [Pd4(L3,4)8]8+. [Pd2(L3,3)4](NO3)4 was isolated in crystalline form revealing two anions within the interior of the C2h-symmetry cage. The cage itself is held together by hydrogen bonding between "head-to-tail" pairs of ligands that reinforces the symmetry generated by the ditopic ligands. In solution, the cage with NO3- has sharp 1H nuclear magnetic resonance (NMR) signals at room temperature, while the BF4- analogue has broad signals that sharpen at higher temperatures or upon addition of (Bu4N)(NO3), highlighting the importance of the anion in templating or otherwise influencing self-assembly in solution. Altering the substitution position of one of the pyridyl rings yields a more "open" complex, with [Pd4(L3,4)8](NO3)8 being isolated as a crystalline solid. The double-walled square complex has a greater Pd···Pd separation due to the increased angle that the pyridyl groups subtend at the core of the ligand. NMR spectroscopy and mass spectrometry studies suggest a single species in the presence of nitrate but multiple species with tetrafluoroborate.

Inorganic-organic hybrid Cu-dipyridyl semiconducting polymers based on the redox-active cluster [SFe3(CO)9]2-: filling the gap in iron carbonyl chalcogenide polymers.

The construction of sulfur-incorporated cluster-based coordination polymers was limited and underexplored due to the lack of efficient synthetic routes. Herein, we report facile mechanochemical ways toward a new series of SFe3(CO)9-based dipyridyl-Cu polymers by three-component reactions of [Et4N]2[SFe3(CO)9] ([Et4N]2[1]) and [Cu(MeCN)4][BF4] with conjugated or conjugation-interrupted dipyridyl ligands, 1,2-bis(4-pyridyl)ethylene (bpee), 1,2-bis(4-pyridyl)ethane (bpea), 4,4'-dipyridyl (dpy), or 1,3-bis(4-pyridyl)propane (bpp), respectively. X-ray analysis showed that bpee-containing 2D polymers demonstrated unique SFe3(CO)9 cluster-armed and cluster-one-armed coordination modes via the hypervalent μ5-S atom. These S-Fe-Cu polymers could undergo flexible structural transformations with the change of cluster bonding modes by grinding with stoichiometric amounts of dipyridyls or 1/[Cu(MeCN)4]+. They exhibited semiconducting behaviors with low energy gaps of 1.55-1.79 eV and good electrical conductivities of 3.26 × 10-8-1.48 × 10-6 S cm-1, tuned by the SFe3(CO)9 cluster bonding modes accompanied by secondary interactions in the solid state. The electron transport efficiency of these polymers was further elucidated by solid-state packing, X-ray photoelectron spectroscopy (XPS), X-ray absorption near-edge spectroscopy (XANES), density of states (DOS), and crystal orbital Hamilton population (COHP) analysis. Finally, the solid-state electrochemistry of these polymers demonstrated redox-active behaviors with cathodically-shifted patterns compared to that of [Et4N]2[1], showing that their efficient electron communication was effectively enhanced by introducing 1 and dipyridyls as hybrid ligands into Cu+-containing networks.

Controllable Topological Transformations of 818 Molecular Metalla-knots by Oxidation of Thiazole-Based Ligands.

By exploiting coordination-driven self-assembly, high yields of two 818 molecular metalla-knots could be obtained using a thiazole-moiety-containing asymmetric dipyridyl ligand 2-(pyridin-4-yl)-5-(pyridin-4-ylethynyl)benzo[d]thiazole (L1 ), as confirmed using X-ray crystallographic analysis, electrospray ionization-time-of-flight/mass spectrometry (ESI-TOF/MS), and detailed liquid-state nuclear magnetic resonance (NMR) spectroscopy. To modulate the self-assembled structures, m-chloroperbenzoic acid (m-CPBA) was utilized to oxidize thiazole-based ligand L1 to N-thiazole-oxide-based ligand 2-(pyridin-4-yl)-5-(pyridin-4-ylethynyl)benzo[d]thiazole 3-oxide (L2 ), which enabled the selective construction of the corresponding tetranuclear macrocycles. Notably, two molecular metalla-knots could be topologically transformed from 818 knots to simple monocycles because the L1 alkyne bond was inert toward m-CPBA, as confirmed by liquid-state NMR spectroscopy, ESI-TOF/MS, and elemental analysis.

Controllable Topological Transformations of 818 Molecular Metalla‐knots by Oxidation of Thiazole‐Based Ligands

AbstractBy exploiting coordination‐driven self‐assembly, high yields of two 818 molecular metalla‐knots could be obtained using a thiazole‐moiety‐containing asymmetric dipyridyl ligand 2‐(pyridin‐4‐yl)‐5‐(pyridin‐4‐ylethynyl)benzo[d]thiazole (L1), as confirmed using X‐ray crystallographic analysis, electrospray ionization‐time‐of‐flight/mass spectrometry (ESI‐TOF/MS), and detailed liquid‐state nuclear magnetic resonance (NMR) spectroscopy. To modulate the self‐assembled structures, m‐chloroperbenzoic acid (m‐CPBA) was utilized to oxidize thiazole‐based ligand L1 to N‐thiazole‐oxide‐based ligand 2‐(pyridin‐4‐yl)‐5‐(pyridin‐4‐ylethynyl)benzo[d]thiazole 3‐oxide (L2), which enabled the selective construction of the corresponding tetranuclear macrocycles. Notably, two molecular metalla‐knots could be topologically transformed from 818 knots to simple monocycles because the L1 alkyne bond was inert toward m‐CPBA, as confirmed by liquid‐state NMR spectroscopy, ESI‐TOF/MS, and elemental analysis.

Rhenium(I) Complexes with Sulfur-Bridged Dipyridyl Ligands: Structural, Photophysical, and Computational Studies.

A series of six new rhenium(I) tricarbonyl complexes [Re(CO)3(N-N)Br] bearing sulfur-bridged dipyridyl (N-N) ligands with three different oxidation states (sulfide (S), sulfoxide (SO), and sulfone (SO2)) are described. Spectroscopic studies show that changing the oxidation state of the ligands influences the photophysical properties of the complexes, with complexes 3 and 6 containing the sulfone ligand exhibiting a lower energy MLCT absorption band tailing into the visible region. Solution-state emission measurements show that these complexes exhibit readily tunable emission energies from 480 to 610 nm, depending on the oxidation state of the sulfur bridge and the presence of substituents on the pyridyl rings. Solid-state emission measurements show that the emission is significantly red-shifted upon oxidation of the sulfur bridge to sulfone with enhanced photoluminescence quantum yield.

Multi-Modular Design of Stable Pore-Space-Partitioned Metal-Organic Frameworks for Gas Separation Applications.

Pore space partition (PSP) is an effective materials design method for developing high-performance small-pore materials for storage and separation of gas molecules. The continued success of PSP depends on broad availability and judicious choice of pore-partition ligands and better understanding of each structural module on stability and sorption properties. Here, by using substructural bioisosteric strategy (sub-BIS), a dramatic expansion of pore-partitioned materials is targeted by using ditopic dipyridyl ligands with non-aromatic cores or extenders, as well as by expanding heterometallic clusters to uncommon nickel-vanadium and nickel-indium clusters rarely known before in porous materials. The dual-module iterative refinement of pore-partition ligands and trimers leads to remarkable enhancement of chemical stability and porosity. Here a family of 23 pore-partitioned materials synthesized from five pore-partition ligands and seven types of trimeric clusters is reported. New materials with such compositionally and structurally diverse framework modules reveal key factors that dictate stability, porosity, and gas separation properties. Among these, materials based on heterometallic vanadium-nickel trimeric clusters give rise to the highest long-term hydrolytic stability and remarkable uptake capacity for CO2 , C2 H2 /C2 H4 /C2 H6 , and C3 H6 /C3 H8 hydrocarbon gases. The breakthrough experiment shows the potential application of new materials for separating gas mixtures such as C2 H2 /CO2 .

Structure–property relationship of dipyridyl−Cu polymers containing inorganic clusters Te/SeFe3(CO)9

AbstractThis mini‐review covers a novel series of 1D and 2D Te/SeFe3(CO)9‐incorporated (Te, 1a; Se, 1b) Cu‐based coordination polymers synthesized by the liquid‐assisted grinding (LAG) method using predesigned compound [TeFe3(CO)9Cu2(MeCN)2] (1a‐Cu2(MeCN)2) with rigid or flexible dipyridyl ligands, or three components of [SeFe3(CO)9]2− (1b), [Cu(MeCN)4]+, and dipyridyls. These polymers displayed various cluster coordination modes, including cluster‐blocked [EFe3(CO)9Cu2(L)]n (E = Te, 1a‐L‐1D, Se, 1b‐L‐1D; L = 1,2‐bis(4‐pyridyl)ethylene (bpee), 1,2‐bis(4‐pyridyl)ethane (bpea)), cluster‐pendant [SeFe3(CO)9Cu2(dpy)3]n (1b‐dpy‐1D, dpy = 4,4′‐dipyridyl) and [EFe3(CO)9Cu2(L)2.5]n (E = Te, 1a‐L‐2D, Se, 1b‐L‐2D; L = bpee, bpea), cluster‐linked [SeFe3(CO)9Cu2(MeCN)(dpy)1.5]n (1b‐dpy‐2D) and [SeFe3(CO)9Cu2(bpp)2]n (1b‐bpp‐2D, bpp = 1,3‐bis(4‐pyridyl)propane), as well as the unique cation‐anion polymer [{Cu2(bpp)4}{(TeFe3(CO)9Cu)2(bpp)}]n (1a‐bpp‐CA). Their dimensionality expansions and reversible transformations accompanied with bonding pattern changes were achieved upon the addition of stoichiometric amounts of appropriate agents. These polymers exhibited pronounced semiconducting properties with tunable energy gaps and optical (dc) or electrical conductivities. The trend of their semiconductivities can be related to bonding patterns, where efficient electron communications were proved to stem from the existence of carbonyl ligands and electron‐rich clusters 1a and 1b. In particular, water−/light‐stable 1b‐based polymers exhibited excellent photodegradation activities toward nitroaromatics and organic dyes, where the efficiency was further rationalized by their structural features and narrow energy gaps.

Cation-Templated Assembly of 613 and 623 Metalla-Links

Facilitated by multiple stacking interactions between components, two kinds of metalla-links containing molecular Borromean rings (623 links) and head-to-tail cyclic [3]catenanes (613 links), as isomers, were constructed in high yield by introducing tri-μ-methoxyl-dinuclear complexes [(Cp*M)2(μ-OCH3)3][OTf] (M = RhIII or IrIII, Cp* = η5-pentamethylcyclopentadienyl, OTf = triflate) as unusual cationic guests during coordination-driven assembly. The topology of these intricate structures was controlled by strategically selecting two dipyridyl ligands that differ in their coordination orientations, as evidenced by X-ray crystallography and electrospray ionization-time-of-flight/mass spectrometry analysis. The behavior of the abovementioned metalla-links in solution was monitored and further studied by the detailed NMR techniques.

Synthetic Receptors with Micromolar Affinity for Chloride in Water.

A water-soluble coordination cage was obtained by reaction of Pd(NO3 )2 with a 1,3-di(pyridin-3-yl)benzene ligand featuring a short PEG chain. The cavity of the metal-organic cage contains one nitrate anion, which is readily replaced by chloride. The apparent association constant for chloride binding in buffered aqueous solution is Ka =1.8(±0.1)×105 M-1 . This value is significantly higher than what has been reported for other macrocyclic chloride receptors. The heavier halides Br- and I- compete with binding or self-assembly, but the receptor displays very good selectivity over common anions such as phosphate, acetate, carbonate, and sulfate. A further increase of the chloride binding affinity by a factor of 3 was achieved using a fluorinated dipyridyl ligand.

Synthetic Receptors with Micromolar Affinity for Chloride in Water

AbstractA water‐soluble coordination cage was obtained by reaction of Pd(NO3)2with a 1,3‐di(pyridin‐3‐yl)benzene ligand featuring a short PEG chain. The cavity of the metal‐organic cage contains one nitrate anion, which is readily replaced by chloride. The apparent association constant for chloride binding in buffered aqueous solution isKa=1.8(±0.1)×105 M−1. This value is significantly higher than what has been reported for other macrocyclic chloride receptors. The heavier halides Br−and I−compete with binding or self‐assembly, but the receptor displays very good selectivity over common anions such as phosphate, acetate, carbonate, and sulfate. A further increase of the chloride binding affinity by a factor of 3 was achieved using a fluorinated dipyridyl ligand.

Construction of Pd-based coordination cages with three geometrically distinct ligands.

Three different dipyridyl ligands were combined with [Pd(CH3CN)4](BF4)2 to give mixtures of homo- and/or heteroleptic coordination cages. The three ligands were chosen so that one ligand shows a parallel orientation of the coordinate vectors, the second ligand a bent angle of 60°, and the third ligand a bent angle of 120°. We have identified ligand mixtures that give rise to integrative self-sorting, and we have characterized a heterotrileptic [Pd4L2L'2L''4]8+ cage by single crystal X-ray crystallography. The structural flexibility of ligands with alkynyl spacers was found to be of importance for the formation of heteroleptic complexes.

Raw data for 'Orientational self-sorting: formation of structurally defined Pd₄L₈ and Pd₆L₁₂ cages from low-symmetry dipyridyl ligands'

raw data for 'Orientational self-sorting: formation of structurally defined Pd₄L₈ and Pd₆L₁₂ cages from low-symmetry dipyridyl ligands'

Exploring the coordination chemistry of a low symmetry, bent dipyridyl ligand

Although dipyridyl ligands are ubiquitous in their use within coordination polymers, the vast majority of these are symmetrical species (i.e. typically having a C2 axis passing through their core) based on para-substituted pyridyl groups which aids in the predictability of the networks or complexes that they form. Less symmetric species are often more difficult to utilize in the formation of predictable networks and are typically reliant on “post-synthetic rationalization” of the materials that are formed. Herein, we report an asymmetric dipyridyl ligand (L) which has a relatively rigid “kink,” and its use in the formation of several coordination polymers. Detailed structural comparison reveals the ligand to be relatively predictable with a predisposition to making M2L2 cyclic motifs due to the angle subtended between the two coordinating groups. In several instances the size of the motif formed provides a cavity in which aromatic species can reside.

Novel CuI coordination polymer self-assembled from 2,5-bis(pyridin-4-yl)-1,3,4-oxadiazole and thiocyanate ions: Synthesis, structural characterization, Hirshfeld surface analysis, thermal and magnetic studies

The synthesis and crystal structure of one-dimensional (1-D) coordination polymer from an angular dipyridyl ligand 2,5-bis(pyridine-4-yl)-1,3,4-oxadiazole (4-pox) and CuCl2⋅2H2O, [CuI(4-poxH)(SCN)(μ1,3-SCN)]n (named complex 1), are reported. The investigated copper(I) complex crystallizes in the monoclinic crystal system with space group P21/n. UV–vis and FTIR suggest the co-presence of the 4-pox ligand and the pseudohalide, in the isolated complex. This was confirmed by a crystallographic study which shows that the copper is in a tetrahedral environment, linked to two thiocyanate groups and to two nitrogen atoms, one belonging to the pyridine ring and the others to thiocyanate group. The crystallographic study also reveals the protonation of the unbound organic ligand pyridine. The crystal cohesion is assured by different intermolecular hydrogen bonds, π–π stacking, and coordination bonds (N–Cu and S–Cu). Therefore, the one-dimensional coordination chains are further interconnected by hydrogen bonds and π–π stacking to from a three-dimensional supramolecular framework. This behaviour was confirmed by Hirshfeld surface analysis. The thermal analysis reveals that complex 1 is thermally stable up to 160 °C. The magnetic measurements indicated the diamagnetic nature of this CuI coordination polymer.

Iodine-Chemisorption, Interpenetration and Polycatenation: Cationic MOFs and CPs from Group 13 Metal Halides and Di-Pyridyl-Linkers.

Eight cationic, two‐dimensional metal‐organic frameworks (MOFs) were synthesized in reactions of the group 13 metal halides AlBr3, AlI3, GaBr3, InBr3 and InI3 with the dipyridyl ligands 1,2‐di(4‐pyridyl)ethylene (bpe), 1,2‐di(4‐pyridyl)ethane (bpa) and 4,4’‐bipyridine (bipy). Seven of them follow the general formula 2 ∞[MX2(L)2]A, M=Al, In, X=Br, I, A−=[MX4]−, I−, I3 −, L=bipy, bpa, bpe. Thereby, the porosity of the cationic frameworks can be utilized to take up the heavy molecule iodine in gas‐phase chemisorption vital for the capture of iodine radioisotopes. This is achieved by switching between I− and the polyiodide I3 − in the cavities at room temperature, including single‐crystal‐to‐single‐crystal transformation. The MOFs are 2D networks that exhibit (4,4)‐topology in general or (6,3)‐topology for 2 ∞[(GaBr2)2(bpa)5][GaBr4]2⋅bpa. The two‐dimensional networks can either be arranged to an inclined interpenetration of the cationic two‐dimensional networks, or to stacked networks without interpenetration. Interpenetration is accompanied by polycatenation. Due to the cationic character, the MOFs require the counter ions [MX4]−, I− or I3 − counter ions in their pores. Whereas the [MX4]−, ions are immobile, iodide allows for chemisorption. Furthermore, eight additional coordination polymers and complexes were identified and isolated that elaborate the reaction space of the herein reported syntheses.

Rational Design and Integrative Assembly of Heteromeric Metalla[2]Catenanes Featuring Cp*Ir/Rh Fragments.

We report a design strategy for integrative assembly of heteromeric [2]catenanes. The design focuses on the shape and functional group match of two different metalla-rectangles. A series of dipyridyl ligands with different lengths, widths and functional groups were designed and used for assembly experiments. Six heteromeric [2]catenanes were obtained both by direct mixture of two pre-assembled metalla-rectangles and one-pot three-component self-assembly. Multiple analytic methods were employed to characterize the catenanes, including single crystal X-ray diffraction analysis, NMR spectroscopy, mass spectroscopy and elemental analysis.

Homochiral coordination polymers based on proline-derivative: structures, magnetic properties, and selective detection of Cr2O72− anion

By incorporating semi-rigid terephthaloyl mono proline-derived ligand [H2TMPro ​= ​terephthaloyl-mono(l-proline)] with the ancillary dipyridyl ligands [bpea ​= ​1,2-bis(4-pyridyl)ethane and bipy ​= ​4,4′-bipyridine], five new homochiral coordination polymers were synthesized. Compounds [Cu3(TMPro)2(μ3-OH)2]·4H2O (1) and [Zn3(TMPro)2(μ3-OH)2]·4H2O (2) are isostructural complicated 3D frameworks, which contain the intertwined right- and left-handed helical chains built from the butterfly-shaped [Cu4(μ3-OH)2(RCOO)6] units. Compound [Cu2(TMPro)2(bpea)2(H2O)2]·7H2O (3) displays a 3D framework composed of Cu1-TMPro left-handed helical chains and Cu2-TMPro right-handed helical chains connected by the bpea ligands. Compound [Cd4(TMPro)4(bpea)6]·10H2O·4C2H5OH (4) features a 3-fold interpenetrating 3D framework with 5-connected hexagonal bnn topological net constructed from the {Cd-TMPro} chains and bpea ligands. Compound [Ni(TMPro)(bipy)(H2O)3] (5) exhibits a {Ni-bipy}2+ 1D chain decorated by the TMPro2− anions. Magnetic susceptibility measurements indicate ferromagnetic exchange interactions between Cu(II) ions in 1. Photoluminescence spectra of 2 show corresponding emission bands of TMPro2− anions. Additionally, for 2, the Ksv value of 553 ​M−1 and detection limit of 70 ​μM imply it can detect the Cr2O72− anion.

Pt(II) diimine complexes bearing varied alkyl chains: Synthesis, tunable photophysical properties and aggregation-induced optical power limiting enhancement

A series of Pt(II) diimine complexes with varied alkyl chains on 2,2′- dipyridyl ligands (Pt-C1–Pt-C3) have been synthesized and characterized. The photophysical properties and nonlinear absorption properties were elucidated using UV–vis absorption, emission and transient absorption spectroscopy, density functional theory (DFT) calculations and electrochemical experiments. It was found that increasing the alkyl chain led to regular changes in the photophysical properties of Pt-C1–Pt-C3. The original conjugated skeleton of the Pt(II) complexes were affected when the alkyl chain was introduced and extended. All complexes exhibited an obvious aggregation-induced phosphorescence emission (AIPE) in a mixed solution comprised of tetrahydrofuran/water. The formation of nanoparticles in the aggregated state induced these complexes to exhibit different excited state properties. When the water content increased, the emission intensity increases 3 ∼ 13-flod and the excited state lifetime increased 98-flod due to the formation of Pt(II) complex nanoparticles. As a result, the optical power limiting (OPL) performance of these complexes was greatly improved. Based on the systematical investigation of nonlinear optical complexes in aggregated state, this work provided a theoretical basis for the development of new OPL materials. Furthermore, the Pt(II) complex nanoparticles will be more conducive to the potential application of OPL devices.

Structure-Property Relationships of Inorganic-Organic Hybrid Semiconducting Se-Fe-Cu-CO Polymers.

A novel family of inorganic-organic-hybrid SeFe3(CO)9-dipyridyl two- and one-dimensional Cu polymers was synthesized via the three-component liquid-assisted grinding (LAG) of [Cu(MeCN)4]+, inorganic cluster [SeFe3(CO)9]2- (1), and rigid conjugated dipyridyls 4,4'-dipyridyl (dpy) and 1,2-bis(4-pyridyl)ethylene (bpee) or flexible conjugation-interrupted dipyridyls 1,2-bis(4-pyridyl)ethane (bpea) and 1,3-bis(4-pyridyl)propane (bpp). They included a cluster-linked 2D polymer, [(μ4-Se)Fe3(CO)9Cu2(MeCN)(dpy)1.5]n (1-dpy-2D), a cluster-pendant 1D chain, [(μ3-Se)Fe3(CO)9Cu2(dpy)3]n (1-dpy-1D), cluster-blocked 1D polymers, [(μ3-Se)Fe3(CO)9Cu2(L)]n (1-L-1D, L = bpee, bpea), and a cluster-linked 2D polymer, [(μ4-Se)Fe3(CO)9Cu2(bpp)2]n (1-bpp-2D). The reversible dimensionality transformations of these three types of polymers accompanied by the change in coordination modes of 1 were achieved by the LAG addition of 1/[Cu(MeCN)4]+ or dipyridyl ligands. These polymers were found to possess tunable low-energy gaps (1.49-1.72 eV) that increased in the order regarding their structural features: cluster-linked 1-dpy-2D and 1-bpp-2D, cluster-blocked 1-bpea-1D and 1-bpee-1D, and cluster-pendant 1-dpy-1D and [(μ3-Se)Fe3(CO)9Cu2(L)2.5]n (L = bpee, 1-bpee-2D; bpea, 1-bpea-2D), indicative of the importance of the participation of cluster 1. The measured electrical conductivities of 1-bpp-2D, 1-bpea-1D, and 1-dpy-1D were 3.13 × 10-7, 2.92 × 10-7, and 2.30 × 10-7 S·cm-1, respectively, which were parallel for the trend in their energy gaps, revealing semiconducting behaviors, supported by XPS, XANES, and DFT calculations. The surprising semiconductivity of the conjugation-interrupted bpp-linked 1-bpp-2D was mainly ascribed to electron transport via C-H···O(carbonyl) hydrogen bonds and aromatic C-H···π contacts within its closely packed 2D layers. Water-/light-stable polymers 1-bpp-2D, 1-bpea-2D, and 1-dpy-1D were also demonstrated to exhibit excellent pseudo-first-order photodegradation toward nitroaromatics and organic dyes, where cluster-linked polymer 1-bpp-2D performed the best, as predicted by its structural features and narrow energy gap.

A Simple Strategy to Obtain Synthetic Ca2+‐Dependent Lectin Mimics

AbstractMany lectins require a Ca2+ ion as structure directing co‐factor to function as carbohydrate binders. Such lectins are implicated in various important biological processes such as inflammation and infection, yet a simple strategy to mimic their function is lacking. Herein, a very simple dipyridyl ligand (6) is reported that can organize around a Pd2+ ion to form the ring‐like complexes [PdCl26] and [Pd62]2+. In CD2Cl2 with 5 % dmso‐d6, ligand 6 does not associate with glycosides, while its Pd2+ complexes selectively bind to β‐n‐octyl‐glycosides over α‐n‐octyl‐glycosides. The highest affinity (Ka1:1≈116 M−1) was found between the dicationic [Pd62]2+ and n‐octyl‐β‐D‐galactoside. Molecular modelling suggests a common binding motif with an important role of C−H⋅⋅⋅π interactions and two charge assisted bifurcated [N−H/C−H]+⋅⋅⋅O hydrogen bonds. Ligand 6 and its metal complexes thus provide a proof‐of‐concept for a very simple strategy to mimicking Ca2+‐dependent lectins.