Crown Molecules Research Articles

Discotic liquid crystals 45 years later. Dendronized discs and crowns increase liquid crystal complexity to columnar from spheres, cubic Frank-Kasper, liquid quasicrystals and memory-effect induced columnar-bundles

In 1977 Chandrasekhar laboratory reported the first examples of a new class of thermotropic liquid crystals self-organized from planar disc-like molecules substituted with alkyl groups. X-ray analysis demonstrated that these disc-like molecules stack on top of each other at irregular spacing in columns located in the paraffin melt of their alkyl groups. These supramolecular columns self-organize in a hexagonal array defined as the new thermotropic discotic or columnar hexagonal liquid crystal phase. This new thermotropic liquid crystal phase has translational periodicity in two dimensions and liquid-like disorder in the third one, along the column axis. In 2002 Bushby and Lozman dedicated a brief review article to the 25 anniversary of discotic liquid crystals. This review also included a brief discussion of supramolecular discs and columns self-organized from self-assembling dendrons and dendrimers. The current publication is not another review but a brief perspective on new liquid crystal phases self-organized from dendronized rigid planar and conformationally flexible discs as well as from crown-like molecules. Crown-like molecules are the most stable conformation of a transient unstable disc. All dendronized disc-like and crown molecules adopt a crown conformation that self-assemble helical columns and spherical helices. A large diversity of new liquid crystalline phases self-organize from these helical columns and spherical helices. They include helical columnar hexagonal phases from crowns and from supramolecular spheres, Frank-Kasper A15 (known as cubic phase of space group Pm3¯n), σ phase (also known as tetragonal of space group P42/mnm), 12-fold quasi liquid crystals (QLC) and supramolecular orientational memory (SOM) derived complex bundles of supramolecular columnar hexagonal arrays that are not yet completely elucidated. The impact of Chandrasekhar on the discovery of self-assembling dendrons and dendrimers via his biaxial nematic liquid crystal concept will also be discussed. This perspective is dedicated to the 45 anniversary of the discovery of discotic liquid crystals and to the memory of Professor Sivaramakrishna Chandrasekhar, a modest, respectful and great scientist.

Discretization and Encapsulation of Palladium inside the Cavity of Crown Ether within the Interlayer of Layered Double Hydroxide for Enhanced Activity: A Case Study with Hydrogenation Reaction

AbstractThe activity of the noble metal‐based heterogeneous catalysts is limited by weak metal–support interactions, aggregation, and low surface to volume (S/V) ratio. The activity can be augmented in many ways. Among them, the discretization of the active sites and redistribution of electron density around the metal atom is an important one. In this work, these two phenomena are studied concerning a model reaction, hydrogenation of p‐nitrophenol (p‐NP). Herein, 1,4,7,10,13‐pentaoxacyclopentadecane ether is introduced in the basal space of layered double hydroxide (LDH) to encapsulate noble Pd0 atom inside the cavity of the crown molecule strategically. The modified LDH (Pda‐ECC‐L0.10@in situ CoAl LDH) augments the properties, like, high S/V ratio and nonaggregation of active sites by forming nonagglomerative discrete catalytic (DNSC) sites within the cavity of crown ether in the basal space. The developed catalyst exhibits higher turnover frequency demonstrating the improved activity due to the formed DNSC sites and redistributes electron density around the Pd atoms by LDH layers and crown molecules. Thus, the present material synthesis route can be considered as a stand‐alone method for preparation of the supported sub‐nanometer noble metal catalyst with higher activity and can be exploited for reactions where noble metal catalyst are used.

Hydro-nium bis-(tri-fluoro-methane-sulfon-yl)amide-18-crown-6 (1/1).

The structure of the title compound, H3O+·C2F6NO4S2 -·C12H24O6 or [H3O+·C12H24O6][N(SO2CF3)2 -], which is an ionic liquid with a melting point of 341-343 K, has been determined at 113 K. The asymmetric unit consists of two crystallographically independent 18-crown-6 mol-ecules, two hydro-nium ions and two bis-(tri-fluoro-methane-sulfon-yl)amide anions; each 18-crown-6 mol-ecule complexes with a hydro-nium ion. In one 18-crown-6 mol-ecule, a part of the ring exhibits conformational disorder over two sets of sites with an occupancy ratio of 0.533 (13):0.467 (13). One hydro-nium ion is complexed with the ordered 18-crown-6 mol-ecule via O-H⋯O hydrogen bonds with H2OH⋯OC distances of 1.90 (6)-2.19 (7) Å, and the other hydro-nium ion with the disordered crown mol-ecule with distances of 1.85 (6)-2.36 (6) Å. The hydro-nium ions are also linked to the anions via O-H⋯F hydrogen bonds. The crystal studied was found to be a racemic twin with a component ratio of 0.55 (13):0.45 (13).

Ion Pairing Limits Crystal Growth in Metal–Oxygen Batteries

Aprotic alkali metal–oxygen batteries are promising high specific energy alternatives to Li-ion batteries. Growth and dissolution of alkali metal oxides such as Li2O2 in Li–O2 batteries and NaO2 and KO2 in Na–O2 and K–O2 batteries, respectively, are central to the discharge and charge processes in these batteries. However, crystal growth and dissolution of the discharge products is poorly understood, especially in aprotic electrolytes. In this work, we chose the growth of NaO2 in Na–O2 batteries as a model system and show a strong correlation between the electrolyte salt concentration and the NaO2 crystal size. With a combination of experiments and theory, we argue that the correlation is a direct manifestation of the strong cation–anion interactions, leading to decreased crystal growth rate at high salt concentrations. Furthermore, we propose and experimentally demonstrate that cation-coordinating crown molecules are electrochemically stable electrolyte additives that weaken ion pairing and enhance discharge capacities in metal–oxygen batteries.

Two Supramolecular Inorganic–Organic Hybrid Crystals Based on Keggin Polyoxometalates and Crown Ethers

New supramolecular structures were designed in this work using large-sized polyoxometalates (POMs) and crown-ether-based supramolecular cations selected as building blocks. Two novel supramolecular inorganic–organic hybrids [(3-F-4-MeAnis)([18]crown-6)]2[SMo12O40]•CH3CN (1) and [(4-IAnis)([18]crown-6)]3[PMo12O40]•4CH3CN (2) (3-F-4-MeAnis = 3-fluoro-4-methylanilinium and 4-IAnis = 4-iodoanilinium) were synthesized. Crystals 1 and 2 have been characterized by infrared spectroscopy (IR) and elemental analysis (EA). Based on X-ray diffraction analysis, Crystals 1 and 2 were constructed through noncovalent bonding interactions and belong to different space groups due to the difference of the building blocks used. Supramolecular cations formed due to strong N–H···O hydrogen bonding interactions between the six oxygen atoms of [18]crown-6 molecules and nitrogen atoms of anilinium derivatives. Crystal 1 has two different supramolecular cations with an anti-paralleled arrangement that forms a dimer through weak hydrogen bonding interactions between adjacent [18]crown-6 molecules. Crystal 2 has three independent supramolecular cations that fill large spaces between the [PMo12O40] polyoxoanions forming a rhombus-shape packing arrangement in the ac plane. Crystals 1 and 2 are unstable at room temperature.

Growth of regular nanometric molecular arrays on a functional 2D template based on a chemical guest-host approach.

A regular 2D array of crown molecules, which would spontaneously self-assemble into disordered molecular clusters, is obtained by exploiting a guest-host process, based on the chemical affinity between amino and carboxylic groups on a gold surface. First a carboxylic organic template is formed, which then serves as a host for amino-functionalized crown molecules. The amino-carboxylic interaction thereby drives the formation of a monolayer of guest molecules, regularly distributed at the nanometer scale, preventing their aggregation in unordered clusters observed on a bare gold surface. This method, which can be applied to other guest molecules, represents a novel route to overcome the shape-matching requirements of the standard guest-host architectures. Furthermore, it is intrinsically selective, due to the chemical nature of the anchoring process.

One-dimensional supramolecular columnar structure of trans-syn-trans-dicyclohexano[18]crown-6 and organic ammonium cations

Supramolecular crystals having one-dimensional (1d) columnar structures were constructed by using supramolecules based on tst-DCH[18]crown-6 (tst-DCH = trans-syn-trans-dicyclohexano). In the crystal of (Ani+)(tst-DCH[18]crown-6)[Ni(dmit)2]− (1) and (m-FAni+)(tst-DCH[18]crown-6)[Ni(dmit)2]− (2) (Ani+ = anilinium+, m-FAni+ = m-fluoroanilinium+, dmit2− = 2-thioxo-1,3-dithiole-4,5-dithiolate), the tst-DCH[18]crown-6 formed supramolecular cations with Ani+ and m-FAni+, respectively, through N–H⋯O hydrogen bonds. The planar conformation of tst-DCH[18]crown-6 molecules in the crystals provided bidirectional hydrogen bonding from the upper and lower side of the molecule that were the driving forces for the construction of the 1d supramolecular architecture. The results provided a method to control arrangements of crown ether-based supramolecules in 1d columns that could be used for channels and/or molecular nanomachines such as molecular rotators.

Synthesis, crystal structure, and magnetic characterization of chiral Schiff-base manganese(III) complex containing cocrystallized crown ether molecule

A chiral Schiff-base Mn(III) compound containing cocrystallized crown ether {Mn[(R,R)-Salcy]·(H2O)2}2(ClO4)2·18-Crown-6 (I), where (R,R)-Salcy = (R,R)-N, N′-(1,2-cyclohexanediylethylene)bis(salicylideneiminato) dianion, has been synthesized by the reaction of {Mn[(R,R)-Salcy](H2O)2}ClO4 with 18-crown-6 ether and K4[Mo(CN)8]. X-ray diffraction analysis revealed that the cationic mononuclear Mn(III) Schiff-base compounds were self-complementary via intermolecular O-H⋯O H-bond formed by coordinated aqua ligand of one molecule and phenolic oxygen atoms of the neighboring molecule, giving supramolecular dimeric structure. The H-bond between O atoms of the cocrystallized crown molecule and that of the mentioned above dimer supported formation of one-dimensional supramolecular chain structure which can be linked to two-dimensional supramolecular network based on intermolecular O-H⋯Cl weak interactions. Our study of its magnetic properties revealed weak antiferromagnetic coupling between the adjacent Mn(III) ions.

An Order–Disorder Ferroelectric Host–Guest Inclusion Compound

The host-guest complex [(DIPA)([18]crown-6)](ClO4) (1; DIPA=2,6-diisopropylanilinium) was constructed and found to undergo a sequence of phase transitions (Ibam-Pbcn-Pna21) at T1=278 K and T2=132 K, respectively. Systematic characterizations, such as differential scanning calorimetry, heat capacity, temperature-dependent dielectric constant, and P-E hysteresis loop, reveal that the centrosymmetric-to-polar phase transition at T2 is a paraelectric-to-ferroelectric transition. The symmetry breaking was also confirmed by temperature-dependent second-harmonic generation effect and X-ray powder diffraction. The ferroelectric mechanism is attributable to the linear motion of the perchlorate counterions accompanied by the order-disorder transition of the [18]crown-6 molecules and the anions.

Molecular motion in pyridazinium/crown ether supramolecular cation salts of a nickel dithiolene complex

Supramolecular cations formed by monoprotonated pyridazinium cations and cis-anti-cis-dicyclohexano[18]-crown-6 (DCH[18]-crown-6) or dibenzo[18]-crown-6 (DB[18]-crown-6) were introduced into [Ni(dmit)2]− salts (where dmit2− = 2-thione-1,3-dithiole-4,5-dithiolate). X-ray crystal structure analysis of (pyridazinium+)(DCH[18]-crown-6)[Ni(dmit)2]− (1) revealed a chair-type conformation of the DCH[18]-crown-6 moiety. A V-shaped conformation of the DB[18]-crown-6 moiety was observed in (pyridazinium+)(DB[18]-crown-6)2[Ni(dmit)2]−(H2O)2 (2). Nitrogen atoms in the pyridazinium cations interacted with the oxygen atoms of the DCH[18]-crown-6 and DB[18]-crown-6 through N–H+O hydrogen bonds, forming 1:1 and 1:2 supramolecular structures, respectively. Sufficient space for molecular motions of the pyridazinium cations, namely flip-flop and in-plane rotations, exists in salt 1. Disorder in nitrogen atoms was observed by X-ray analysis, indicating dynamic motion of the pyridazinium cation, namely flip-flop motion and in-plane motion. A potential energy calculation further supported the possibility of dynamic motion of cations in the crystal. By contrast, the flip-flop motion of the pyridazinium group in salt 2 is restricted by the two nearest-neighbouring DB[18]-crown-6 molecules. Weak antiferromagnetic intermolecular interactions between the [Ni(dmit)2]− anions in the two-dimensional layers of salt 1 were observed, resulting in alternating antiferromagnetic Heisenberg chain-type magnetic susceptibility. Quasi-one-dimensional intermolecular interactions between the [Ni(dmit)2]− anions were observed in salt 2, whose magnetic behaviour followed the Bonner–Fisher model.

Supramolecular cations of the m-fluoroanilinium(dibenzo[18]crown-6) in ferromagnetic salt

A supramolecular cation of (m-FAni(+))(DB[18]crown-6), where m-FAni(+) and DB[18]crown-6 denote m-fluoroanilinium(+) and dibenzo[18]crown-6, respectively, which is the polar unit rotating in the ferroelectric crystal of (m-FAni(+))(DB[18]crown-6)[Ni(dmit)(2)](-), was introduced into a ferromagnetic [MnCr(oxalate)(3)](-) salt as the counter cation. The crystal structure of (m-FAni(+))(DB[18]crown-6)[MnCr(oxalate)(3)](-)(CH(3)OH)(CH(3)CN) (1) is constructed from alternating layers of a two-dimensional honeycomb layer of [MnCr(oxalate)(3)](-) and (m-FAni(+))(DB[18]crown-6) supramolecular cations. The anionic layer is composed of Mn(II) and Cr(III) ions with S = 5/2 and S = 3/2 spins, respectively, bridged by the oxalate anions, which show ferromagnetic ordering at 5.5 K. The supramolecular structure is formed through the formation of hydrogen bonds between the ammonium hydrogen atoms of the m-FAni(+) cations and the oxygen atoms of the DB[18]crown-6 cavity. No orientational disorder of the fluorine atoms was observed in our X-ray structural analysis, suggesting that a two-fold flip-flop motion of the m-FAni(+) cations does not occur in the salt. The rotational freedom of the m-FAni(+) cations in the salt is restricted by the steric hindrance from neighbouring DB[18]crown-6 molecules. A design strategy for the rotation in a salt is discussed, based on the volume that the supramolecular cations occupy in the unit cell.

Different metal-ion-induced dimeric self-assembling cavities based on thiacalix[4]benzocrown-4 isomers

To construct the self-assembly of metal-ion-induced well-ordered architectures based on calixcrowns, isomeric thiacalix[4]benzocrowns-4 1 and 2 with rigid and small crown units were employed as the new scaffolds. They all show remarkable selectivity for Ag(+) and their complexation ability towards Ag(+) results in two novel dimeric aggregates of calixcrowns, which were first evidenced by ESI-MS, (1)H and DOSY-NMR spectra. Ultimately, X-ray diffraction experiments confirmed unambiguously the existence of the two metal-ion-induced dimers in lower rim/lower rim mode, and showed that dimerization of calixcrown 1 or 2 in the presence of Ag(+) could form dimeric supramolecular cavity with a small inner room. Moreover, the positional isomerism of their crown units (o-benzocrown unit for ligand 1 and m-benzocrown unit for 2) led to a dramatic change in the configuration of the two dimeric cavities 1·Ag(+) and 2·Ag(+). For dimeric cavity 1·Ag(+), two silver centers seamed two thiacalix[4]crown molecules together and resided at the edge of the dimeric self-assembling cavity; for dimeric cavity 2·Ag(+), one Ag(+) stitched two thiacalixcrowns together and was encapsulated in the center of the self-assembling cavity, while the other Ag(+) is tied down to one end of the dimer. Consequently, as a result of the different construction of dimeric cavities 1·Ag(+) and 2·Ag(+) the extended structures of the complexes are also different. The neighbour self-assembling cavities 1·Ag(+) are mutually oriented side-by-side and form a 1-D rectilineal polymeric chain. While, the neighbour self-assembling cavities 2·Ag(+) arrange themselves in a typical head-to-tail fashion to form a zig-zag polymeric chain.

Guest⊂Guest⊂Host Multicomponent Molecular Crystals: Entrapment of Guest⊂Guest in Honeycomb Networks Formed by Self‐Assembly of 1,3,5‐Tri(4‐hydroxyaryl)benzenes

Sterically-engineered rigid trigonal molecular modules based on 1,3,5-tri(4-hydroxyphenyl)benzenes H1 and H2 undergo O-H...O hydrogen-bonded self-assembly into eight-fold catenated hexagonal (6,3) and two-fold interpenetrated undulated square (4,4) networks, respectively. In the presence of [18]crown-6 as a guest, the triphenol H1 is found to self-assemble into a honeycomb network with hexagonal voids created between three triphenol building blocks. The guest [18]crown-6 molecules are found to be nicely nested in hexagonal enclosures. The empty spaces within the crowns can be further filled with neutral (MeOH/water, MeOH/MeNO(2)) or ionic guest species such as KI/KAcAc to furnish novel multicomponent assemblies, that is, guest subset guest subset host, that typify Russian dolls. In contrast, triphenol H2 is found to yield analogous multicomponent molecular crystals in which the guest crown-K(+) acts as a spacers in the hydrogen-bonded self-assembly that leads to distorted chicken wire networks.

Inclusion of triphenylmethane derivatives by crown and linear O-containing molecules : selective interactions and crystal structures

The sulfamide derivative of triphenylmethanol, 3-[hydroxy(diphenyl)methyl]benzenesulfonamide (H2NSO2Ph)Ph2COH was synthesized and, alongside with the parent triphenylmethanol and triphenylmethylamine, was investigated for selective interactions with crown ethers of different dimensionality (12-18-membered cycles). The molecule of 12-crown-4 (12C4) appeared to be the best candidate for Ph3COH, Ph3CNH2 and Ph3CNH3·NCS, while (H2NSO2Ph)Ph2COH forms the complex exclusively with 18-crown-6 (18C6). The triphenylammonia trifluoroacetate, Ph3CNH3·CF3COO, selectively forms the complex only with 2-methoxyethanol. The crystalline products of the compositions (Ph3COH)2·12C4, (Ph3CNH2)2·12C4, (Ph3CNH3·NCS)2·12C4, [(H2NSO2Ph)Ph2COH]2·18C6 and Ph3CNH3·CF3COO CH3OCH2CH2OH were obtained and studied by X-ray single crystal diffraction.

Biphasic Electrospray Ionization for the Study of Interfacial Complexes

Biphasic electrospray ionization (BESI) mass spectrometry is achieved by using a dual-channel microsprayer, where channels filled with different immiscible phases meet at the Taylor cone. Two types of interfacial complexation reactions have been studied: the interfacial complexation of aqueous lead ions by thioether crown molecules, and the interfacial complexation of an aqueous dipeptide by dibenzo-18-crown-6 as ionophore. The mass spectra also give valuable information on the stoichiometry of the complexation reaction.

Structure of benzo- and dibenzocrown ethers and their H-bonded adducts. 4. Structural motifs in the 2,4-dithiouracil complexes with 4-bromo- and 4-nitrobenzo-18-crown-6, [2.4]dibenzo- and thia[1.5]dibenzo-18-crown-6

Four novel complexes of 2,4-dithiouracil (pyrimidine-2,4(1H,3H)-dithione, DTU) with 18-membered benzo- and dibenzo-crown ethers were synthesized in approximately the same conditions and studied by single crystal diffraction. Hydrogen bonding was observed to be the most important for the complexation in the solid state but π–π interactions also contribute to it. The crystalline monohydrates of the 1:1:1 stoichiometry are recorded for 4-bromo- and 4-nitrobenzo-18-crown-6 (complexes 1 and 2), while complexes with [2.4]dibenzo- and thia[1.5]dibenzo-18-crown-6 (complexes 3 and 4) represent anhydrous adducts of the 2:2 ratio. The crystal structures reveal three supramolecular structural motifs: the alternative chain for the ternary complex 1 and two types of capsules for complexes 2−4 where the DTU dimers are encapsulated inside the space restricted by two crown molecules.

Supramolecular approach for solid state Brownian rotators

Artificial molecular rotators were designed in an attempt to achieve unidirectional molecular rotation. Supramolecular assemblies of cations and crown ethers in the solid state were shown to form rotator structures, diverse in their rotational symmetry and frequency. The counter cation of [Ni(dmit)2]- anion, bearing one S=1/2 spin, was used to couple molecular rotation to magnetic properties. Random rotation of [18]crown-6 molecules was first observed in the Cs(+)2([18]crown-6)(3) supramolecule, where the rotational freedom of [18]crown-6 rotators was evidently coupled to the magnetic properties of [Ni(dmit)2]-pi-dimer. In other cases, dual rotary motions of anilinium([18]crown-6) and rotator-stator assemblies of (adamantylammonium)(dibenzo[18]crown-6) were investigated as a means to control rotational symmetries and frequencies in the solid state. The supramolecular approach for construction of molecular rotator-stator assemblies in the solid state is a convenient approach to the design of molecular rotary functionality in [Ni(dmit)2]- salts.

Structure of oxonium hexafluoroniobate and hexafluorotantalate complexes with crown ethers of different dimensionality

Two synthetic pathways, the interaction of Nb 2O 5 or Ta 2O 5 with an aqueous solution of hydrofluoric acid, HF, in the presence of 18-crown-6 (18C6), 15-crown-5 (15C5), benzo-15-crown-5 (B15C5) or benzo-12-crown-4 (B12C4), and the direct interaction of the corresponding pentafluorides, MF 5 (M = Ta, Nb), in the presence of HF with the same crown ethers result in crystalline complexes of the same composition, [18C6 · H 3O][NbF 6] ( 1), [18C6 · H 3O][TaF 6] ( 2), [15C5 · H 5O 2][TaF 6] ( 3), [(B15C5) 2 · H 5O 2][(B15C5) 2 · H 3O][TaF 6] 2 ( 4) and [(B12C4) 2 · H 3O][TaF 6] ( 5). Complexes 1– 5 were identified by elemental and X-ray structural analysis. Compounds 1 and 2 are isostructural, with the [H 3O] + oxonium ion embedded in one crown molecule via OH⋯O hydrogen bonds. Complexes 3– 5 represent sandwich-like adducts with the [H 3O] + or [H 5O 2] + cations encapsulated. A plethora of weak C–H⋯F interactions with NbF 6 - and TaF 6 - anions is responsible for the extended supramolecular architectures.

Polymeric waveguide biosensors with calixarene monolayer for detecting potassium ion concentration

Biophotonic sensors based on a polymer waveguide with Bragg reflection gratings are proposed in this work. For developing low-cost disposable sensors, UV curable polymer materials are utilized to demonstrate the waveguide sensors. The grating pattern is formed on the core layer of a polymer waveguide by exposing a laser interference pattern on a photoresist. To detect a small amount of analyte molecule through a specific binding, a calixarene crown molecule is immobilized on a sensing interface. Bragg reflection peak movement is observed depending on the potassium ion concentration dissolved in phosphate buffered saline solution. It has been confirmed experimentally that the sensor could detect the potassium ion concentration on the order of 1pM.

Structure of Dibenzocrown Ethers and their H-bonded Adducts. 3. Isolation of Oxonium Ions by Biphenyl-20-crown-6 and [1.5]Dibenzo-18-Crown-6 in Complexes with [NbF6]− and [TaF6

The reaction of Nb2O5 and Ta2O5 with an aqueous solution of hydrofluoric acid, HF in the presence of biphenyl-20-crown-6 (BP20C6, L1) or [1.5]dibenzo-18-crown-6 ([1.5]DB18C6, L2) results in the complexes [L1·(H3O)][NbF6] (1), [L1 (H3O)][TaF6] (2), [2L2·(H7O3)][NbF6] (3) and [2L2·(H7O3)][TaF6] (4). Complexes 1–4 were identified by the elemental and X-ray structural analysis and IR spectroscopy. Complexes 1 and 2 are isostructural, with the H3O+ oxonium ion embedded in one crown molecule via OH···O hydrogen bonds. Complexes 3 and 4 represent the supramolecular isomers distinctive by the crown conformations and crystal packing, with the (H7O3)+ cation enclosed in the cage of two crown molecules. Being poor H-bond acceptors, NbF 6 − and TaF 6 − anions do not compete with the crown oxygen atoms for the oxonium hydrogen atoms, but are involved in the numerous C–H···F short contacts responsible for the extended supramolecular architectures in all cases. A change of crown ethers’ conformation in complexes 1–4 and a correlation between the degree of proton hydration and an accessibility of the crown ether oxygen atoms is observed.