Fluorescence study of inclusion complexes between star-shaped cholic acid derivatives and polycyclic aromatic fluorescent probes and the size effects of host and guest molecules

Star-shaped host molecules containing two, three, and four cholic acid moieties have been used to form inclusion complexes with polycyclic aromatic hydrocarbon probes (guests) varying in size from four (pyrene) to five (benzo(e)pyrene) and seven aromatic rings (coronene) and investigated by steady-state fluorescence measurements and fluorescence lifetime techniques. The results indicated that these hydrophobic guest probes prefer to locate in the hydrophobic cavities formed by the host molecules in an aqueous solution. Further studies showed that the stoichiometric ratios of the complexes depended on the relative size of both the host and the guest. The complexes of 1:1 ratio (guest:host) were formed between pyrene and the host molecules of different sizes, while the complexes of 1:2 ratio (guest:host) were found for coronene in all cases. For benzo(e)pyrene with an intermediate size, the complexes with 1:1 and 1:2 ratios (guest:host) were formed depending on the relative sizes of the host molecules. The stability of the inclusion complexes was observed to change with the solvent polarity, indicative of an adaptation of the hydrophobicity of the host pockets to the polarity of the solvent. The formation of the complexes was driven by the solvophobic interactions.     

环双(对-蒽基-对草快)的分子识别与谱学性质

环双(对-蒽基-对草快)是一种新型的缺电子大环仿生主体, 分子识别是其最重要的应用之一. 考察主体对一系列客体分子如水、氨、醇及杂环等的识别能力, 用密度泛函理论(DFT)中的B3LYP/3-21G基组对主客体复合物的结构进行优化. 在B3LYP/6-31G(d)水平上进行单点能计算, 校正后得到复合物的结合能. 用B3LYP/3-21G方法计算13C和3He化学位移. 结果表明, 主体对客体分子的识别主要靠客体上的杂原子与主体上的氢原子之间的氢键进行. 复合物的稳定化能受氢键的数目和距离影响. 氢键的形成导致部分复合物LUMO与HOMO能隙增大, 同时导致与氢键相连的C—H键上C原子的化学位移向低场移动. 复合物的芳香性与其结合能的大小及结合方式有关. 主体的芳香性因其与客体之间的弱相互作用而提高, 但太强的相互作用及客体在主体空腔内都将影响主体的环电流, 从而削弱其芳香性.     

Cyclic tetranuclear and hexanuclear palladium(II) complexes and their host-guest chemistry

Cyclic tetrameric complexes have been prepared by the reaction of Pd(en)Cl2 or Pd(dapol)Cl2, or their nitrato analogues, with Na2(5'GMP) in aqueous solution, where en=1,2-diaminoethane, dapol=1,3-diamino-2-propanol, and 5'GMP=guanosine 5'-monophosphate. Addition of certain small molecules containing hydrophobic groups resulted in the expansion of the tetramer to a cyclic hexamer with strong bonding of one guest per hexameric host. At pH 5-6, the guest molecule can be a cation, anion, or neutral, and those species containing trimetylsilyl and t-butyl groups bonded the most strongly. The size of the central cavity of the [Pd(en)(5'GMP)]6 host has been estimated to be 5.2 A. Formation of the host-guest complex caused a large upfield shift (Deltadelta) of 2.5-2.9 ppm in the 1H NMR spectrum of the most highly affected guest protons, which were those in closest proximity to the guanine nucleobases. NOESY spectra were used to determine the interaction sites between the host and the guest. Apparent association constants determined at 26 degrees C and pD 5.4 for the [Pd(en)(5'GMP)]6-DSS and [Pd(en)(5'GMP)]6-t-butanol systems, where DSS is 3-(trimethylsilyl)-1-propanesulfonate anion, were 1.36+/-0.11x10(4) and 2.74+/-0.95x10(4) M(-3/2), respectively. The Pd(dapol)-5'GMP system forms hexameric host-guest complexes, similar in nature to those of the Pd(en)-5'GMP system. The molecular and crystal structures of Pd(dapol)Cl2 are also reported.     

Effects of tert-butyl halide molecular siting in crystalline NaX faujasite on the infrared vibrational spectra

Experimental, analytical, and modeling techniques employed in this study elucidate interactions between adsorbate molecules and the interior surfaces of the porous host faujasite. The vibrational spectroscopies of guest and host offer opportunities to locate the guest site in the host. We present Fourier transform (FT) infrared (IR) studies of sodium-X (NaX) faujasite supercage-included tert-butyl halides, (CH(3))(3)C-X (X=Cl, Br, I) in comparison with the adsorbate molecular gas-phase and host solid-state spectra at 295 K. Four observations of guest (nu(5,) nu(6), nu(7), and {nu(3), nu(16), nu(17)}) vibrational mode changes, three of them concomitant with host mode changes, together with modeling studies, point to a particular preferred siting of the guest molecules at host hexagonal prisms (D6R). The siting involved simultaneous interactions of the host with methyl group axial protons and the halide atom. All three methyl group axial protons interact preferentially with a single D6R O1 oxygen atom via C-H...O bonding. The halide atom also interacts with a site III' Na cation. The cation, in turn, is coordinated by three O atoms (two O1 and an O4). Two of these O atoms (O1) bridge the double six-rings that form the hexagonal prism part of the NaX substructure. O4 connects the two D6R units.     

Electron Density Shift in Imidazolium Derivatives upon Complexation with Cucurbit[6]uril

In this study, we have investigated the supramolecular interaction between series of 1‐alkyl‐3‐methylimidazolium guests with variable alkyl substituent lengths and cucurbit[6]uril (CB6) in the solution and the solid state. Correct interpretation of ¹H NMR spectra was a key issue for determining the binding modes of the complexes in solution. Unusual chemical shifts of some protons in the ¹H NMR spectra were explained by the polarization of the imidazolium aromatic ring upon the complexation with the host. The formation of 1:1 complex between 1‐ethyl‐3‐methylimidazolium and CB6 is in disagreement with previously reported findings describing an inclusion of two guest molecules in the CB6 cavity.     

Spherical shape complementarity as an overriding motif in the molecular recognition of noncharged organic guests by p-sulfonatocalix[4]arene: complexation of bicyclic azoalkanes

[reaction: see text] The complexation of p-sulfonatocalix[4]arene (CX4) with 2,3-diazabicyclo[2.2.1]hept-2-ene (1), 2,3-diazabicyclo[2.2.2]oct-2-ene (2), 2,3-diazabicyclo[3.2.2]non-2-ene (3), 1-methyl-4-isopropyl-2,3-diazabicyclo[2.2.2]oct-2-ene (4), and 1-phenyl-2,3-diazabicyclo[2.2.2]oct-2-ene (5) was studied in D2O at pD 7.4 by 1H NMR spectroscopy. The formation of deep inclusion complexes was indicated by large upfield 1H NMR shifts of the guest protons (up to 2.6 ppm), which were also used to assign, in combination with 2D ROESY spectra, a preferential inclusion of the isopropyl group of 4 and a dominant inclusion of the azo bicyclic residue for 5. The bicyclic azoalkanes 1-3 showed exceptionally high binding constants on the order of 1000 M(-1), 1-2 orders of magnitude larger than for previously investigated noncharged organic guest molecules. The strong binding was attributed to the spherical shape complementarity between the guest and the conical cavity offered by CX4. Interestingly, although the derivatives 4 and 5 are more hydrophobic, they showed a 2-3 times weaker binding, which was again attributed to the deviation from spherical shape in these bridgehead-substituted derivatives. The preferential inclusion of the hydrophilic but spherical bicyclic residue of 5 rather than the hydrophobic aromatic phenyl group provides a unique observation in aqueous host-guest chemistry and corroborates the pronounced spherical shape affinity of CX4.     

Guest-controlling effects on ER behaviors of beta-cyclodextrin polymer

An effective and novel approach to obtaining electrorheological particles with high performance through the formation of host-guest complexes has been achieved. The significant preponderance of the host-guest complex formation is that the host structure can be controlled easily by adding different guests. Based on this point, six supramolecular complexes of beta-cyclodextrin cross-linking polymer with salicylic acid (beta-CDP-1), 5-chlorosalicylic acid (beta-CDP-2), 3,5-dichlorosalicylic acid (beta-CDP-3), 5-nitrosalicylic acid (beta-CDP-4), 3,5-dinitrosalicylic acid (beta-CDP-5), or 3-hydroxy-2-naphthoic acid (beta-CDP-6) particles were synthesized. The electrorheological yield stresses of the suspensions of these particles in silicone oil have been investigated under DC electric fields. It was found that the yield stress of the typical beta-CDP-1 ER fluid was 5.6 kPa in 4 kV/mm, which is much higher than that of pure beta-cyclodextrin polymer (beta-CDP), that of pure salicylic acid as well as that of the mixture of the host with the guest. It is clearly indicated that the formation of supramolecular complexes between beta-CDP and salicylic acid can enhance the ER properties of the host. The similar results for other supramolecular complexes with different guests have also been obtained under the same DC electric fields. The yield stress of supramolecular complexes is strongly affected by the structure of guests. Among the six investigated guests, 3-hydroxy-2-naphthoic acid gave the highest ER property having a yield stress of 9.8 kPa under 4 kV/mm DC while cross-linked with beta-CDP to form beta-CDP-6. The yield stress of beta-CDP-6 was significantly increased by 72% in comparison with that of the pure beta-CDP. However, the yield stress of beta-CDP-1-5 slightly increased by 34-41% as compared with that of the pure beta-CDP. The achieved results indicate that the ER effect of host-guest complexes can be greatly affected by the changes of the tremendous guest structure, whereas the slight guest structural transposition, such as altering different groups of a guest, can only obtain the adjacent electrorheological behavior. The dielectric properties of these host-guest complexes also proved that the ER effect can be affected by the properties of guest.     

NMR Studies of Host–guest Complexes Between Monocarboxylic Acids and Amide-based Cyclophanes in Chloroform

Formation of host–guest complexes with acetic acid and benzoic acid was studied by NMR for amide-based octaazacyclophanes having pendant methyl ester arms; the cyclophanes were tetramethyl 2,9,18,25-tetraoxo-1,4,7,10,17,20,23,26-octaaza[10.10]paracyclophane-4,7,20,23-tetraacetate, its meta-isomer and analogues. Amide NH proton and CH₂ proton adjacent to amide C = O in every cyclophane host showed down-field NMR shifts in the presence of the guest acids in CHCl₃-d, suggesting the formation of 1:1 complexes in which the carboxyl group of an acid molecule formed two hydrogen bonds with the amide NH and C = O moieties of a host molecule. Since the complex formation competed with the dimerization of the guest acids, the monomer–dimer equilibrium was restudied by NMR and the equilibrium constant was determined to be 330 M^? 1 for acetic acid and 518 M^? 1 for benzoic acid. By using these values, the formation constants of the host–guest complexes were determined to be 8–51 M^? 1. The close contact between the host and guest molecules via hydrogen bonding was consistently confirmed by NMR shifts due to the ring current of aromatic group.     

Synthesis of carbosilane dendritic wedges and their use for the construction of dendritic receptors

A divergent route for the synthesis of carbosilane wedges that contain either a bromine or amine as focal point has been developed. These new building blocks enable the construction of various core-functionalized carbosilane dendrimers. As a typical example carbosilane dendrimers up to the third generation containing a N,N',N'-1,3,5-benzenetricarboxamide core (G1-G3) have been synthesized. This new class of molecules has been studied as host molecules and they have been found to bind protected amino acids as guest molecules via hydrogen bonding interactions. A decrease in the association constants was observed for the higher generation dendritic hosts, which is attributed to the increased steric hindrance around the core where the binding site is located. The binding properties of the dendritic host molecules can be tuned by modifying the binding motif at the core of the carbosilane dendrimers. A higher association constant for N-CBZ-protected glutamic acid 1-methyl ester (5) was observed when the third generation N,N',N'-1,3,5-tris(L-alaninyl)benzenetricarboxamide core-functionalized carbosilane dendrimer (G3') was used as the host molecule compared to G3. Different association constants for the formation of the diastereomeric G3'.L-5(K=295 M(-1)) and G3'.(D-5)(2) (K=236 M(-1)) host-guest complexes were observed, pointing to a small enantioselective recognition effect. The difference between the association constants for the formation of the G3'.(L-5)(2) and G3'.(D-5)(2) host-guest complexes was much more pronounced, K=37 M(-1)versus K=10 M(-1), respectively.     

Preparation and Spectroscopic Study of Different Stoichiometric Solid Supramolecular Inclusion Complexes of β-Cyclodextrin with Short Chain Aliphatic Amines

The solid Supramolecular complexes of β-cyclodextrin (β-CD) with ethylenediamine 1, diethylenetriamine 2 and triethylamine 3 were obtained and characterized using elemental analysis, powder X-ray diffraction, infrared spectroscopy, thermogravimetric analysis, and 1H nuclear magnetic resonance spectroscopy. Based on the results of elemental analysis and 1H NMR, the guest-host stoichiometries of the three solid complexes were determined to be 5:2 for 1-β-CD, 1:1 for 2-β-CD, and 1:3 for 3-β-CD. The yields were relative to the molar volume ratio of guest toβ-CD cavity, and increased in the order: 1-β-CD<2-β-CD<3-β-CD. X-ray diffraction patterns of the inclusion complexes gave very good exhibitions not only in location of diffraction peaks but also in shape and diffraction intensity of the peaks due to the intermolecular complexations betweenβ-CD and the guests. The formation of host-guest inclusion complexes exhibited obviously enhanced phase change temperatures of the complexed guests such as 1 and 3. The H-5 protons located at the narrower rim inside the CD cavity experienced a higher shift upon inclusion while all other protons experienced lower shifts.     

NMR Investigations of Inclusion Complexes between β-Cyclodextrin and Naphthalene/Anthraquinone Derivatives

A ¹H and ¹³C NMR study on the inclusion complex between β-cyclodextrin and naphthalene, 1,5-dichloronaphthalene and 9,10-anthraquinone was carried out in order to define the stoichiometry of the association and the possible conformations. The upfield variation of the chemical shifts from the protons locate inside the cavity (H-3, H-5) coupled with the downfield variation of the other protons which locate outer sphere of the β-CD (H-1, H-2, H-4 and H-6,6′) provided clear evidence of the inclusion phenomena. The NMR spectra revealed the formation of 1:1 inclusion complex in which aromatic ring of the guest is tightly held by the host cavity. The signal degeneration of ¹H & ¹³C NMR spectra still exist for naphthalene and 1,5-dichloronaphthalene upon complexation revealed a symmetrical conformation of the guest molecules in the cavity of β-cyclodextrin, respectively. However, in 9,10-anthraquinone, the signal degeneration of ¹H & ¹³C NMR spectra was removed upon complexation which revealed an unsymmetrical conformation of the guest molecule inside the cavity. According to theoretical calculations and NMR studies, the possible conformations of the inclusion complexes are given here.     

Structural study of the inclusion compounds of thymol, carvacrol and eugenol in β-cyclodextrin by X-ray crystallography

The crystal structures of the inclusion compounds of thymol, carvacrol and eugenol, (components of essential oils of vegetable origin) in β-cyclodextrin have been determined. Thymol/β-CD crystallizes in the space group P1 containing two host molecules in its asymmetric unit whereas both carvacrol/β-CD and eugenol/β-CD complexes crystallize in the space group C2. In all three complexes two host molecules form head-to-head dimers their guest/host stoichiometry being: 1/2 (carvacrol/β-CD), 2/2 (thymol/β-CD) and 3/2 (eugenol/β-CD). In the cases of the thymol/β-CD and the carvacrol/β-CD complexes the β-CD dimers are arranged according to the channel packing mode. The accommodation of the geometrical isomer guests is performed solely by their hydrophobic groups revealing the leading role of the hydrophobic driving forces in the complexation process whereas the position of their hydroxyl group affects the stoichiometry of the formed dimeric complexes. In the case of the eugenol/β-CD dimeric complex one guest molecule is found lying between the β-CD groups in a sandwich fashion whereas the other two symmetry related guests protrude outwards the narrower rim of the hosts with only their hydrophobic allyl-chain located inside the hosts’ cavities. This arrangement prohibits the formation of a channel and the observed crystal packing is that of a Tetrad mode.     

Cyclic homooligomers from sugar amino acids: synthesis, conformational analysis, and significance

Sugar amino acids (SAAs) were designed as new building blocks carrying an amino group and a carboxyl group on a carbohydrate scaffold. By exploiting standard solid- and solution-phase coupling procedures, linear and cyclic homooligomers containing glucosyluronic acid methylamine (Gum) were synthesized. We achieved a high yield and a very short coupling time for the oligomerization and cyclization of sequences encompassing two, three, four, and six Gum units. The synthesis of cyclic oligomers containing only SAAs as repetitive units has not been reported before. The conformational preferences in aqueous solution of the cyclic derivatives and their applications as potential host molecules are described herein. Benzoic acid and p-nitrophenol were chosen as model guest molecules to study the formation of cyclodextrin-like inclusion complexes. The complexation behavior of the cyclic hexamer was proved from three different points of view: chemical shifts, longitudinal relaxations (T(1)), and diffusion coefficients. All of them showed different values for host and guest molecules measured independently and in the presence of each other.     

Photoresponsive molecular recognition and adhesion of vesicles in a competitive ternary supramolecular system

A competitive photoresponsive supramolecular system is formed in a dilute aqueous solution of three components: vesicles of amphiphilic α-cyclodextrin host 1a, divalent p-methylphenyl guest 2 or divalent p-methylbenzamide guest 3, and photoresponsive azobenzene monovalent guest 5. Guests 2 and 3 form weak inclusion complexes with 1a (K(a)≈10(2) M(-1)), whereas azobenzene guest 5 forms a strong inclusion complex (K(a)≈10(4) M(-1)), provided it is in the trans state. The aggregation and adhesion of vesicles of host 1a is mediated by guest 2 (or 3) due to the formation of multiple intervesicular noncovalent links, as confirmed by using isothermal titration calorimetry (ITC), optical density measurements at 600 nm (OD600), dynamic light scattering (DLS), and cryogenic transmission electron microscopy (cryo-TEM). The addition of excess monovalent guest trans-5 to vesicles of 1a aggregated by divalent guest 2 (or 3) causes the dispersion of vesicles of 1a because trans-5 displaces 2 (as well as 3) from the vesicle surface. Upon UV irradiation of a dilute ternary mixture of vesicles of 1a, guest 2 (or 3), and competitor trans-5, compound trans-5 isomerizes to cis-5, and renewed aggregation of vesicles of 1a by guest 2 (or 3) occurs because 2 (as well as 3) displaces cis-5 from the vesicle surface. Subsequent visible irradiation causes the redispersion of vesicles of 1a because cis-5 reisomerizes into trans-5, which again displaces guest 2 (or 3) from the vesicle surface. In this way, the competitive photoresponsive aggregation and dispersion of vesicles can be repeated for several cycles.     

Structure and Dynamics of Ternary Complexes of Cucurbit[8]uril with Spin-Labeled Indicators and Biologically Active Analytes

Ternary host–guest complexes have been first obtained from cucurbituril CB[8] as a host molecule and two guest molecules: nitroxyl probes of different structures and biologically important amino acids (AA) and aromatic compounds. To characterize the binding of the guests, parameters of the polarity of the environment and the rotational mobility of the spin probes have been used. These parameters have been shown to depend on the nature of the analytes. For the ternary complexes, in addition to the usual triplet ESR spectra from nitroxyl probes (S3), supramolecular ensembles consisting of three equivalent ternary complexes (“triads”) have been found, whose ESR spectra have a seven-component hyperfine structure (S7) due to delocalization of the unpaired electron over three nitrogen nuclei. The relative intensity of the S7 spectra increases with increasing NaCl concentration in the solution, and also depends significantly on the nature of the analyte and the spin probe. Quantum chemical calculations have shown that (1) to determine the stability of the complexes, it is necessary to allow for the van der Waals interaction, and (2) the complexes involving the zwitterionic form of AA are much more stable than those with the neutral form of AA.     

Atom-atom potential analysis of the complexing characteristics of cyclodextrins (host) with benzene and p-dihalobenzenes (guest)

Abstract

Intermolecular interaction and modelling calculations on the complexes of α-, β- and γ-cyclodextrins (host) with benzene and p-dihalobenzenes (guest) were performed. The complex formation mechanism between the host and guest molecules was evaluated from three-dimensional potential maps generated by the atom-atom potential method, and the molecular packing of the complexed compounds was visualized by a space-fill representation. Stable inclusion complexes only form when both the host and guest molecules experience a significant decrease in the complexing potential. The host and guest molecules have a maximum molecular surface contact at the minimum potential, which depends on both the cavity size and the molecular volumes of the guest molecules. The calculated interaction energies can be correlated to the association constants of complex formation determined from experiment. The molecular dynamics of the guest molecules are also discussed.     

A New Functional Cyclophane Host. Synthesis, Complex Formation and Crystal Structures of Three Inclusion Compounds

A new macrocyclic host compound 2 having an octamethylsubstituted cyclophane structure with two intra-annular carboxylic acid functions has beensynthesized. The properties of crystalline inclusion formation are studied and X-ray crystalstructures of three inclusion complexes including acetic acid, propionic acid and acetone asthe guest molecules are reported. Inter-host channel formation with complexed guest moleculesaccommodated into the channels are typical features of the acetic acid and acetone 1 : 4 (host : guest) stoichiometric complexes being also hydrated species, while the propionicacid 1 : 2 complex is of the close packing type containing no additional water molecules.Systems of hydrogen bonds involving the host and guest functional groups are common toall structures. In the case of the acetic acid inclusion compound, a complex supramolecularhydrogen-bonded array comprising a bordering tricyclic assembly of eight molecular species exists.     

Inclusion Compounds Formed from N,N-bis(2-hydroxybenzyl)alkylamine Derivatives and Transition Metal Ions via Molecular Assembly

A series of N,N-bis(2-hydroxybenzyl)alkylamine derivatives (1–5) have been found to form host–guest compounds with transition metal ions. The inclusion phenomena in solution are confirmed from the new peak at 415?nm observed by UV-Vis (ultraviolet-visible) spectroscopy and the aromatic and methylene peak shifts observed by ¹H NMR (proton nuclear magnetic resonance) spectroscopy. Comparative studies on 1–5 by liquid–liquid extraction studies suggest that the bulky group at the aza position of the derivatives obstructs the ion interaction resulting in the decrease in ion extraction ability. Inclusion depends on the interaction of the transition metal ions with the compounds 1–5 at the aza and hydroxyl groups as identified by the two-dimensional nuclear Overhauser enhancement technique (¹H–¹H NOESY). The results from Job's plot and electrospray ionization mass spectroscopy (ESIMS) imply molecular assembly of the host–guest system in a 2:1 ratio. Comparative studies among different ions, i.e., Cu²⁺, Zn²⁺ and Cd²⁺ suggest that the host–guest formation is effective when electron sharing is possible through the outer orbital of the transition metal ions. In the case of inclusion in the solid state, the FTIR (Fourier transform infrared) spectra show the changes in vibrational mode of the functional groups in host molecules whereas the X-ray diffraction (XRD) patterns suggest a change in the packing structure of the host molecules. After host–guest formation, the thermal stability of the host molecules decreases as a result of the change in the packing structure from a hydrogen-bonded network to one of ionic interaction with the guest.     

Control of release properties of guest molecules by the type of benzoheterocyclic ring in supramolecular host complexes

Three types of supramolecular benzoheterocyclic host complexes were successfully prepared using (1R,2S)-2-amino-1,2-diphenylethanol and three types of benzoheterocyclic (benzothiophene, benzofuran, and benzopyrrole) acid derivatives. The host complexes had one-dimensional (1D) channel-like cavities that were formed by the assembly of two-component 2₁-helical columnar network structures, which included guest alcohol molecules. The release behavior of the guest molecules could be tuned by the type of heterocyclic ring in the supramolecular host complex.     

A Study of the Interaction Between Cucurbit[8]uril and Alkyl‐Substituted 4‐Pyrrolidinopyridinium Salts

The interaction between cucuribit[8]uril (Q[8]) and a series of 4‐pyrrolidinopyridinium salts bearing aliphatic substituents at the pyridinium nitrogen, namely 4‐(C₄H₈N)C₅H₅NRBr, where R=Et (g1), n‐butyl (g2), n‐pentyl (g3), n‐hexyl (g4), n‐octyl (g5), n‐dodecyl (g6), has been studied in aqueous solution by ¹H NMR spectroscopy, electronic absorption spectroscopy, isothermal titration calorimetry and mass spectrometry. Single crystal X‐ray diffraction revealed the structure of the host–guest complexes for g1, g2, g3, and g5. In each case, the Q[8] contains two guest molecules in a centrosymmetric dimer. The orientation of the guest molecule changes as the alkyl chain increases in length. Interestingly, in the solid state, the inclusion complexes identified are different from those observed in solution, and furthermore, in the case of g3, Q[8] exhibits two different interactions with the guest. In solution, the length of the alkyl chain plays a significant role in determining the type of host–guest interaction present.