Supramolecular Host-Guest Hydrogel Based on γ-Cyclodextrin and Carboxybenzyl Viologen Showing Reversible Photochromism and Photomodulable Fluorescence.

Much effort has been devoted to the development of supramolecular hydrogels due to their broad applications and conveniently controllable properties. Here, we demonstrate a novel supramolecular host-guest hydrogel, which is constructed by the host γ-CD complexed with the guest 1-(4-carboxybenzyl)-4,4'-bipyridinium chloride (1+·Cl-) through the π···π interaction, hydrogen bonding, and host-guest interactions. The supramolecular hydrogel [1+@γ-CD]n exhibits reversible electron transfer photochromic behavior and photomodulable fluorescence. The excellent photochromic and fluorescence properties support the practical utility of the supramolecular hydrogel as a visual display and anti-counterfeiting material.

An inclusion complex of cucurbit[7]uril with benzimidazolyl benzyl viologen exhibits fluorescence and photochromic properties.

In order to investigate the photochromic mechanism of photochromic materials based on supramolecular host-guest systems, we designed and synthesized a unique viologen derivative (benzimidazolyl benzyl viologen, guest 1·Cl3), which does not contain oxygen atoms. The binding interaction of guest 13+ with host cucurbit[7]uril (Q[7]) was investigated by various techniques. The obtained supramolecular host-guest complex 13+@Q[7] exhibits interesting fluorescence emission and reversible photochromism. The ESR and XPS experimental data suggest that the photochromic process of the complex 13+@Q[7] comes from the electron transfer from the carbonyl O atoms of the host Q[7] to the bipyridinium N atoms of the guest 13+.

A light-responsive molecular switch based on cucurbit[7]uril and 1,1'-bis(benzyl)-4-[2-(4-pyridyl)-vinyl]-pyridinium dibromide displaying white light emission.

By using 1H NMR, ESI-MS and UV spectra, a novel light-responsive molecular switch constructed using 1,1'-bis(benzyl)-4-[2-(4-pyridyl)-vinyl]-pyridinium (12+) and cucurbit[7]uril (Q[7]) is demonstrated. The E- to Z-isomerization of the double bond in 12+ results in the transition of the switching states from the 1 : 2 complex E-12+@Q[7]2 to the stable 1 : 1 complex Z-12+@Q[7]. In particular, both the 1 : 2 complex and the 1 : 1 complex can emit cold white fluorescence under UV light.

Detecting Pesticide Dodine by Displacement of Fluorescent Acridine from Cucurbit[10]uril Macrocycle.

According to a simple guest-replacement fluorescence turn-on mechanism, we constructed a fluorescent probe system based on cucurbit[10]uril (Q[10]) and protonated acridine (AD) to detect the pesticide dodine (DD). Formation of a homoternary inclusion complex AD2@Q[10] in both aqueous solution and solid state was studied by means of 1H NMR spectroscopy and X-ray crystallography. Although AD can emit strong fluorescence in aqueous solution, the homoternary inclusion complex AD2@Q[10] does not exhibit any fluorescence. Upon the addition of the pesticide DD into the aqueous solution of AD2@Q[10], the AD molecules in the Q[10] cavity are displaced by the pesticide DD, and strong fluorescence recovers. The fluorescent probe system based on Q[10] and AD provided a wide determination of DD from 0 to 4.0 × 10-5 mol·L-1 with a low limit of detection of 1.827 × 10-6 mol·L-1. The guest-replacement fluorescence turn-on mechanism is also confirmed by 1H NMR spectroscopy. Further, the fluorescent probe can directly detect DD residues in real agricultural products, and obvious fluorescence signal was observed under UV irradiation.

Selective Recovery and Detection of Gold with Cucurbit[n]urils (n = 5-7).

Environmentally benign methods for gold recovery and detection are highly desirable for a sustainable future. Herein, we demonstrate a selective recovery and detection strategy of gold with cucurbit[n]urils (Q[n = 5-7]) by means of outer-surface interactions. Tetrachloroaurate anion ([AuCl4]-) is able to be rapidly precipitated with Q[n] in forms of supramolecular adducts. X-ray crystallography of four Q[n = 5-7]·[AuCl4]- complexes reveal that strong outer-surface interactions between Q[n = 5-7] and [AuCl4]- are the major driving force for the formation of Q[n = 5-7]·[AuCl4]- complexes. Impressively, each Q[6] macrocycle is surrounded by 12 [AuCl4]- anions. Each of these 12 [AuCl4]- anions is connected to four adjacent [AuCl4]- anions, leading to the formation of a three-dimensional supramolecular framework with tubular channels. In addition, we found an interesting inclusion complex [Au(OH2)4]3+⊂Q[7] in the Q[7]·[AuCl4]- complex, which is the first example of hydrated metal cation encapsulated inside the cavity of Q[n]. Spectroscopic data suggest that Q[n = 5-7] possess a high affinity and selectivity for [AuCl4]- even in the presence of other transition-metal ions. Q[n] modified electrodes are found to be an effective material for the detection of trace gold in dilute solutions.

Symmetrical-Tetramethyl-Cucurbit[6]uril-Driven Movement of Cucurbit[7]uril Gives Rise to Heterowheel [4]Pseudorotaxanes.

Two novel heterowheel [4]pseudorotaxanes consisting of cucurbit[7]uril (Q[7]) and symmetrical-tetramethyl-cucurbit[6]uril (TMeQ[6]) were constructed via the multirecognition mechanism, in which Q[7] can rotate freely around the horizontal axis, while TMeQ[6] cannot. In the construction process, due to strong repulsive forces between carbonyl portals of two neighboring wheels, the dethreading and movement of the wheels along the axle was observed. The dissociation of the [4]pseudorotaxanes was also discussed.

Selective recognition and determination of phenylalanine by a fluorescent probe based on cucurbit[8]uril and palmatine.

This paper demonstrated a simple and validated fluorescence enhancing method to selectively recognize and discriminate the amino acid phenylalanine (Phe). 1H NMR spectroscopy reveal that the palmatine (PAL) can be encapsulated into the cucurbit [8]uril (Q [8]) in aqueous solution to form stable 1:2 host-guest inclusion complex PAL2@Q [8], which exhibits moderate intensity fluorescence property. Interestingly, the addition of the Phe into the inclusion complex PAL2@Q [8] leads to dramatically enhancing of the fluorescence intensity. In contrast, the addition of any other natural amino acids into the inclusion complex PAL2@Q [8] gives no fluorescence variation. Furthermore, it is easy to detect the concentration of Phe in target aqueous solution according to the linear relationship between fluorescence intensity and concentration of the Phe.

Host-guest complexation of cucurbit[8]uril with two enantiomers.

Host-guest complexation of cucurbit[8]uril (Q[8]) with two enantiomers, D-3-(2-naphthyl)-alanine (D-NA) and L-3-(2-naphthyl)-alanine (L-NA), has been fully investigated. Experimental data indicate that double guests reside within the cavity of Q[8] in both aqueous solution and solid state, generating highly stable homoternary complexes D-NA2@Q[8] and L-NA2@Q[8].

Construction of a Molecular Switch and Selector under Electrochemical Control.

In this work, we designed and synthesized a special axle guest hexyldimethyl(ferrocenylmethyl)ammonium (1 + ) bromide. The binding interactions of 1 + and its oxidized form 1 2+ with cucurbit[7]uril (Q[7]) and cyclohexanocucurbit[6]uril (Cy6Q[6]) were investigated by 1H NMR, cyclic voltammogram, and isothermal titration calorimetry techniques. Our data indicate that both hosts Cy6Q[6] and Q[7] can form stable [2]pseudorotaxanes with 1 + in their different redox states. Most importantly, the combination and dissociation of the hosts with the guest as well as the binding location can be controlled by electrochemical means, which develops a special molecular switch and selector.

Aniline-containing guests recognized by α,α',δ,δ'-tetramethyl-cucurbit[6]uril host.

The host-guest complexation of symmetrical α,α',δ,δ'-tetramethyl-cucurbit[6]uril (TMeQ[6]) and cucurbit[7]uril (Q[7]) with a series of aniline-containing guests has been investigated by various experimental techniques including NMR, ITC, and X-ray crystallography. Experimental results indicate that both TMeQ[6] and Q[7] hosts can encapsulate aniline-containing guests to form stable inclusion complexes. However, the oval cavity of TMeQ[6] is more complementary in size and shape to the aromatic ring of the guests than the spherical cavity of Q[7]. Shielding and deshielding effects of the aromatic ring on guests lead to the remarkable chemical shifts of the TMeQ[6] host protons. The rotational restriction of the guests in the oval cavity of TMeQ[6] results in the large negative values of entropy. The X-ray crystal structure of the 1:1 inclusion complex between TMeQ[6] and N,N'-diethyl-benzene-1,4-diamine unambiguously reveals that the aromatic ring of the guest resides in the oval cavity of TMeQ[6].

Host-guest complexation of di-cyclohexanocucurbit[6]uril and hexa-cyclohexanocucurbit[6]uril with alkyldiammonium ions: a comparative study.

The host-guest complexation of symmetrical di-cyclohexanocucurbit[6]uril (Cy2Q[6]) and hexa-cyclohexanocucurbit[6]uril (Cy6Q[6]) with a series of alkyldiammonium ions (H(3+)N(CH(2))nNH(3+), n = 2-8) has been studied both in solution and in the gas phase. (1)H NMR data indicate that all alkyldiammonium ions have inclusion interactions with both hosts except for the ethanediammonium ion. In addition, if the alkyl chain of the alkyldiammonium ion is longer than n = 5 methylene groups, compressed conformation may occur, which depends on the cavity shape of the hosts and the length of the alkyl chain. Isothermal titration calorimetry (ITC) studies point out that the host-guest complexations of both hosts with the latter five alkyldiammonium ions are enthalpically driven. The comparison of the thermodynamic data reveals that the enthalpies of the van der Waals interactions contribute more to the host-guest complexation enthalpy than the ion-dipole interactions. The enthalpic gain arises from the van der Waals interactions and the reduction of entropy upon the host-guest complexation is strongly affected by the cavity shape of the host. Gas phase structures of long alkyldiammonium guests within both hosts are completely different from those in aqueous solution.

The Binding Interactions between Cyclohexanocucurbit[6]uril and Alkyl Viologens Give Rise to a Range of Diverse Structures in the Solid and the Solution Phases.

The binding interactions between the cyclohexanocucurbit[6]uril (Cy6CB6) host and a series of dialkyl-4,4'-bipyridinium (viologen) dicationic guests were investigated in the solution phase, using (1)H NMR spectroscopy, and in the solid phase, using X-ray diffraction methods. In D2O solution, methyl viologen (MV(2+)) and ethyl viologen (EV(2+)) form 1:1 complexes in which the bipyridinium aromatic nucleus is partially included inside the Cy6CB6 cavity. Propyl viologen (PV(2+)), butyl viologen (BV(2+)), pentyl viologen (FV(2+)), and heptyl viologen (HV(2+)) form 2:1 complexes with Cy6CB6, in which each of the viologen aliphatic chains is included by a host molecule. In the solid state, EV(2+) forms a polypseudorotaxane via pseudorotaxane interdigitation of Cy6CB6 hosts. The PV(2+) guest forms a dumbbell-shaped structure with a Cy6CB6 host residing over each of the terminal propyl groups of the guest. In contrast to this, the BV(2+) guest and Cy6CB6 form a different polypseudorotaxane structure in which dumbbell-shaped structures, formed by two host molecules interacting with a single guest, are interconnected through metal-host coordination.

Mixed behavior of p-phenylenediaminium guest binding with the inverted cucurbit[6]uril host.

The binding interaction between inverted cucurbit[6]uril (iQ[6]) and p-phenylenediaminium both in the solid state and in aqueous solution has been investigated by X-ray crystallography, (1)H NMR spectroscopy and isothermal titration calorimetry (ITC). The experimental results suggest that the binding interaction between iQ[6] and p-phenylenediaminium may generate two different types of complexes in the solid state: one is an inclusion structure and the other is a sandwich structure. In aqueous solution, the iQ[6] host has an ability to accommodate the p-phenylenediaminium guest and in-out guest exchange is fast on the NMR time scale. ITC data indicate that the complexation of iQ[6] with p-phenylenediaminium is entropy driven.