Excitation Energy Transfer in Dendritic Host–Guest Donor–Acceptor Systems

We report on a study of a physically formed host–guest system, which was designed to be investigated by fluorescence energy transfer. All donor and acceptor molecules used were cyanine dyes. Investigation was performed at the ensemble level as well as at the single‐molecule level. The ensemble measurements revealed a distribution of binding sites as well for the donor as for the acceptor. Accordingly, we found a distribution of the energy transfer efficiency. At the single‐molecule level, these distributions are still present. We could discriminate entities that show very efficient energy transfer, some that do not show any energy transfer and systems whose energy transfer efficiency is only about 50 %. The latter allowed the time‐resolved detection of energy transfer of single entities through the acceptor decay. Finally, we discuss the observation that the energy transfer efficiency fluctuates as a function of time.     

Interplay of Hole Transfer and Host–Guest Interaction in a Molecular Dyad and Triad: Ensemble and Single‐Molecule Spectroscopy and Sensing Applications

A new molecular dyad consisting of a Cy5 chromophore and ferrocene (Fc) and a triad consisting of Cy5, Fc, and β‐cyclodextrin (CD) are synthesized and their photophysical properties investigated at both the ensemble and single‐molecule levels. Hole transfer efficiency from Cy5 to Fc in the dyad is reduced upon addition of CD. This is due to an increase in the Cy5‐Fc separation (r) when the Fc is encapsulated in the macrocyclic host. On the other hand, the triad adopts either a Fc‐CD inclusion complex conformation in which hole transfer quenching of the Cy5 by Fc is minimal or a quasi‐static conformation with short r and rapid charge transfer. Single‐molecule fluorescence measurements reveal that r is lengthened when the triad molecules are deposited on a glass substrate. By combining intramolecular charge transfer and competitive supramolecular interaction, the triad acts as an efficient chemical sensor to detect different bioactive analytes such as amantadine hydrochloride and sodium lithocholate in aqueous solution and synthetic urine.     

Host–Guest Interaction of Chaperonin GroEL and Water‐Soluble CdTe Quantum Dots and its Size‐Selective Inclusion

Some nanoparticles, such as quantum dots (QDs), are widely used in the biological and biomedical fields due to their unique optical properties. However, little is currently known about the interaction between these nanoparticles and biomolecules. Herein, we systemically investigated the interaction between chaperonin GroEL and water‐soluble CdTe QDs based on fluorescence correlation spectroscopy (FCS), capillary electrophoresis, and fluorescence spectrometry. We observed that some water‐soluble CdTe QDs were able to enter the inner cavity of GroEL and formed an inclusion complex after the activation of chaperonin GroEL with ATP. The inclusion of GroEL was size‐selective to QDs and only small QDs were able to enter the inner cavity. The inclusion could suppress the fluorescence quenching of the QDs. Meanwhile, we evaluated the association constant between chaperonin GroEL and CdTe QDs by FCS. Our results further demonstrated that FCS was a very useful tool for study of the interaction of QDs and biomolecules.     

Metal–Organic Cyclohelicates as Optical Receptors for Glutathione: Syntheses,Structures, and Host–Guest Behaviors

Two trinuclear zinc‐based cyclohelicates, Zn–PDB (PDB=[5‐(dibenzylamino)‐N1′,N3′‐bis(pyridin‐2‐ylmethylene)isophthalohydrazide]) and Zn–PMB (PMB=[5‐(bodipy‐oxy)‐N1′,N3′‐bis(pyridin‐2‐ylmethylene)isophthalohydrazide]) containing dibenzylamino and BODIPY groups, respectively, were generated by incorporating two amide‐containing tridentate chelators into meta‐positions of a substituted phenyl ring. Single‐crystal structure analysis and related spectroscopic characterizations demonstrated the formation of macrocyclic helicals both in the solid state and in solution. The host–guest behavior of the cyclohelical hosts towards γ‐glutamyl‐cysteinyl‐glycine (GSH) and its component amino acids was investigated by spectroscopic titrations. UV/Vis absorption titration and NMR titrations of Zn–PDB and Zn–PMB upon addition of the above‐mentioned guests suggested that the Glu residue of GSH was positioned within the cavity. The COO⁻ groups interacted with metal ions through static interactions. The Cys moiety of GSH interacted with the amide groups sited in host molecules through hydrogen‐bonding interactions to produce measurable spectral changes. Fluorescent titrations of Zn–PMB upon the addition of GSH and ESI‐MS investigations of the titration solutions confirmed the host–guest interaction modes and revealed the possible 1:1 complexation stoichiometry. These results showed that the recognition of a substrate within the cavity of functionalized metal–organic cage‐like receptors could be a useful method to produce supramolecular sensors for biomolecules.     

Lower Activation Energy for Catalytic Reactions through Host–Guest Cooperation within Metal–Organic Frameworks

Industrial synthesis is driven by a delicate balance of the value of the product against the cost of production. Catalysts are often employed to ensure product turnover is economically favorable by ensuring energy use is minimized. One method, which is gaining attention, involves cooperative catalytic systems. By inserting a flexible polymer into a metal–organic framework (MOF) host, the advantages of both components work synergistically to create a composite that efficiently fixes carbon dioxide to transform various epoxides into cyclic carbonates. The resulting material retains high yields under mild conditions with full reusability. By quantitatively studying the kinetic rates, the activation energy was calculated, for a physical mixture of the catalyst components to be about 50 % higher than that of the composite. Through the unification of two catalytically active components, a new opportunity opens up for the development of synergistic systems in multiple applications.     

Structure–Performance Correlations of Organic Dyes with an Electron‐Deficient Diphenylquinoxaline Moiety for Dye‐Sensitized Solar Cells

The high performances of dye‐sensitized solar cells (DSSCs) based on seven new dyes are disclosed. Herein, the synthesis and electrochemical and photophysical properties of a series of intentionally designed dipolar organic dyes and their application in DSSCs are reported. The molecular structures of the seven organic dyes are composed of a triphenylamine group as an electron donor, a cyanoacrylic acid as an electron acceptor, and an electron‐deficient diphenylquinoxaline moiety integrated in the π‐conjugated spacer between the electron donor and acceptor moieties. The DSSCs based on the dye DJ104 gave the best overall cell performance of 8.06 %; the efficiency of the DSSC based on the standard N719 dye under the same experimental conditions was 8.82 %. The spectral coverage of incident photon‐to‐electron conversion efficiencies extends to the onset at the near‐infrared region due to strong internal charge‐transfer transition as well as the effect of electron‐deficient diphenylquinoxaline to lower the energy gap in these organic dyes. A combined tetraphenyl segment as a hydrophobic barrier in these organic dyes effectively slows down the charge recombination from TiO₂ to the electrolyte and boosts the photovoltage, comparable to their Ru^II counterparts. Detailed spectroscopic studies have revealed the dye structure–cell performance correlations, to allow future design of efficient light‐harvesting organic dyes.     

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.     

Unexpected Carbon Dioxide Inclusion in Water‐Saturated Pores of Metal–Organic Frameworks with Potential for Highly Selective Capture of CO2

Unusual CO₂ storage in water‐saturated MOFs was investigated by combining experiment and simulation. It was found that the micropores of HKUST‐1 saturated with water provide an environment that is thermodynamically and kinetically favorable for CO₂ capture, but not for N₂ and H₂ capture. We expect that this phenomenon have potential to be used for successful separation of CO₂ from versatile flue streams and pre‐combustion gas.     

Inclusion Behavior of β‐Cyclodextrin with Bipyridine Molecules: Factors Governing Host‐Guest Inclusion Geometries

Guest Effect : The differences of nitrogen atom positions and the bridge bonds linked to two pyridine rings of some bipyridine guests can significantly affect the binding abilities and inclusion geometries of β‐cyclodextrin with the guests in both the solution and solid states.

     

pH‐Switchable Macroscopic Assembly through Host–Guest Inclusion

A novel pH‐switchable macroscopic assembly is reported using alginate‐based hydrogels functionalized with host (α‐cyclodextrin, αCD) and guest (diethylenetriamine, DETA) moieties. Since the interaction of αCD and DETA is pH sensitive, the host hydrogel and guest hydrogel could adhere together when the pH is 11.5 and separate when the pH is 7.0. Furthermore, this pH‐controlled adhesion and dissociation shows a good reversibility. The host and guest polymers have good biocompatibility; therefore, this pH‐sensitive macroscopic assembly shows great potential in biotechnological and biomedical applications.

     

Generation‐Dependent Host–Guest Interactions: Solution States of Polyglycerol Dendrimers of Generations 3 and 4 Modulate the Localization of a Guest Molecule

Host–guest interactions between polyglycerol dendrimers of generations 3 and 4 (PGD‐G3 and G4) and 4‐amino‐3‐hydroxynapthalene‐2‐sulphonic acid (AHSA) were investigated by fluorescence spectroscopy, isothermal titration calorimetry (ITC), and dynamic light scattering (DLS). PGD‐G3 molecules were found to form an associated state with an average diameter of 82.7 nm in aqueous solution, in which PGD‐G3 provided a much more polar microenvironment than glycerol. PGD‐G3 and AHSA interacted attractively, showing a binding constant of 5.3×10⁵ M ^?1 with a 2:1 stoichiometry. On the other hand, AHSA interacted with the periphery of PGD‐G4, the majority of which existed as a unimer, forming a less polar microenvironment. The driving force of the interactions for PGD‐G3 and ‐G4 were mainly enthalpically and entropically driven, respectively. The generation‐dependent host–guest interactions were described in conjunction with thermodynamic parameters.     

Self‐Assembled Tetragonal Prismatic Molecular Cage Highly Selective for Anionic π Guests

The metal‐directed supramolecular synthetic approach has paved the way for the development of functional nanosized molecules. In this work, we report the preparation of the new nanocapsule 3? (CF₃SO₃)₈ with a A₄B₂ tetragonal prismatic geometry, where A corresponds to the dipalladium hexaazamacrocyclic complex Pd‐1 , and B corresponds to the tetraanionic form of palladium 5,10,15,20‐tetrakis(4‐carboxyphenyl)porphyrin ( 2 ). The large void space of the inner cavity and the supramolecular affinity for guest molecules towards porphyrin‐based hosts converts this nanoscale molecular 3D structure into a good candidate for host–guest chemistry. The interaction between this nanocage and different guest molecules has been studied by means of NMR, UV/Vis, ESI‐MS, and DOSY experiments, from which highly selective molecular recognition has been found for anionic, planar‐shaped π guests with association constants (K_a) higher than 10⁹ M ^?1, in front of non‐interacting aromatic neutral or cationic substrates. DFT theoretical calculations provided insights to further understand this strong interaction. Nanocage 3? (CF₃SO₃)₈ can not only strongly host one single molecule of M(dithiolene)₂ complexes (M=Au, Pt, Pd, and Ni), but also can finely tune their optical and redox properties. The very simple synthesis of both the supramolecular cage and the building blocks represents a step forward for the development of polyfunctional supramolecular nanovessels, which offer multiple applications as sensors or nanoreactors.     

Self‐Assembled Hexanuclear Organometallic Cages: Synthesis,Characterization, and Host–Guest Properties

A series of iridium‐ and rhodium‐based hexanuclear organometallic cages containing 2,5‐dichloro‐3,6‐dihydroxy‐1,4‐benzoquinone, 9,10‐dihydroxy‐1,4‐anthraquinone, and 6,11‐dihydroxynaphthacene‐5,12‐dione ligands were synthesized from the self‐assembly of the corresponding molecular “clips” and 2,4,6‐tri(4‐pyridyl)‐1,3,5‐triazine ligands in good yields. These organometallic cages can form inclusion systems with a wide variety of π‐donor substrates, including coronene, pyrene, [Pt(acac)₂], and hexamethoxytriphenylene. The 1:1 complexation of the resulting supramolecular assemblies was confirmed by ¹H NMR spectroscopy. Large complexation shifts (Δδ>1 ppm) were observed in the ¹H NMR spectra of guests in the presence of cage [Cp*₆M₆(μ‐DHNA)₃(tpt)₂](OTf)₆ ( 6a ; M=Ir, tpt=2,4,6‐tri(4‐pyridyl)‐1,3,5‐triazine). The formation of discrete 1:1 donor–acceptor complexes, pyrene ?6 b (M=Rh), coronene ?6 a , coronene ?6 b , and [Pt(acac)₂] ?6 a was confirmed by their single‐crystal X‐ray analyses. In these systems, the most important driving force for the formation of guest–host complexes is clearly the donor–acceptor π???π stacking interaction, including charge‐transfer interactions between the electron‐donating and electron‐accepting aromatic components. These structures provide compelling evidence for the existence of strong attractive forces between the electron‐deficient triazine core and electron‐rich guest. The results presented here may provide useful guidance for designing artificial receptors for functional biomolecules.     

Host–Guest Interactions in ExBox4+

The host–guest interaction between poly aromatic hydrocarbon/azine and the newly synthesized ExBox⁴⁺ complex is studied with the help of density functional theory. The solvent‐phase interaction energy is found to decrease with gradual substitution of methine groups (?CH?) from the six‐membered ring of guest molecules with N atoms in the resultant azine@ExBox⁴⁺ complex. The nature of the binding interaction is studied with the help of newly developed noncovalent interaction (NCI) plot program package along with energy decomposition analysis and charge decomposition analysis. The interactions are mostly π‐type van der Waals interactions.