ABSTRACT
Dynamic fluorophore 9,14-diphenyl-9,14-dihydrodibenzo[a,c]phenazine (DPAC) affords a new platform to produce diverse emission outputs. In this paper, a novel DPAC-containing crown ether macrocycle D-6 is synthesized and characterized. Host-guest interactions of D-6 with different ammonium guests produced a variety of fluorescence with hypsochromic shifts up to 130 nm, which are found to be affected by choice of solvent or guest and host/guest stoichiometry. Formation of supramolecular complexes were confirmed by UV-vis titration, 1H NMR and HRMS spectroscopy.
ABSTRACT
Dynamic control over molecular emission, especially in a time-dependent manner, holds great promise for the development of smart luminescent materials. Here we report a series of dynamic multicolor fluorescent systems based on the time-encoded locking and unlocking of individual vibrational emissive units. The intramolecular cyclization reaction driven by adding chemical fuel acts as a chemical lock to decrease the conformational freedom of the emissive units, thus varying the fluorescence wavelength, while the resulting chemically locked state can be automatically unlocked by the hydrolysis reaction with water molecules. The dynamic molecular system can be driven by adding chemical fuels for multiple times. The emission wavelength and lifetime of the locking states can be readily controlled by elaborating the molecular structures, indicating this strategy as a robust and versatile way to modulate multi-color molecular emission in a time-encoded manner.
ABSTRACT
Regulating the fluorescent properties of organic small molecules in a controlled and dynamic manner has been a fundamental research goal. Although several strategies have been exploited, realizing multi-color molecular emission from a single fluorophore remains challenging. Herein, we demonstrate an emissive system by combining pyrene fluorophore and acylhydrazone units, which can generate multi-color switchable fluorescent emissions at different assembled states. Two kinds of supramolecular tools, amphiphilic self-assembly and γ-cyclodextrin mediated host-guest recognition, are used to manipulate the intermolecular aromatic stacking distances, resulting in the tunable fluorescent emission ranging from blue to yellow, including a pure white-light emission. Moreover, an external chemical signal, amylase, is introduced to control the assembly states of the system on a time scale, generating a distinct dynamic emission system. The dynamic properties of this multi-color fluorescent system can be also enabled in a hydrogel network, exhibiting a promising potential for intelligent fluorescent materials.
ABSTRACT
A light-responsive supramolecular polymer was constructed by an AB-type monomer containing a light-responsive overcrowded alkene. The primary assemblies of the supramolecular polymer can further undertake secondary self-assembly by interfacial host-guest connections, which can be manipulated by light stimuli to convert into discrete primary assemblies.
ABSTRACT
The design of tunable dynamic self-assembly of nanoparticles with switchable assembled dimensions and morphologies is a challenging goal whose realization is vital for the evolution of smart nanomaterials. Herein, we report on chitosan polymer as an effective supramolecular "glue" for aldehyde-modified Au nanoparticles to reversibly modulate the states of self-assembled nanocomposites. By simultaneous integration of dynamic covalent Schiff base interactions and noncovalent hydrogen bonds, the chitosan/Au nanocomposites could reversibly transform their assembled morphologies from one-dimensional nanowires to three-dimensional nanosponges in response to the variation of pH value. Moreover, the obtained nanosponges could be used as an efficient pH-controlled cargo release system.
