Porphyrin nanostructures with well-controlled size, shape and functionality can be used for visible-light photocatalysis. In this work, a graphene@porphyrin nanofibre composite was successfully fabricated via arginine-mediated self-assembly of tetrakis (4-carboxyphenyl) porphyrin (TCPP) on graphene nanoplates (GNPs). The formation and crystallisation of the graphene@porphyrin nanofibre composite was fully characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD), fourier transform infrared (FTIR), ultraviolet-visible (UV-vis) and fluorescence spectroscopy. The assembled TCPP nanofibers were 50–200 nm in diameter with length in micrometers long, which were densely and uniformly distributed on the surface of graphene. The GNPs@TCPP nanofibers showed enhanced visible-light photocatalytic activity in comparison with free-standing TCPP nanorods for the degradation of Rhodamine B (RhB) and methyl orange (MO). The possible photodegradation mechanism of these dyes by the GNPs@TCPP nanofiber photocatalyst was proposed.
A naphthalene diimide motif bearing phosphonic acid functionalities has been found to be self-assembled with L- and D-arginine through chirality induced molecular recognitions and leads to the formation of micrometre long nanobelts and spherical aggregates at pH 9 in water, respectively.
A new pyrene-phosphonate colorimetric receptor 1 has been designed and synthesized in a one-step process via amide bond formation between pyrene butyric acid chloride and phosphonate-appended aniline. The pyrene-phosphonate receptor 1 showed aggregation-induced enhanced emission (AIEE) properties in water/acetonitrile (ACN) solutions. Dynamic light scattering (DLS) characterization revealed that the aggregates of receptor 1 at 80% water fraction have an average size of ≈142 nm. Field emission scanning electron microscopy (FE-SEM) analysis confirmed the formation of spherical aggregates upon solvent evaporation. The sensing properties of receptor 1 were investigated by UV-vis, fluorescence emission spectroscopy, and other optical methods. Among the tested metal ions, receptor 1 is capable of recognizing the Fe3+ ion selectively. The changes in spectral measurements were explained on the basis of complex formation. The composition of receptor 1 and Fe3+ ions was determined by using Job’s plot and found to be 1:1. The receptor 1–Fe3+ complex showed a reversible UV-vis response in the presence of EDTA.
Donor–acceptorDonor–acceptor–π–acceptor–donor (D1-A1-π-A2/A3-D2)-type small molecules, such TPA-MC-2 and TPA-MC-3, were designed and synthesized starting from donor-substituted alkynes (TPA-MC-1) via [2 + 2] cycloaddition−retroelectrocyclization reaction with tetracyanoethylene (TCNE) and 7,7,8,8-tetracyanoquinodimethane (TCNQ) units, respectively. TPA-MC-2 and TPA-MC-3 chromophores differ on the A2/A3 acceptor subunit, which is 1,1,4,4-tetracyanobutadiene (TCBD) and a dicyanoquinodicyanomethane (DCQDCM), respectively. Both the derivative bearing same donors D1 (triphenylamine) and D2 (trimethylindolinm) and also same A1 (monocyano) as an acceptor, tetracyano with an aryl rings as the π-bridging moiety. The incorporation of TCNE and TCNQ as strong electron withdrawing units led to strong intramolecular charge-transfer (ICT) interactions, resulting in lower LUMO energy levels. Comparative UV–Vis absorption, fluorescence emission, and electrochemical and computational studies were performed to understand the effects of the TCNE and TCNQ subunits incorporated on TPA-MC-2 and TPA-MC-3, respectively.
The Tetraphenylethylene (TPE) based dumbbell shaped molecules TPE-Pi, TPE-Su, TPE-Az, and TPE-Se were synthesised bearing odd-even alkyl chains containing 7, 8, 9 and 10 carbons respectively. These molecules reveal typical Aggregation Induced Emission (AIE) behaviour. The influence of the odd or even alkyl chain length was shown by studying the morphology of self-assembled nanostructures formed in a range of tetrahydrofuran (THF)/water solvent systems. For example, with a water fraction of 80%, TPE derivatives with odd alkyl chains (TPE-Pi and TPE-Az) self-assembled into nanosphere structures, while TPE-Su with 8 alkyl chains formed microbelts and TPE-Se with 10 alkyl chains aggregated into flower-like superstructures. These TPE derivatives also revealed interesting mechanochromic properties upon grinding, fuming and heating, which reveal the importance of molecular stacking in the crystal structure to the luminescent properties of the aggregates .The mechanochromic properties of TPE-Pi, TPE-Su, and TPE-Az were also demonstrated by the process of grounding, fuming, and heating.