Xiaofeng Fang

AIE (AIEE) and mechanofluorochromic performances of TPE-methoxylates: effects of single molecular conformations

Two methoxy-substituted tetraphenylethylene (TPE) derivatives, tetra(4-methoxyphenyl)ethylene (TMOE) and tetra(3,4-dimethoxyphenyl)ethylene (TDMOE), were synthesized by McMurry reaction in high yields. The nearly centrosymmetric and natural propeller shape of TMOE and TDMOE excluded intermolecular effects, such as H or J-aggregation and π–π stacking, on their AIE (AIEE) and mechanofluorochromic performance. The crystal structures of TMOE and TDMOE, and theoretical calculations proved that their emission colours are determined by single molecular conjugation. These molecules were used to investigate pure conformational effects on molecular emissions. The spectral properties of these molecules in five environments of crystal(s), THF solution, THF–water binary solution, solidified THF and amorphous states, were investigated. The crystalline to amorphous phase transition by grinding resulted in good mechanofluorochromic performances with high quantum yields and distinguishable emission change, which was further explored as anti-counterfeiting inks on banknotes.

Full-color tunable mechanofluorochromism and excitation-dependent emissions of single-arm extended tetraphenylethylenes

We propose a new single-arm extension strategy on traditional tetraphenylethylene and successfully develop a new series of full-color (from ∼450 nm to ∼740 nm) tunable mechanofluorochromic materials. These materials exhibit efficient solid-state emission (quantum yield Φf > 10%) and high mechanofluorochromic contrast (wavelength shift from ∼50 nm to ∼100 nm). More importantly, we discover an unexpected excitation-dependent emission phenomenon of mechanofluorochromic materials and propose to utilize this new excitation-dependent emission behavior of materials to evaluate their mechanical-responsive performances more comprehensively. Finally, the unique feature of abundant emissions of mechanofluorochromic materials by changing the excitation light has shown application potential in dual channel anti-counterfeiting.

Reversible Piezofluorochromic Property and Intrinsic Structure Changes of Tetra(4-methoxyphenyl)ethylene under High Pressure

During the past decade, luminescent mechanochromism has received much attention. Despite the garnered attention, only a few studies have reported the effect of internal molecular structure change on the performance of mechanochromic fluorescence. Here, we chose tetra(4-methoxyphenyl)ethylene (TMOE) as a model molecule to study the correlation between structure and fluorescence property under a hydrostatic pressure produced by a diamond anvil cell (DAC). TMOE is a methoxy-substituted tetraphenylethylene (TPE) derivative and has a nearly centrosymmetric structure and a natural propeller shape. Ultraviolet-visible absorption and fluorescence spectra of TMOE and TPE in solution proved that the presence of methoxy groups in TMOE is responsible for the difference in fluorescence emissions of TMOE and TPE. Under a hydrostatic pressure, the in situ fluorescence spectra of TMOE at different concentrations show that the fluorescence intensity gradually weakens, accompanied by an obvious redshift. The Raman peak intensities decrease gradually, and the peaks disappear eventually with the pressure increasing. These spectral changes are attributed to the changes in the intramolecular conformation, that is, the strengthening of the weak C-H···O hydrogen bonds in TMOE molecules, which is caused by the twisted dihedral angle between the benzene ring and the carbon rigid plane of ethylene. Density functional theory simulation further confirms that the decreased dihedral angle could weaken Raman peak intensity, which is consistent with our experimental results.

Multicolor Photo-Crosslinkable AIEgens toward Compact Nanodots for Subcellular Imaging and STED Nanoscopy

Aggregation induced emission (AIE) has attracted considerable interest for the development of fluorescence probes. However, controlling the bioconjugation and cellular labeling of AIE dots is a challenging problem. Here, this study reports a general approach for preparing small and bioconjugated AIE dots for specific labeling of cellular targets. The strategy is based on the synthesis of oxetane-substituted AIEgens to generate compact and ultrastable AIE dots via photo-crosslinking. A small amount of polymer enriched with oxetane groups is cocondensed with most of the AIEgens to functionalize the nanodot surface for subsequent streptavidin bioconjugation. Due to their small sizes, good stability, and surface functionalization, the cell-surface markers and subcellular structures are specifically labeled by the AIE dot bioconjugates. Remarkably, stimulated emission depletion imaging with AIE dots is achieved for the first time, and the spatial resolution is significantly enhanced to ≈95 nm. This study provides a general approach for small functional molecules for preparing small sized and ultrastable nanodots.

Fabrication and photoelectric properties of bio-inspired honeycomb film based on semiconducting polymer

Organic semiconducting materials have attracted significant attention for use in optoelectronic devices, as they can significantly improve device performance. Herein, a donor-acceptor conjugated polymer (poly(isoindigo-thiopheneylbenzothiadiazole, PID-TBT) was synthesized, which has strong and broad absorption in the visible region (400-800nm). The band gap of PID-TBT is 1.65eV. The PID-TBT honeycomb film with a porous structure was easily fabricated by the breath figure method. Compared with the smooth PID-TBT film, the honeycomb film shows significant enhancement in light capture capability and the efficiency of photoelectric conversion. The reflectance of the honeycomb film is reduced by 7% and the photocurrent is tenfold higher than that of the smooth film. Apart from designing new molecules by complex reactions, this work demonstrated that photoelectric conversion can be easily improved by introducing micro or nanostructures into devices.