Figure 6. Plots of (A) fluorescence quantum yield of HPS vs water fraction in acetone/water mixtures and (B) its PL peak intensity vs glycerol fraction in glycerol/methanol mixtures; [HPS] = 10 μM. (C) PL spectra of 2 in 1,4-dioxane at different temperatures and (D) effect of temperature on its PL peak intensity; [2] = 10 μM. Panels A−D are reprinted from ref 46.

"United we stand, divided we fall."--Aesop. Aggregation-induced emission (AIE) refers to a photophysical phenomenon shown by a group of luminogenic materials that are non-emissive when they are dissolved in good solvents as molecules but become highly luminescent when they are clustered in poor solvents or solid state as aggregates. In this Review we summarize the recent progresses made in the area of AIE research. We conduct mechanistic analyses of the AIE processes, unify the restriction of intramolecular motions (RIM) as the main cause for the AIE effects, and derive RIM-based molecular engineering strategies for the design of new AIE luminogens (AIEgens). Typical examples of the newly developed AIEgens and their high-tech applications as optoelectronic materials, chemical sensors and biomedical probes are presented and discussed.

It has been difficult to decipher the mechanistic issue whether E/Z isomerization is involved in the aggregation-induced emission (AIE) process of a tetraphenylethene (TPE) derivative, due to the difficulty in the synthesis of its pure E and Z conformers. In this work, pure stereoisomers of a TPE derivative named 1,2-bis{4-[1-(6-phenoxyhexyl)-4-(1,2,3-triazol)yl]phenyl}-1,2-diphenylethene (BPHTATPE) are successfully synthesized. Both isomers show remarkable AIE effect (α(AIE) ≥ 322) and high fluorescence quantum yield in the solid state (Φ(F) 100%). The conformers readily undergo E/Z isomerization upon exposure to a powerful UV light and treatment at a high temperature (>200 °C). Such conformational change, however, is not observed under normal fluorescence spectrum measurement conditions, excluding the involvement of the E/Z isomerization in the AIE process of the TPE-based luminogen. The molecules of (E)-BPHTATPE self-organize into ordered one-dimensional nanostructures such as microfibers and nanorods that show obvious optical waveguide effect. BPHTATPE shows rich chromic effects, including mechano-, piezo-, thermo-, vapo-, and chronochromisms. Its emission peak is bathochromically shifted by simple grinding and pressurization and the spectral change is reversed by fuming with a polar solvent, heating at a high temperature, or storing at room temperature for some time. The multiple chromic processes are all associated with changes in the modes of molecular packing.

Efficient room temperature phosphorescence is observed in natural compounds and polymers such as starch, cellulose, bovine serum albumin (BSA), and some other carbohydrates. Whereas being practically nonluminescent in solutions and TLC plates, they emit bright phosphorescence in the crystalline states with lifetime up to microseconds, exhibiting crystallization-induced phosphorescence (CIP) characteristics. The CIP of these natural products without any conventional chromophores offers a new platform for the exploration of conceptually novel luminogens. room temperature phosphorescence, natural products, cellulose, starch, bovine serum albumin

Luminescent bioprobes are powerful analytical means for biosensing and optical imaging. Luminogens featured with aggregation-induced emission (AIE) attributes have emerged as ideal building blocks for high-performance bioprobes. Bioprobes constructed with AIE luminogens have been identified to be a novel class of FL light-up probing tools. In contrast to conventional bioprobes based on the luminophores with aggregation-caused quenching (ACQ) effect, the AIE-based bioprobes enjoy diverse superiorities, such as lower background, higher signal-to-noise ratio and sensitivity, better accuracy, and more outstanding resistance to photobleaching. AIE-based bioprobes have been tailored for a vast variety of purposes ranging from biospecies sensing to bioimaging to theranostics (i.e., image-guided therapies). In this review, recent five years' advances in AIE-based bioprobes are briefly overviewed in a perspective distinct from other reviews, focusing on the most appealing trends and progresses in this flourishing research field. There are altogether 11 trends outlined, which have been classified into four aspects: the probe composition and form (bioconjugtes, nanoprobes), the output signal of probe (far-red/near-infrared luminescence, two/three-photon excited fluorescence, phosphorescence), the modality and functionality of probing system (dual-modality, dual/multifunctionality), the probing object and application outlet (specific organelles, cancer cells, bacteria, real samples). Typical examples of each trend are presented and specifically demonstrated. Some important prospects and challenges are pointed out as well in the hope of intriguing more interests from researchers working in diverse areas into this exciting research field.

Hyperbranched polytriazoles with spring-like architectures exhibit the feature of aggregation-induced emission (AIE) due to the high compressibility of polymer spheres from solution to aggregate. Thanks to their AIE effect, the polymer nanoaggregates can detect explosives with superamplification effect.

Stepwise locking of phenyl rings of tetraphenylethene increases the emission efficiency of luminogen solutions gradually, thus verifying the restriction of intramolecular rotation (RIR) mechanism of the aggregation induced emission phenomenon. The emission of the luminogen with one "O" bridge could be tuned reversibly in solid state through repeated heating and grinding.

Poly(N-isopropylacrylamide) was labelled using a fluorogen with an aggregation-induced emission feature by direct polymerization; the label served as a fluorogenic probe that reveals fine details in the thermal transitions in the aqueous solution of the polymer; the working mode was readily tuned between non-monotonic and monotonic by changing the labelling degree of the polymer.