Tunable solid-state fluorescent materials are ideal for applications in security printing technologies. A document possesses a high level of security if its encrypted information can be authenticated without being decoded, while also being resistant to counterfeiting. Herein, we describe a heterorotaxane with tunable solid-state fluorescent emissions enabled through reversible manipulation of its aggregation by supramolecular encapsulation. The dynamic nature of this fluorescent material is based on a complex set of equilibria, whose fluorescence output depends non-linearly on the chemical inputs and the composition of the paper. By applying this system in fluorescent security inks, the information encoded in polychromic images can be protected in such a way that it is close to impossible to reverse engineer, as well as being easy to verify. This system constitutes a unique application of responsive complex equilibria in the form of a cryptographic algorithm that protects valuable information printed using tunable solid-state fluorescent materials.

Light has profoundly impacted modern medicine and healthcare, with numerous luminescent agents and imaging techniques currently being used to assess health and treat diseases. As an emerging concept in luminescence, aggregation-induced emission (AIE) has shown great potential in biological applications due to its advantages in terms of brightness, biocompatibility, photostability, and positive correlation with concentration. This review provides a comprehensive summary of AIE luminogens applied in imaging of biological structure and dynamic physiological processes, disease diagnosis and treatment, and detection and monitoring of specific analytes, followed by representative works. Discussions on critical issues and perspectives on future directions are also included. This review aims to stimulate the interest of researchers from different fields, including chemistry, biology, materials science, medicine, etc., thus promoting the development of AIE in the fields of life and health.

Small, apolar aromatic groups, such as phenyl rings, are commonly included in the structures of fluorophores to impart hindered intramolecular rotations, leading to desirable solid-state luminescence properties. However, they are not normally considered to take part in through-space interactions that influence the fluorescent output. Here, we report on the photoluminescence properties of a series of phenyl-ring molecular rotors bearing three, five, six, and seven phenyl groups. The fluorescent emissions from two of the rotors are found to originate, not from the localized excited state as one might expect, but from unanticipated through-space aromatic-dimer states. We demonstrate that these relaxed dimer states can form as a result of intra- or intermolecular interactions across a range of environments in solution and solid samples, including conditions that promote aggregation-induced emission. Computational modeling also suggests that the formation of aromatic-dimer excited states may account for the photophysical properties of a previously reported luminogen. These results imply, therefore, that this is a general phenomenon that should be taken into account when designing and interpreting the fluorescent outputs of luminescent probes and optoelectronic devices based on fluorescent molecular rotors.

The active transport of ions and molecules across cell membranes is essential to creating the concentration gradients that sustain life in all living organisms, be they bacteria, fungi, plants, animals or Homo sapiens. Nature uses active transport everywhere for everything. Molecular biologists have long been attracted to the study of active transport and continue to this day to investigate and elucidate the tertiary structures of the complex motor proteins that sustain it, while physicists, interested in nonequilibrium statistical mechanics, have developed theoretical models to describe the driven ratcheting motions that are crucial to its function. The increasingly detailed understanding that contemporary science has acquired relating to active transport, however, has yet to lead to the design and construction of artificial molecular motors capable of employing ratchet-driven motions that can also perform work against concentration gradients. Mechanically interlocked molecules (MIMs) in the form of pseudo- and semirotaxanes are showing some encouraging signs in meeting these goals. This review summarizes recent progress in making artificial molecular motors that can perform work by “pumping” tetracationic rings into high-energy states. The launching pad is a bistable [2]rotaxane whose dumbbell component contains two electron-donating recognition sites, one, a tetrathiafulvalene (TTF) unit, which interacts more strongly with the ring component, cyclobis(paraquat-p-phenylene) (CBPQT⁴⁺), containing two electron-accepting bipyridinium units, than does the other 1,5-dioxynaphthalene (DNP) unit. Switching can be induced electrochemically by oxidizing the TTF unit to a TTF^•+ radical cation, whereupon Coulombic repulsion takes care of moving the ring to the DNP unit. Reduction of the radical cation resets the switch. Molecular switches operate at, or close to, equilibrium. Any work done during one switching event is undone during the reset. Molecular motors, on the other hand, rely on a flux of energy, and a ratchet mechanism to make periodic changes to the potential energy surface of a system in order to move molecules uphill to higher energy states. Forging a path from molecular switches to motors involved designing a molecular pump prototype. An asymmetric dumbbell with a 2-isopropylphenyl (neutral) end and a 3,5-dimethylpyridinium (charged) end with a DNP recognition site to entice CBPQT⁴⁺ rings out of solution exhibits relative unidirectional movement of the rings with respect to the dumbbell. Redox chemistry does the trick. During the oxidative cycle, the rings enter the dumbbell by passing over the neutral end onto the recognition site; in the reduction cycle, much of the recognition is lost and the rings find their way back into solution by leaving the dumbbell from the charged end. This on-one-end, off-the-other process can be repeated over and over again using light as the energy source in the presence of a photosensitizer and a compound that shuttles electrons back and forth. Although this prototype demonstrates ratchet-driven translational motion, no work is done. A ring enters the dumbbell from one end and leaves from the other end. Another deficiency of the prototype is the fact that, although the recognition site is muted on reduction, it retains some attraction for the ring. What if the recognition site was attractive initially and then became repulsive? This question was answered by turning to radical chemistry and employing the known stabilization behavior of a bipyridinium radical cation and the bisradical dication, generated on reduction of the CBPQT⁴⁺ ring, to pluck rings out of solution and thread them over the charged end of the pump portion of a semidumbbell. On subsequent oxidation, the pump is primed and the rings pass through a one-way door, given a little thermal energy, onto a collecting-chain where they find themselves accumulating where they would rather not be present. In this manner, an artificial molecular pump mimics the pumping machinery commonplace in biological systems. Looking beyond this state-of-the-art artificial molecular pump, we discuss, from a theoretical standpoint, the measures that would need to be taken in order to render its operation autonomous.