Controllable π-π coupling of intramolecular dimer models in aggregated states.

π-π coupling as a common interaction plays a key role in emissions, transport and mechanical properties of organic materials. However, the precise control of π-π coupling is still challenging owing to the possible interference from other intermolecular interactions in the aggregated state, usually resulting in uncontrollable emission properties. Herein, with the rational construction of intramolecular dimer models and crystal engineering, π-π coupling can be subtly modulated by conformation variation with balanced π-π and π-solvent interactions and visualized by green-to-blue emission switching. Moreover, it can rapidly respond to temperature, pressure and mechanical force, affording a facile way to modulate π-π coupling in situ. This work contributes to a deeper understanding of the internal mechanism of molecular motions in aggregated states.

Enhanced Gain in Organic Photodetectors Using the Polymer with Singlet Open-Shell Ground State.

Photodetectors are critical components in intelligent optoelectronic systems, and photomultiplication-capable devices are essential for detecting weak optical signals. Despite significant advances, developing photomultiplication-type organic photodetectors with high gain and low noise current simultaneously remains challenging. In this work, a new conjugated polymer PDN with singlet open-shell ground state is introduced in active layers for electron capture, and the corresponding PDN-based photodetectors exhibited an enhanced photoelectric gain and decreased dark current density at a low forward bias. At 1.5 V, the PDN-based ternary photodetector has the external quantum efficiency (EQE) up to 2552.3 % and the specific detectivity of 1.4×1014  Jones at 710 nm calculated by the measured noise current, with the gain 22 times higher than that of the control group. This study provides an approach for exploiting polymers with singlet open-shell ground state to enhance the gain of organic photodetectors.

Organic Persistent RTP Crystals: From Brittle to Flexible by Tunable Self-Partitioned Molecular Packing.

Aiming to solve the trade-off of "room-temperature phosphorescence (RTP)-flexibility" in principle, organic RTP crystals with elastic/plastic deformation are realized. These properties are mainly due to the divisional aggregation structures of aromatics and alkoxy chains, and can be modulated by the controllable molecular configurations. The longest RTP lifetime of 972.3 ms is achieved as the highest record for organic flexible crystals. Plastic crystals with persistent RTP are realized, which can be applied into biomedical optical technologies by afterglow delivery. Moreover, the relationship among elastic/plastic deformation, RTP property, and aggregated structures is established. The elastic/plastic deformation is mainly determined by the difference of interaction energies from the aromatics and the alkoxy chains. For the BP-OR series with twisted configurations, the alkoxy chain with the middle length is favorable for the RTP property, while the strength of the π-π coupling is the cruical factor to the RTP property of the Xan-OR series with planar skeletons. A new way to promote the development of flexible RTP crystals, by modulation of aggregated structures as well as rational distribution of intermolecular interactions, is explored.

Promoting photothermal antibacterial activity through an excited-state intramolecular proton transfer process.

The construction of an efficient photothermal antibacterial platform is a promising strategy for the treatment of drug-resistant bacterial infections. Herein, through the introduction of excited-state intramolecular proton transfer to promote the photothermal effect, N-(2,4-dihydroxybenzylidene)-4-aminophenol (DOA)-polyvinyl alcohol (PVA) systems (DPVA) can reach 55 °C within 10 s under irradiation. They show superior antibacterial behavior against drug-resistant bacteria and a therapeutic effect on infected skin wounds with only 100 s of irradiation, much faster than those of reported photothermal materials (5-10 min). This work provides a convenient approach to fabricate broad-spectrum antibacterial wound dressings for treating bacteria-infected wounds, greatly contributing to the design and applications of photothermal antibacterial platforms.

Expounding the Relationship between Molecular Conformation and Room-Temperature Phosphorescence Property by Deviation Angle.

Room-temperature phosphorescence (RTP) emitters with ultralong lifetimes are attracting more and more attention for their wide applications. However, it is still a big challenge to achieve persistent organic afterglow because of the undefined relationship between molecular structures and RTP effect. Herein, diphenylamine (DPA) as a commonly used building block is selected as the molecular skeleton. Through incorporation of various alkyl moieties by ortho-substitution in different numbers and positions, RTP lifetimes can increase from 129 to 661 ms with the subtle adjustment of molecular conformations. It is summarized that the deviation angle (θ) of phenyl units in the DPA skeleton from the ideal p-π conjugated plane can act as the key parameter determining RTP lifetime, and the larger the θ values, the longer the RTP lifetimes. Furthermore, this result has been successfully applied as the universal principle to explain the RTP properties of various organic luminogens with DPA blocks and similar structures.

Multi-photoresponsive triphenylethylene derivatives with photochromism, photodeformation and room temperature phosphorescence.

A series of triphenylethylene derivatives exhibited multi-photoresponsive properties, including photochromism, photodeformation and room temperature phosphorescence (RTP), which are strongly related to molecular conformations and packing in the aggregated states. Accordingly, these properties can be subtly adjusted by substituents to the center double bond and/or peripheral phenyl moieties. The introduction of bromine atom was beneficial to photochromism and photodeformation properties as a result of the additional C-H⋯Br interactions and electron-withdrawing property. Also, it can promote the RTP effect via heavy atom effect, resulting in persistent afterglow lasting up to 150 min as detected by chemiluminescent imaging system.

Tunable Photocontrolled Motions of Anil-Poly(ethylene terephthalate) Systems through Excited-State Intramolecular Proton Transfer and Trans-Cis Isomerization.

With the combination of excited-state intramolecular proton transfer and trans-cis isomerization as microscopic molecular motions under light stimulus, multiple photodeformable processes are achieved in anil-poly(ethylene terephthalate) systems, including simple bending, dancing butterflies, and switches. The doping films can realize light-driven contraction as large as 70% and bending angle of about 141°, upon a simple stretching process. The internal mechanism is confirmed by transient absorption spectra, and the relationship between molecular structure and photocontrolled motion is investigated by theoretical calculations and crystal analysis. This work provides a convenient approach by utilizing anils to fabricate reversible actuations with desirable geometries, greatly contributing to the applications and manufacturing of soft robots and related research.

Mechanoluminescence or Room-Temperature Phosphorescence: Molecular Packing-Dependent Emission Response.

Mechanoluminescence (ML) and room-temperature photophosphorescence (RTP) were achieved in polymorphisms of a triphenylamine derivative with ortho-substitution. This molecular packing-dependent emission afforded crucial information to deeply understand the intrinsic mechanism of different emission forms and the possible packing-function relationship. With the incorporation of solid-state 13 C NMR spectra of single crystals, as well as the analysis of crystal structures, the preferred packing modes for ML and/or RTP were investigated in detail, which can guide the reasonable design of organic molecules with special light-emission properties.