Fully Fused Boron-Doped Polycyclic Aromatic Hydrocarbons: Their Synthesis, Structure–Property Relationships, and Self-Assembly Behavior in Aqueous Media

Planarized triarylboranes are attracting increasing attention not only as models of boron-doped graphenes, but also as promising materials for organic optoelectronics. In particular, polycyclic aromatic hydrocarbon (PAH) skeletons with embedded...

Core-Substituted Naphthalene-diimides (cNDI) and Related Derivatives: Versatile Scaffold for Supramolecular Assembly and Functional Materials

Naphthalene-diimide (NDI) derived building blocks have been explored extensively for supramolecular assembly as they exhibit attractive photophysical properties, suitable for applications in organic optoelectronics. Core-substituted derivatives of the NDI chromophore (cNDI) differ significantly from the parent NDI dye in terms of optical and redox properties. Adequate molecular engineering opportunities and substitution-dependent tunable optoelectronic properties make cNDI derivatives highly promising candidates for supramolecular assembly and functional material. This short review discusses recent development in the area of functional supramolecular assemblies based on cNDIs and related molecules.

AIE-Active Poly(phenyleneethynylene)s for Fluorescence and Raman Dual-Modal Imaging and Drug-Resistant Bacteria Killing

Poly(phenyleneethynylene) (PPE) is a widely used functional conjugated polymer with applications ranging from organic optoelectronics and fluorescence sensors to optical imaging and theranostics. However, the fluorescence efficiency of PPE in aggregate states is generally not as good as their solution states, which greatly compromises their performance in fluorescence-related applications. Herein, we design and synthesize a series of PPE derivatives with typical aggregation-induced emission (AIE) properties. In these PPEs, the diethylamino-substituted tetraphenylethene units function as the long-wavelength AIE source and the alkyl side chains serve as the functionalization site. The obtained AIE-active PPEs with large π-conjugation show strong aggregate-state fluorescence, interesting self-assembly behaviors, inherently enhanced alkyne vibrations in the Raman-silent region of cells, and efficient antibacterial activities. The PPE nanoparticles with good cellular uptake capability can clearly and sensitively visualize the tumor region and residual tumors via their fluorescence and Raman signals, respectively, to benefit the precise tumor surgery. After post-functionalization, the obtained PPE-based polyelectrolyte can preferentially image bacteria over mammalian cells and possesses efficient photodynamic killing capability against Gram-positive and drug-resistant bacteria. This work provides a feasible design strategy for developing multifunctional conjugated polymers with multimodal imaging capability as well as photodynamic antimicrobial ability.

AIE-Active Poly(phenyleneethynylene)s for Fluorescence and Raman Dual-Modal Imaging and Drug-Resistant Bacteria Killing

Poly(phenyleneethynylene) (PPE) is a widely used functional conjugated polymer with applications ranging from organic optoelectronics and fluorescence sensors to optical imaging and theranostics. However, the fluorescence efficiency of PPE in aggregate states is generally not as good as their solution states, which greatly compromises their performance in fluorescence-related applications. Herein, we design and synthesize a series of PPE derivatives with typical aggregation-induced emission (AIE) properties. In these PPEs, the diethylamino-substituted tetraphenylethene units function as the long-wavelength AIE source and the alkyl side chains serve as the functionalization site. The obtained AIE-active PPEs with large π-conjugation show strong aggregate-state fluorescence, interesting self-assembly behaviors, inherently enhanced alkyne vibrations in the Raman-silent region of cells, and efficient antibacterial activities. The PPE nanoparticles with good cellular uptake capability can clearly and sensitively visualize the tumor region and residual tumors via their fluorescence and Raman signals, respectively, to benefit the precise tumor surgery. After post-functionalization, the obtained PPE-based polyelectrolyte can preferentially image bacteria over mammalian cells and possesses efficient photodynamic killing capability against Gram-positive and drug-resistant bacteria. This work provides a feasible design strategy for developing multifunctional conjugated polymers with multimodal imaging capability as well as photodynamic antimicrobial ability.

On the Role of LiF in Organic Optoelectronics

Organic optoelectronic device behaviour is heavily dependent on interfacial effects due to the device architecture and thickness. Interfaces between the inorganic electrodes and the active organic layers play a defining role in the all of the electronic and stability processes that occur in organic light emitting diodes (OLEDs) and organic solar cells (OPVs). Amongst the many interlayers introduced at these interfaces to improve charge carrier movement and stability, LiF has proven to be the most successful and it is almost ubiquitous in all organic semiconductor devices. Implemented at both top and bottom contact interfaces, doped into the charge transporting layers, and used as encapsulants, LiF has played major roles in device performance and lifetime. This review highlights the use of LiF at both top and bottom contacts in organic optoelectronics, discusses the various mechanisms proposed for the utility of LiF at each interface, and explores its impact on device lifetimes. From examples relating to charge carrier flow, interfacial electronic level modification, and interfacial stability, a comprehensive picture of the role of LiF in organic devices can be formed. This review begins with a brief overview of the role of the interface in OLEDs and OPVs, and the general properties of LiF. Then, it discusses the implementation of LiF at the top contact electrode interface, followed by the bottom substrate contact electrode, examining both performance and degradation effects in both cases.

One-step preparation of metal-free phthalocyanine with controllable crystal form

Metal-free phthalocyanine (H2Pc) has been widely used as photosensitive semiconductors in the organic optoelectronics field because of its unique planar molecular structure and high photocarriers’ generation efficiency. Herein, this paper related to a new facile and efficient one-step method for preparing specific crystal form of H2Pc with high crystallinity through ball-milling process, in which α-H2Pc can be prepared directly by dry ball-milling, and β-H2Pc and X-H2Pc can be simply obtained through wet ball-milling in butanone solvent at different temperatures. X-ray diffraction (XRD) was used to characterize the crystal stability of α-H2Pc, β-H2Pc, and X-H2Pc, which revealed that all the three crystalline H2Pc prepared had excellent crystal stability under different mechanical conditions.

Deciphering the unusual fluorescence in weakly coupled bis-nitro-pyrrolo[3,2-b]pyrroles

Electron-deficient π-conjugated functional dyes lie at the heart of organic optoelectronics. Adding nitro groups to aromatic compounds usually quenches their fluorescence via inter-system crossing (ISC) or internal conversion (IC). While strong electronic coupling of the nitro groups with the dyes ensures the benefits from these electron-withdrawing substituents, it also leads to fluorescence quenching. Here, we demonstrate how such electronic coupling affects the photophysics of acceptor–donor–acceptor fluorescent dyes, with nitrophenyl acceptors and a pyrrolo[3,2-b]pyrrole donor. The position of the nitro groups and the donor-acceptor distance strongly affect the fluorescence properties of the bis-nitrotetraphenylpyrrolopyrroles. Concurrently, increasing solvent polarity quenches the emission that recovers upon solidifying the media. Intramolecular charge transfer (CT) and molecular dynamics, therefore, govern the fluorescence of these nitro-aromatics. While balanced donor-acceptor coupling ensures fast radiative deactivation and slow ISC essential for large fluorescence quantum yields, vibronic borrowing accounts for medium dependent IC via back CT. These mechanistic paradigms set important design principles for molecular photonics and electronics.