Jiadong Zhou

Structure-modulated ICzs with flexible/rigid six-membered rings embedded in melamine-formaldehyde composites show efficient organic afterglow with a phosphorescence quantum yield ( Φ _Phos. ) of up to 17.59% and a lifetime ( τ _Phos. ) of up to 3.05 s.

A series of windmill‐shape heterocyclic molecules containing three N−B←N units, TBN and its derivatives, with quasi‐planar C ₃ symmetric backbone, are synthesized. The parent TBN exhibits a strongly allowed, doubly degenerate lowest excited state but suffers from very low fluorescence, due to very fast nonradiative decay rate through a conical intersection (CI) as revealed by femtosecond transient absorption spectroscopy and quantum‐chemical calculations. Introducing peripheral phenyl‐ or thienyl‐groups (Ph‐TBN or Th‐TBN) induces pronounced bathochromic shifts and enhances fluorescence, which is beneficial from inhibited nonradiative pathway by the increased energy barriers to access the CI at excited state. The understanding of this rather uncommon behaviour may open routes for the design of novel fluorescence materials.

A series of windmill‐shape heterocyclic molecules containing three N−B←N units, TBN and its derivatives, with quasi‐planar C ₃ symmetric backbone, are synthesized. The parent TBN exhibits a strongly allowed, doubly degenerate lowest excited state but suffers from very low fluorescence, due to very fast nonradiative decay rate through a conical intersection (CI) as revealed by femtosecond transient absorption spectroscopy and quantum‐chemical calculations. Introducing peripheral phenyl‐ or thienyl‐groups (Ph‐TBN or Th‐TBN) induces pronounced bathochromic shifts and enhances fluorescence, which is beneficial from inhibited nonradiative pathway by the increased energy barriers to access the CI at excited state. The understanding of this rather uncommon behaviour may open routes for the design of novel fluorescence materials.

Exploring approaches to utilize abundant water to synthesize functional molecules and polymers with efficient clusteroluminescence properties is highly significant but has yet to be reported. Herein, a chemistry of water and alkyne is developed. The synthesized products are proven as nonaromatic clusteroluminogens that could emit visible light. Their emission colors and luminescent efficiency could be adjusted by manipulating through-space interaction using different starting materials. Besides, the free-standing polymeric films with much high photoluminescence quantum yields (up to 45.7%) are in situ generated via a water-involved interfacial polymerization. The interfacial polymerization-enhanced emission of the polymeric films is observed, where the emission red-shifts and efficiency increases when the polymerization time is prolonged. The synthesized polymeric film is also verified as a Janus film. It exhibits a vapor-triggered reversible mechanical response which could be applied as a smart actuator. Thus, this work develops a method to synthesize clusteroluminogens using water, builds a clear structure-property relationship of clusteroluminogens, and provides a strategy to in situ construct functional water-based polymeric films.

Perylene bisimide (PBI) dyes are known as red, maroon and black pigments, whose colors depend on the close π−π stacking arrangement. However, contrary to the luminescent monomers, deep-red and black PBI pigments are commonly non- or only weakly fluorescent due to (multiple) quenching pathways. Here, we introduce N-alkoxybenzyl substituted PBIs that contain close π stacking arrangement (exhibiting d_π−π ≈ 3.5 Å, and longitudinal and transversal displacements of 3.1 Å and 1.3 Å); however, they afford deep-red emitters with solid-state fluorescence quantum yields (Φ_F) of up to 60%. Systematic photophysical and computational studies in solution and in the solid state reveal a sensitive interconversion of the PBI-centred locally excited state and a charge transfer state, which depends on the dihedral angle (θ) between the benzyl and alkoxy groups. This effectively controls the emission process, and enables high Φ_F by circumventing the common quenching pathways commonly observed for perylene black analogues.

Efficient long-range exciton migration and charge transport are the key parameters for organic photovoltaic materials, which strongly depend on the molecular stacking modes. Herein, we extracted the stacked structures of the archetype fused-ring electron acceptor molecule, ITIC, based on the information on four polymorphic crystals and investigated the relationship between molecular stacking modes and exciton migration/charge transport properties through the intermolecular Coulomb coupling and charge transfer integral calculation. Experimentally, the thin film texture is crystallized through a post-annealing treatment through grazing-incidence wide-angle X-ray scattering (GIWAXS) measurements, which lead to the enhanced exciton migration through exciton-exciton annihilation in the femtosecond transient absorption (fs-TA) measurements. This work demonstrates the relationship between the molecular arrangement and the exciton migration and electron transport and highlights the significance of optimizing molecular stacking for the development of high-performance electron acceptor materials.

Water is always used by nature to construct complex species. Learning from nature, the exploration of artificial approaches to utilize abundant water to synthesize functional molecules and polymers with efficient clusteroluminescence properties (CLgens) is highly significant but has yet to be reported. Herein, a new chemistry of water and alkyne was developed. The synthesized products were proved as nonaromatic CLgens that could emit visible light. Their emission colors and luminescent efficiency could be adjusted by manipulating through-space interaction via using different water and alkyne. Besides, the free-standing polymeric films with much high photoluminescence quantum yields (up to 45.7%) were in situ generated via a new H₂O-involved interfacial polymerization. The interfacial polymerization-induced emission of the polymeric films was observed, where the emission red-shifted and efficiency increased when the polymerization time was prolonged. The synthesized polymeric film was also verified as a "Janus film". It exhibits a vapor-triggered reversible mechanical response which could be applied as a smart actuator. Thus, this work develops a new method to synthesize CLgens using water, builds a clear structure-property relationship of CLgens, and provides a novel strategy to in situ construct functional H₂O-based polymeric films.

A starlike heterocyclic molecule containing an electron‐deficient nonaaza‐core structure and three peripheral isoquinolines locked by three tetracoordinate borons, namely isoquinoline‐nona‐starazine (QNSA), is synthesized by using readily available reactants through a rather straightforward approach. This new heteroatom‐rich QNSA possesses a quasi‐planar π‐backbone structure, and bears phenyl substituents on borons which protrude on both sides of the π‐backbones endowing it with good solubility in common organic solvents. Contrasting to its starphene analogue, QNSA shows intense fluorescence with a quantum yield (PLQY) of up to 62 % in dilute solution.

Coexistence of rotationally π–π stacked columns and discrete slip-stacked dimers of perylene bisimide (PBI) chromophores is revealed by single crystal X-ray diffraction in the lamellar crystal of a head-to-tail linked PBI dyad. The rotary π–π stacked columnar moieties show H-type spectral character with relatively higher excitation energy, while the discrete slip-stacked π–π dimers have J-type spectral behavior with lower excitation energy. The lamellar crystals show relatively low photoluminescence efficiency of 12% at room temperature, while this dramatically increases to ∼90% at low temperature (80 K). Both of the rotary and slip-stacked moieties are emissive, and the nonradiative energy transfer processes between them are suppressed at low temperature, ensuring the highly efficient excimer-like long-lived fluorescence.