Bismuth organic frameworks exhibiting enhanced phosphorescence

Bismuth-based organic frameworks (BiOFs) can display interesting phosphorescent properties, but the relationship between structure and optical activity remains underexplored. The structure-dependent phosphorescence properties in the BiOFs are investigated using different multidentate ligands. In-depth analysis of the luminescence properties confirms that the densely packed framework shows long-lasting phosphorescence at room temperature, owing to an efficient electron-hole separation. The combination of spectroscopic analysis and single-crystal structural analysis provides important insights into the emission control through BiOFs structural change, which can be a useful strategy for modulating the optical properties of various metal organic frameworks. Furthermore, taking the advantage of long-lasting phosphorescence, the potential usage as an eco-friendly photocatalyst is demonstrated.

Excited State Mechanisms in Crystalline Carbazole: The Role of Aggregation and Isomeric Defects

The molecule of Carbazole (Cz) is commonly used as a building block in organic materials for optoelectronic applications, acting as light-absorbing, electron donor and emitting moiety. Crystals from Cz and derivatives display ultralong phosphorescence at room temperature. However, different groups have reported inconsistent quantum efficiencies for the same compounds. In a recent experimental study by Liu et al. (<i>Nature Materials</i> <b>2021</b>, 20, 175-180), the ultralong phosphoresce properties of Cz have been associated with the presence of small fractions of isomeric impurities from commercially available Cz. In this paper, we use state-of-the-art computational approaches to investigate light-induced processes in crystalline and doped Cz. We revisit the role of aggregation and isomeric impurities on the excited state pathways and analyse the mechanisms for exciton, Dexter energy transfer and electron transport based on Marcus and Marcus-Levich-Jortner theories. Our excited state mechanisms provide a plausible interpretation for the experimental results and support the formation of charge-separated states at the defect/Cz molecular interface. These results contribute to a better understanding of the factors enhancing the excited state lifetimes in organic materials and the role of doping with organic molecules.

Excited State Mechanisms in Crystalline Carbazole: The Role of Aggregation and Isomeric Defects

The molecule of Carbazole (Cz) is commonly used as a building block in organic materials for optoelectronic applications, acting as light-absorbing, electron donor and emitting moiety. Crystals from Cz and derivatives display ultralong phosphorescence at room temperature. However, different groups have reported inconsistent quantum efficiencies for the same compounds. In a recent experimental study by Liu et al. (<i>Nature Materials</i> <b>2021</b>, 20, 175-180), the ultralong phosphoresce properties of Cz have been associated with the presence of small fractions of isomeric impurities from commercially available Cz. In this paper, we use state-of-the-art computational approaches to investigate light-induced processes in crystalline and doped Cz. We revisit the role of aggregation and isomeric impurities on the excited state pathways and analyse the mechanisms for exciton, Dexter energy transfer and electron transport based on Marcus and Marcus-Levich-Jortner theories. Our excited state mechanisms provide a plausible interpretation for the experimental results and support the formation of charge-separated states at the defect/Cz molecular interface. These results contribute to a better understanding of the factors enhancing the excited state lifetimes in organic materials and the role of doping with organic molecules.

Halogenation of a twisted non-polar π-system as a tool to modulate phosphorescence at room temperature

Halogenation of a twisted three-fold symmetric hydrocarbon with F, Cl or Br leads to strong modulation of triplet-triplet annihilation and dual phosphorescence, one thermally activated and the other very persistent...

A new silver cluster that emits bright-blue phosphorescence

A new stable hexanuclear silver(i) cluster features brightly blue phosphorescence at room temperature, which is integrated with yellow phosphors (YAG:Ce3+) to white-light-emission film and demonstrates interesting mechanoresponsive luminescence.

On the Nature of Luminescence Thermochromism of Multinuclear Copper(I) Benzoate Complexes in the Crystalline State

A model luminescent [(PhCO2)4Cu4] (Cu4) complex in the crystalline state was investigated via combined crystallographic and spectroscopic techniques contributed substantially by theoretical modelling. The complex appeared to exhibit luminescence thermochromism, i.e., red phosphorescence at room temperature which changes to green when lowering the temperature to 90 K. The low-energy emissive state was assigned as a cluster-centred triplet, 3CC. The emission from this state predicted in TDDFT (~635 nm) matches the experimental red band observed at 660–715 nm. In contrast, the nature of the high-energy “green” band was less straightforward. The next reached cluster-centred triplet excited state occurred to be energetically close to the experimental value of ~545 nm. The two excited states also exhibit significant metal-to-ligand and ligand-to-metal charge transfer characteristics, especially for solid-state distorted geometries. In both cases the cluster core was expected to become notably contracted when compared to the ground state. Time-resolved photocrystallographic results supported the computationally predicted core contraction upon excitation. Additionally, the differences between the spectroscopic behaviour of the related tetra- and hexanuclear copper(I) complexes, Cu4 and Cu6 (i.e., [(PhCO2)6Cu6]) in the crystalline state were discussed and examined. It appeared that crystal packing may constitute an important factor as far as the lack of luminescence thermochromism in the latter case is concerned. Synopsis: Structure–property relationships characterising a model luminescent [(PhCO2)4Cu4] (Cu4) complex in the crystalline state were investigated via combined crystallographic and spectroscopic techniques contributed by theoretical modelling, and compared with the properties of the related [(PhCO2)6Cu6] (Cu6) complex.

Use of silylmethoxy groups as inducers of efficient room temperature phosphorescence from precious-metal-free organic luminophores

Crystals of and PMMA films doped with 2,5-bis(silylmethoxy)-1,4-diaroylbenzenes exhibit efficient green phosphorescence at room temperature.