White-light emission from a single heavy atom-free molecule with room temperature phosphorescence, mechanochromism and thermochromism.

Two heavy atom-free luminophores (SHB2t and SDB2t) with simple molecular structures have been synthesized via Suzuki coupling reactions in which both display white-light emission with prompt fluorescence and room temperature phosphorescence (RTP) in the solid state. The impressive RTP of the luminophores is produced by a synergistic effect of the strong intermolecular hydrogen bonding in addition to the spin-orbit coupling of the sulfonyl oxygen atoms and the moderate singlet-triplet energy gaps (ΔEST). These factors facilitate the intersystem crossing (ISC) process to generate triplet excitons in which the molecular conformations become immobilized to effectively suppress radiationless decay. Under the stimuli of mechanical force and solvent vapor, the RTP of SHB2t and SDB2t can be simply turned off and on by breaking and reforming the robust hydrogen bonding, which leads to remarkable and reversible mechanochromism between white and deep-blue emission. Moreover, two different thermochromic processes have been observed for the pristine and ground samples of SDB2t, in which a tricolor switching system between white, deep-blue and blue emission has been successfully achieved through the sequential control of grinding, heating and fuming. From detailed studies we have determined that the mechanism for the thermochromism of SDB2t is correlated with the rearrangement of the white-light emitting molecules to a new packing mode without RTP emission.

Intermolecular Electronic Coupling of Organic Units for Efficient Persistent Room-Temperature Phosphorescence.

Although persistent room-temperature phosphorescence (RTP) emission has been observed for a few pure crystalline organic molecules, there is no consistent mechanism and no universal design strategy for organic persistent RTP (pRTP) materials. A new mechanism for pRTP is presented, based on combining the advantages of different excited-state configurations in coupled intermolecular units, which may be applicable to a wide range of organic molecules. By following this mechanism, we have developed a successful design strategy to obtain bright pRTP by utilizing a heavy halogen atom to further increase the intersystem crossing rate of the coupled units. RTP with a remarkably long lifetime of 0.28 s and a very high quantum efficiency of 5 % was thus obtained under ambient conditions. This strategy represents an important step in the understanding of organic pRTP emission.

Achieving very bright mechanoluminescence from purely organic luminophores with aggregation-induced emission by crystal design.

Although bright organic mechanoluminescence (ML) has been observed for a few luminophores with aggregation-induced emission (AIE), details of the positive effect of AIE on ML performance remain unclear and a feasible design principle for AIE-ML compounds has not yet been presented. Herein, an effective strategy for the molecular design of efficient AIE-ML materials is demonstrated, based on tetraphenylethene (TPE) building blocks with formyl substituents, which yield non-centrosymmetric crystal structures with prominent piezoelectric properties for molecular excitation combined with AIE features for intense emission. Following this approach, three AIE-active compounds have been developed and are found to show unique ML characteristics. Furthermore, the results of single crystal X-ray analysis and density functional theory (DFT) calculations suggest that the ML performance would probably be further enhanced by creating molecules with larger dipolar moments and enhanced AIE properties.

Achieving remarkable mechanochromism and white-light emission with thermally activated delayed fluorescence through the molecular heredity principle.

Achieving high contrast mechanochromism (Δλem,max > 100 nm) and white-light emission under mild conditions from a single compound with a simple structure is a great challenge. Herein, we report a novel dual-emissive compound, namely SCP, with an asymmetric molecular structure that fully inherits the photophysical properties of the parent molecules SC2 and SP2. SCP shows high contrast, linearly tunable mechanochromism and bright white-light emission arising from a combination of traditional fluorescence and thermally activated delayed fluorescence (TADF). The origin of the dual-emission for SCP was demonstrated based on the analysis of the white-emitting single crystals. In addition, a mechanism of luminochromism for SCP driven by the application of mechanical force is proposed. These observations present a rational design strategy for the development of high performance multi-functional materials for white-light emission.