Xiang Ma

Organic room‐temperature phosphorescence materials are valuable for information storage, encryption, and sensing. In most systems, heating accelerates non‐radiative decay, leading to monotonic weakening and loss of phosphorescence. High‐temperature tolerance, tunable color, and heating‐activated emission are seldom combined in one system. A triphenylamine derivative is doped into a calcium polyacrylate matrix to construct a material in which heating activates phosphorescence. The hydrated network shows no phosphorescence at room temperature. Heating induces a phase separation that initiates and intensifies the emission, which is opposite to typical thermal quenching. Continued heating removes water and locks the rigid microenvironment, yielding a phosphorescent xerogel. In this xerogel, emission is reversibly tuned from 505 nm to 450 nm, a visible afterglow persists to 473 K, and a lifetime of about 9 ms remains detectable at 573 K. Mechanistic studies attribute this behavior to multi‐force synergy within the matrix: hydrogen bonding provides baseline rigidity for triplet stabilization, Ca ²⁺ –COO ⁻ coordination imparts thermal stability and triggers phase separation, and the resulting phase‐separated domains form the confined microenvironment responsible for phosphorescence. These results demonstrate that thermally induced phase separation can build molecular rigidity on demand, so that heat acts as an activator rather than a quencher of phosphorescence.

Organic room‐temperature phosphorescence materials are valuable for information storage, encryption, and sensing. In most systems, heating accelerates non‐radiative decay, leading to monotonic weakening and loss of phosphorescence. High‐temperature tolerance, tunable color, and heating‐activated emission are seldom combined in one system. A triphenylamine derivative is doped into a calcium polyacrylate matrix to construct a material in which heating activates phosphorescence. The hydrated network shows no phosphorescence at room temperature. Heating induces a phase separation that initiates and intensifies the emission, which is opposite to typical thermal quenching. Continued heating removes water and locks the rigid microenvironment, yielding a phosphorescent xerogel. In this xerogel, emission is reversibly tuned from 505 nm to 450 nm, a visible afterglow persists to 473 K, and a lifetime of about 9 ms remains detectable at 573 K. Mechanistic studies attribute this behavior to multi‐force synergy within the matrix: hydrogen bonding provides baseline rigidity for triplet stabilization, Ca ²⁺ –COO ⁻ coordination imparts thermal stability and triggers phase separation, and the resulting phase‐separated domains form the confined microenvironment responsible for phosphorescence. These results demonstrate that thermally induced phase separation can build molecular rigidity on demand, so that heat acts as an activator rather than a quencher of phosphorescence.

Developing sustainable luminescent materials that integrate biodegradability, high optical transparency and long‐lived room‐temperature phosphorescence (RTP) remains an important challenge. Here we report a series of amino‐acid‐derived noncovalent biomolecular glasses (NBGs) as versatile hosts for organic luminophores. The dense noncovalent interaction network within the NBGs matrix confines the embedded luminophores and suppresses nonradiative relaxation, thereby enabling ultralong RTP. The resulting doped glasses exhibit color‐tunable afterglow from 430 to 610 nm, high transmittance of up to 93%, phosphorescence lifetimes of up to 4.11 s and photoluminescence quantum yields of up to 74.9%. The doped systems also display phosphor‐dependent photophysical behaviors, including excitation‐wavelength‐dependent emission. In addition, the pronounced viscosity changes during NBGs formation endow the materials with strong, substrate‐adaptive adhesion to diverse surfaces. Combining afterglow performance, optical transparency, reprocess ability, recyclability and biodegradability, these NBGs offer a sustainable supramolecular‐glass platform for multifunctional organic phosphorescent materials.

Developing sustainable luminescent materials that integrate biodegradability, high optical transparency and long‐lived room‐temperature phosphorescence (RTP) remains an important challenge. Here we report a series of amino‐acid‐derived noncovalent biomolecular glasses (NBGs) as versatile hosts for organic luminophores. The dense noncovalent interaction network within the NBGs matrix confines the embedded luminophores and suppresses nonradiative relaxation, thereby enabling ultralong RTP. The resulting doped glasses exhibit color‐tunable afterglow from 430 to 610 nm, high transmittance of up to 93%, phosphorescence lifetimes of up to 4.11 s and photoluminescence quantum yields of up to 74.9%. The doped systems also display phosphor‐dependent photophysical behaviors, including excitation‐wavelength‐dependent emission. In addition, the pronounced viscosity changes during NBGs formation endow the materials with strong, substrate‐adaptive adhesion to diverse surfaces. Combining afterglow performance, optical transparency, reprocess ability, recyclability and biodegradability, these NBGs offer a sustainable supramolecular‐glass platform for multifunctional organic phosphorescent materials.

Photoactivation‐enabled tunable room‐temperature phosphorescence (RTP) and thermally activated delayed fluorescence (TADF) are rarely realized in crystalline materials because of their rigid molecular packing. Existing crystalline photoactivated RTP systems generally require pretreatment and have not enabled RTP/TADF regulation. Here, we demonstrate for the first time that intrinsic photoactivated RTP can be achieved in a pretreatment‐free crystalline system, while the occurrence of TADF can be switched on or off through rational host‐guest engineering. Dinaphtho[2,1‐b:1′,2′‐d]furan (OA) exhibits intrinsic photoactivated RTP at 77 K, when incorporated into three crystalline hosts, forms a general crystalline photoactivated platform at room temperature. Experimental and calculational results indicate that energy level matching and exciton lifetime govern RTP/TADF modulation. Specifically, long‐lived excitons in host dibenzofuran (DBF) enable simultaneous RTP and TADF through host‐guest energy transfer, whereas methyl 4‐(methylamino)benzoate (MAB) and boric acid (BA) as hosts suppress TADF due to mismatched energy levels or rapid exciton quenching. Nevertheless, their RTP emission is facilitated by high crystallinity and rigid hydrogen‐bonding networks. Mechanistic analysis indicates that UV irradiation regulates excited‐state carrier concentration and transition probability, thereby enabling photoactivation. This work establishes a design strategy for crystalline photoactivated luminescent materials with potential applications for time‐dependent anti‐counterfeiting.

Elucidating supramolecular chiral evolution remains challenging, owing to weak chiroptical signals and poorly characterized conformationally diverse chiral dimers. Here, we adopt liquid crystal matrices to amplify chiroptical signals for real-time monitoring of monomer-to-aggregate chiral evolution. In this pyrene-based supramolecular system, π–π stacking and C–H···π interactions drive the formation of discrete dimers within nematic liquid crystals. The significantly amplified CPL signals with glum values up to 10–1 enable direct visualization of chiral transformation. Structural analyses verify that offset face-to-face dimers possess reversed handedness relative to monomers, thus inducing chiroptical inversion. TCNB allosteric encapsulation induces spatial rearrangement of BP dimers within liquid crystal and modulates their helicity-dependent chiroptical activity. A maximum glum value of 0.97 is achieved at the bandgap edge. Such structure reshaping confirms that assembly concentration regulation and molecular intervention enable precise engineering of chiral aggregates, offering fundamental insights into chiral evolution in supramolecular assembly systems.

Near-infrared room-temperature phosphorescence holds significant promise for applications in bioimaging, diagnosis, and treatment. However, their development is constrained by the energy gap law; especially, systems that combine structural simplicity with high efficiency remain extremely scarce. Herein, a “conformation matching” strategy based on aromatic thioketone units is proposed, enabling the rational construction of highly efficient host–guest near-infrared phosphorescent materials. This high efficiency is attributed to the conformation match between the guest and host, whereby the molecular stacking and conformation could be optimized to realize exciton localization. The longest emission peak of the obtained material is at 715 nm, and the maximum phosphorescence quantum yield is as high as 55.5%. Mechanistic studies further reveal that “conformation matching” can simultaneously regulate nonradiative decay, radiative transition rates, and triplet–triplet energy transfer processes, leading to a synergistic enhancement of performance. This work not only provides a new design strategy for highly efficient and compact near-infrared phosphorescent materials but also establishes conformation engineering as a crucial new dimension for tuning host–guest phosphorescence properties.

Host–guest doping has emerged as a powerful platform for constructing organic room‐temperature phosphorescence (RTP) materials, owing to its structural tunability and facile fabrication. However, molecular design has largely focused on guest molecules, while host screening lacks systematic theoretical guidance. Here, we propose a host dearomatization strategy that prolongs the afterglow of doped systems. By converting the benzene ring into a cyclohexane structure in the host, the RTP lifetimes of the doped systems are significantly prolonged, with the maximum enhancement reaching a 58.65‐fold increase. Mechanistic studies indicate that the extended lifetime arises from enhanced triplet‐triplet energy transfer and electronic coupling, enabled by the reduced intermolecular distance upon dearomatization. This strategy exhibits universality across diverse host and guest systems. These doped systems are further applied in time‐resolved information encryption systems and switchable adhesive materials. Starting from the host molecular framework, this study provides a universal and efficient strategy for the rational design of organic RTP materials.

Host–guest doping has emerged as a powerful platform for constructing organic room‐temperature phosphorescence (RTP) materials, owing to its structural tunability and facile fabrication. However, molecular design has largely focused on guest molecules, while host screening lacks systematic theoretical guidance. Here, we propose a host dearomatization strategy that prolongs the afterglow of doped systems. By converting the benzene ring into a cyclohexane structure in the host, the RTP lifetimes of the doped systems are significantly prolonged, with the maximum enhancement reaching a 58.65‐fold increase. Mechanistic studies indicate that the extended lifetime arises from enhanced triplet‐triplet energy transfer and electronic coupling, enabled by the reduced intermolecular distance upon dearomatization. This strategy exhibits universality across diverse host and guest systems. These doped systems are further applied in time‐resolved information encryption systems and switchable adhesive materials. Starting from the host molecular framework, this study provides a universal and efficient strategy for the rational design of organic RTP materials.

Phosphorescence, stemming from triplet excitons, is highly susceptible to thermal quenching as elevated temperatures trigger nonradiative transitions. Achieving efficient and persistent organic phosphorescence under extreme heat remains a formidable challenge. We introduce a dehydration-shrinkage strategy to obtain doped organic phosphorescence systems with extreme-temperature tolerance, which achieves gradual anchoring of the phosphors within the ionic network of hydrated sodium borate. These doped systems exhibit efficient phosphorescence spanning 400 to 680 nm at room temperature and 573 K, achieving a phosphorescence quantum yield of 81.2% and a lifetime of 1.64 s at room temperature. Remarkably, the doped systems can remain operational for at least 6 months at 573 K. Mechanistic studies reveal that temperature-induced water departure triggers network shrinkage, which rigidifies the local environment and suppresses triplet exciton deactivation, thereby stabilizing the phosphorescence. This strategy opens a perspective for constructing high-temperature phosphorescent materials, safety indicators, and information security devices.