Facile,Quick, and Gram‐Scale Synthesis of Ultralong‐Lifetime Room‐Temperature‐Phosphorescent Carbon Dots by Microwave Irradiation

Long‐lifetime room‐temperature phosphorescence (RTP) materials are important for many applications, but they are highly challenging materials owing to the spin‐forbidden nature of triplet exciton transitions. Herein, a facile, quick and gram‐scale method for the preparation of ultralong RTP (URTP) carbon dots (CDs) was developed via microwave‐assisted heating of ethanolamine and phosphoric acid aqueous solution. The CDs exhibit the longest RTP lifetime, 1.46 s (more than 10 s to naked eye) for CDs‐based materials to date. The doping of N and P elements is critical for the URTP which is considered to be favored by a n→π* transition facilitating intersystem crossing (ISC) for effectively populating triplet excitons. In addition, possibilities of formation of hydrogen bonds in the interior of the CDs may also play a significant role in producing RTP. Potential applications of the URTP CDs in the fields of anti‐counterfeiting and information protection are proposed and demonstrated.     

A Universal Strategy for Activating the Multicolor Room‐Temperature Afterglow of Carbon Dots in a Boric Acid Matrix

Carbon dots (CDs) have attracted attention in metal‐free afterglow materials, but most CDs were heteroatom‐containing and the afterglow emissions are still limited to the short‐wavelength region. A universal approach to activate the room‐temperature phosphorescence (RTP) of both heteroatom‐free and heteroatom‐containing CDs was developed by one‐step heat treatment of CDs and boric acid (BA). The introduction of an electron‐withdrawing boron atom in composites can greatly reduce the energy gap between the singlet and triplet state; the formed glassy state can effectively protect the excited triplet states of CDs from nonradiative deactivation. A universal host for embedding CDs to achieve long‐lifetime and multi‐color (blue, green, green‐yellow and orange) RTP via a low cost, quick and facile process was developed. Based on their distinctive RTP performances, the applications of these CD‐based RTP materials in information encryption and decryption are also proposed and demonstrated.     

Carbon Dots with Dual‐Emissive,Robust, and Aggregation‐Induced Room‐Temperature Phosphorescence Characteristics

Carbon dots (CDs) with dual‐emissive, robust, and aggregation‐induced RTP characteristics are reported for the first time. The TA‐CDs are prepared via hydrothermal treatment of trimellitic acid and exhibit unique white prompt and yellow RTP emissions in solid state under UV excitation (365 nm) on and off, respectively. The yellow RTP emission of TA‐CDs powder should be resulted from the formation of a new excited triplet state due to their aggregation, and the white prompt emission is due to their blue fluorescence and yellow RTP dual‐emissive nature. The RTP emission of TA‐CDs powder was highly stable under grinding, which is very rare amongst traditional pure organic RTP materials. To employ the unique characteristics of TA‐CDs, advanced anti‐counterfeiting and information encryption methodologies (water‐stimuli‐response producing RTP) were preliminarily investigated.     

Stimuli‐Responsive Circularly Polarized Organic Ultralong Room Temperature Phosphorescence

Purely organic materials showing room temperature phosphorescence (RTP) and ultralong RTP (OURTP) have recently attracted much attention. However, it is challenging to integrate circularly polarized luminescence (CPL) into RTP/OURTP. Here, we show a strategy to realize CPL‐active OURTP (CP‐OURTP) by binding an achiral phosphor group directly to the chiral center of an ester chain. Engineering of this flexible chiral chain enables efficient chirality transfer to carbazole aggregates, resulting in strong CP‐OURTP with a lifetime of over 0.6 s and dissymmetry factor of 2.3×10^?3 after the conformation regulation upon photo‐activation. The realized CP‐OURTP is thus stable at room temperature but can be deactivated quickly at 50 °C to CP‐RTP with high CPL stability during the photo‐activation/thermal‐deactivation cycles. Based on this extraordinary photo/thermal‐responsive and highly reversible CP‐OURTP/RTP, a CPL‐featured lifetime‐encrypted combinational logic device has been successfully established.     

Carbon Dots in a Matrix: Energy‐Transfer‐Enhanced Room‐Temperature Red Phosphorescence

High‐efficiency red room‐temperature phosphorescence (RTP) emissions have been achieved by embedding carbon dots (CDs) in crystalline Mn‐containing open‐framework matrices. The rationale of this strategy relies on two factors: 1) the carbon source, which affects the triplet energy levels of the resulting CDs and thus the spectral overlap and 2) the coordination geometry of the Mn atoms in the crystalline frameworks, which determines the crystal‐field splitting and thus the emission spectra. Embedding the carbon dots into a matrix with 6‐coordinate Mn centers resulted in a strong red RTP with a phosphorescence efficiency of up to 9.6 %, which is higher than that of most reported red RTP materials. The composite material has an ultrahigh optical stability in the presence of strong oxidants, various organic solvents, and strong ultraviolet radiation. A green‐yellow RTP composite was also prepared by using a matrix with 4‐coordinate Mn centers and different carbon precursors.     

Molecular Engineering for Metal‐Free Amorphous Materials with Room‐Temperature Phosphorescence

Materials displaying room‐temperature phosphorescence (RTP) have been attracting wide attention in recent years due to their distinctive characteristics including long emissive lifetime and large Stokes shift, and their various applications. Most synthesized RTP materials are metal complexes that display enhanced intersystem crossing and crystallization is a common way to restrict nonradiative transition. Amorphous metal‐free RTP materials, which do not rely on expensive and toxic metals and can be prepared in a straightforward fashion, have become an important branch of the field. This Minireview summarizes recent progress in amorphous RTP materials according to the approaches used to immobilize phosphors: host–guest interactions, molecule doping, copolymers, and small‐molecule self‐assembly. Some existing challenges and insightful perspectives are given at the end of the Minireview, which should benefit the future design and development of amorphous metal‐free RTP materials.     

Induction of Strong Long‐Lived Room‐Temperature Phosphorescence of N‐Phenyl‐2‐naphthylamine Molecules by Confinement in a Crystalline Dibromobiphenyl Matrix

The design and preparation of metal‐free organic materials that exhibit room‐temperature phosphorescence (RTP) is a very attractive topic owing to potential applications in organic optoelectronic devices. Herein, we present a facile approach to efficient and long‐lived organic RTP involving the doping of N‐phenylnaphthalen‐2‐amine (PNA) or its derivatives into a crystalline 4,4′‐dibromobiphenyl (DBBP) matrix. The resulting materials showed strong and persistent RTP emission with a quantum efficiency of approximately 20 % and a lifetime of a few to more than 100 milliseconds. Bright white dual emission containing blue fluorescence and yellowish‐green RTP from the PNA‐doped DBBP crystals was also confirmed by Commission Internationale de l'Eclairage (CIE) coordinates of (x=0.29–0.31, y=0.38–0.41).     

New Wine in Old Bottles: Prolonging Room‐Temperature Phosphorescence of Crown Ethers by Supramolecular Interactions

Supramolecular macrocyclic hosts have long been used in smart materials. However, their triplet emission and regulation at crystal level is rarely studied. Herein, ultralong and universal room‐temperature phosphorescence (RTP) is reported for traditional crown ethers. A supramolecular strategy involving chain length adjustment and morphological locking through complexation with K⁺ was explored as a general method to tune the phosphorescence lifetime in the solid state. A maximum 10‐fold increase of lifetime after complex formation accompanied with by invisible to visible phosphorescence was achieved. A deep encryption based on this activated RTP strategy was also facilely fabricated. This work thus opens a new world for supramolecular macrocycles and their intrinsic guest responsiveness offers a new avenue for versatile smart luminescent materials.     

Designing Efficient and Ultralong Pure Organic Room‐Temperature Phosphorescent Materials by Structural Isomerism

Pure organic materials with ultralong room‐temperature phosphorescence (RTP) are attractive alternatives to inorganic phosphors. However, they generally show inefficient intersystem crossing (ISC) owing to weak spin–orbit coupling (SOC). A design principle based on the realization of small energy gap between the lowest singlet and triplet states (ΔE_ST) and pure ππ* configuration of the lowest triplet state (T₁) via structural isomerism was used to obtain efficient and ultralong RTP materials. The meta isomer of carbazole‐substituted methyl benzoate exhibits an ultralong lifetime of 795.0 ms with a quantum yield of 2.1 %. Study of the structure–property relationship shows that the varied steric and conjugation effects imposed by ester substituent at different positions are responsible for the small ΔE_ST and pure ππ* configuration of T₁.     

Matrix‐Free and Highly Efficient Room‐Temperature Phosphorescence Carbon Dots towards Information Encryption and Decryption

Designing efficient room‐temperature phosphorescence (RTP) carbon dots (C‐dots) without the need of an additional matrix is important for various applications. Herein, matrix‐free and highly efficient C‐dots with yellow‐green RTP emission have been successfully synthesized towards information encryption and decryption. Phytic acid (PA) and triethylenetetramine are used as molecular precursors, and a facile microwave‐assisted heating method is selected as synthesis method. The obtained C‐dots exhibit a maximum phosphorescence emission at around 535 nm under an excitation wavelength of 365 nm and a long average lifetime up to 750 ms (more than 9 s to the naked eye). PA containing six phosphate groups and serving as P source plays a significant role in producing the RTP C‐dots. Furthermore, potential applications of the RTP C‐dots in the field of information encryption and decryption are successfully demonstrated.     

Amorphous Pure Organic Polymers for Heavy‐Atom‐Free Efficient Room‐Temperature Phosphorescence Emission

Pure organic, heavy‐atom‐free room‐temperature phosphorescence (RTP) materials have attracted much attention and have potential applications in photoelectric and biochemical material fields owing to their rich excited state properties. They offer long luminescent lifetime, diversified design, and facile preparation. However, recent achievements of efficient phosphorescence under ambient conditions mainly focus on ordered crystal lattices or embedding into rigid matrices, which require strict growth conditions and have poor reproducibility. Herein, we developed a concise approach to give RTP with a decent quantum yield and ultralong phosphorescence lifetime in the amorphous state by radical binary copolymerization of acrylamide and different phosphors with oxygen‐containing functional groups. The cross‐linked hydrogen‐bonding networks between the polymeric chains immobilize phosphors to suppress non‐radiative transitions and provide a microenvironment to shield quenchers.     

Organic Nanocrystals with Bright Red Persistent Room‐Temperature Phosphorescence for Biological Applications

Persistent room‐temperature phosphorescence (RTP) in pure organic materials has attracted great attention because of their unique optical properties. The design of organic materials with bright red persistent RTP remains challenging. Herein, we report a new design strategy for realizing high brightness and long lifetime of red‐emissive RTP molecules, which is based on introducing an alkoxy spacer between the hybrid units in the molecule. The spacer offers easy Br−H bond formation during crystallization, which also facilitates intermolecular electron coupling to favor persistent RTP. As the majority of RTP compounds have to be confined in a rigid environment to quench nonradiative relaxation pathways for bright phosphorescence emission, nanocrystallization is used to not only rigidify the molecules but also offer the desirable size and water‐dispersity for biomedical applications.     

An Unexpected Chromophore–Solvent Reaction Leads to Bicomponent Aggregation‐Induced Phosphorescence

Organic luminogens with persistent room‐temperature phosphorescence (RTP) have found a wide range of applications. However, many RTP luminogens are prone to severe quenching in the crystalline state. Herein, we report a strategy to construct a donor‐sp³‐acceptor type luminogen that exhibits aggregation‐induced emission (AIE) while the donor‐sp²‐acceptor counterpart structure exhibits a non‐emissive solid state. Unexpectedly, it was discovered that a trace amount (0.01 %) of the structurally similar derivative, produced by a side reaction with the DMF solvent, could induce strong RTP with an absolute RTP yield up to 25.4 % and a lifetime of 48 ms, although the substance does not show RTP by itself. Single‐crystal XRD‐based calculations suggest that n–σ* orbital interactions as a result of structural similarity may be responsible for the strong RTP in the bicomponent system. This study provides a new insight into the design of multi‐component, solid‐state RTP materials from organic molecular systems.     

Carbon Dots with Dual-Emissive,Robust, and Aggregation-Induced Room-Temperature Phosphorescence Characteristics

Carbon dots (CDs) with dual-emissive, robust, and aggregation-induced RTP characteristics are reported for the first time. The TA-CDs are prepared via hydrothermal treatment of trimellitic acid and exhibit unique white prompt and yellow RTP emissions in solid state under UV excitation (365 nm) on and off, respectively. The yellow RTP emission of TA-CDs powder should be resulted from the formation of a new excited triplet state due to their aggregation, and the white prompt emission is due to their blue fluorescence and yellow RTP dual-emissive nature. The RTP emission of TA-CDs powder was highly stable under grinding, which is very rare amongst traditional pure organic RTP materials. To employ the unique characteristics of TA-CDs, advanced anti-counterfeiting and information encryption methodologies (water-stimuli-response producing RTP) were preliminarily investigated.     

Triple‐Mode Emission of Carbon Dots: Applications for Advanced Anti‐Counterfeiting

Photoluminescence (PL), up‐conversion PL (UCPL), and phosphorescence are three kinds of phenomena common to light‐emitting materials, but it is very difficult to observe all of them simultaneously when they are derived from a single material at room temperature. For the first time, triple‐mode emission (that is, PL, UCPL, and room temperature phosphorescence (RTP)) is reported, which relies on a composite of the luminescent carbon dots (CDs) prepared from m‐phenylenediamine and poly(vinyl alcohol) (PVA). Moreover, the CDs‐PVA aqueous dispersion is nearly colorless and demonstrates promise as a triple‐mode emission ink in the field of advanced anti‐counterfeiting.     

Crystal‐State Photochromism and Dual‐Mode Mechanochromism of an Organic Molecule with Fluorescence,Room‐Temperature Phosphorescence,and Delayed Fluorescence

A D‐A‐D′ type pure organic molecule, named ODFRCZ, has unique triple‐emission character covering fluorescence, phosphorescence, and delayed fluorescence (DF). The phosphorescence of ODFRCZ has a rather long lifetime of about 350 ms at room temperature. One dimer of ODFRCZ with enhanced parallel molecular packing acts more effectively to prompt ISC processes, which further generates room‐temperature phosphorescence (RTP), owing to the larger transition dipole moment and closer energy level between S₁ and T_n. ODFRCZ is a rare example of an organic RTP molecule that shows dual‐stimuli responsiveness of dual‐mode mechanochromism (fluorescence red‐shift and RTP/DF on‐off switch) and reversible crystal‐state photochromism. This work may broaden the knowledge for stimuli‐responsive RTP organic molecules and lay the foundation for their wide‐scale applications.     

Visible‐Light‐Excited Room‐Temperature Phosphorescence in Water by Cucurbit[8]uril‐Mediated Supramolecular Assembly

Solid‐state materials with efficient room‐temperature phosphorescence (RTP) emissions have found widespread applications in materials science, while liquid or solution‐phase pure organic RTP emission systems has been rarely reported, because of the nonradiative decay and quenchers from the liquid medium. Reported here is the first example of visible‐light‐excited pure organic RTP in aqueous solution by using a supramolecular host‐guest assembly strategy. The unique cucurbit[8]uril‐mediated quaternary stacking structure allows tunable photoluminescence and visible‐light excitation, enabling the fabrication of multicolor hydrogels and cell imaging. The present assembly‐induced emission approach, as a proof of concept, contributes to the construction of novel metal‐free RTP systems with tunable photoluminescence in aqueous solution, providing broad opportunities for further applications in biological imaging, detection, optical sensors, and so forth.     

Crystal‐State Photochromism and Dual‐Mode Mechanochromism of an Organic Molecule with Fluorescence,Room‐Temperature Phosphorescence,and Delayed Fluorescence

A D‐A‐D′ type pure organic molecule, named ODFRCZ, has unique triple‐emission character covering fluorescence, phosphorescence, and delayed fluorescence (DF). The phosphorescence of ODFRCZ has a rather long lifetime of about 350 ms at room temperature. One dimer of ODFRCZ with enhanced parallel molecular packing acts more effectively to prompt ISC processes, which further generates room‐temperature phosphorescence (RTP), owing to the larger transition dipole moment and closer energy level between S₁ and T_n. ODFRCZ is a rare example of an organic RTP molecule that shows dual‐stimuli responsiveness of dual‐mode mechanochromism (fluorescence red‐shift and RTP/DF on‐off switch) and reversible crystal‐state photochromism. This work may broaden the knowledge for stimuli‐responsive RTP organic molecules and lay the foundation for their wide‐scale applications.     

Carbon Dots: Bottom‐Up Syntheses,Properties, and Light‐Harvesting Applications

The development of cost‐effective and environmentally friendly photocatalysts and photosensitizers has received tremendous attention because of their potential utilization in solar‐light‐harvesting applications. In this respect, carbon dots (CDs) prepared by bottom‐up methods have been considered to be promising light‐harvesting materials. Through their preparation from various molecular precursors and synthetic methods, CDs exhibit excellent optical and charge‐transfer properties. Furthermore, their photophysical properties can be readily optimized and enhanced by means of doping, functionalization, and post‐synthetic treatment. In this review, we summarize the recent progress in CDs synthesized using bottom‐up approaches. These CDs exhibit strong light absorption and unique electron donor/acceptor capabilities for light‐harvesting applications. We anticipate that this review will provide new insights into novel types of photosensitizers and photocatalysts for a wide range of applications.     

Photo-induced ultralong phosphorescence of carbon dots for thermally sensitive dynamic patterning

Stimuli-responsive films with a dynamic long afterglow feature have received considerable attention in the field of optical materials. Herein, we report the unique dynamic ultralong room temperature phosphorescence (URTP) in flexible solid films made of luminescent carbon dots (CDs) and polyvinylpyrrolidone (PVP). Impressively, fully reversible photo-activation and thermal deactivation of the dynamic long afterglow was achieved in this material, with a lifetime on–off ratio exceeding 3900. Subsequently, ultra-fine URTP patterns (resolution > 1280 dpi) with thermally sensitive retention time were readily photo-printed onto the films and utilized as time–temperature indicating logistics labels with multi-editing capacity. These findings not only enrich the library of dynamic URTP materials, but also extend the scope of the potential applications of luminescent CDs.

A flexible CD–polymer composite with a reversibly editable photo-induced URTP long afterglow was rationally designed and successfully applied in dynamic optical patterning with built-in time–temperature indicating functionality.