Hydrogen‐Bonded Organic Aromatic Frameworks for Ultralong Phosphorescence by Intralayer π–π Interactions

Ultralong organic phosphorescence (UOP) based on metal‐free porous materials is rarely reported owing to rapid nonradiative transition under ambient conditions. In this study, hydrogen‐bonded organic aromatic frameworks (HOAFs) with different pore sizes were constructed through strong intralayer π–π interactions to enable ultralong phosphorescence in metal‐free porous materials under ambient conditions for the first time. Impressively, yellow UOP with a lifetime of 79.8 ms observed for PhTCz‐1 lasted for several seconds upon ceasing the excitation. For PhTCz‐2 and PhTCz‐3, on account of oxygen‐dependent phosphorescence quenching, UOP could only be visualized in N₂, thus demonstrating the potential of phosphorescent porous materials for oxygen sensing. This result not only outlines a principle for the design of new HOFs with high thermal stability, but also expands the scope of metal‐free luminescent materials with the property of UOP.     

Subtle structure tailoring of metal-free triazine luminogens for highly efficient ultralong organic phosphorescence

Ultralong organic phosphorescent materials have invoked considerable attention for their great potential in sensing, data encryption, information anti-counterfeiting and so forth. However, effective ways to achieve highly efficient ultralong organic phosphorescence (UOP) in metal-free organic materials remain a great challenge. Herein, we designed three isomers based on asymmetric triazines with various bromine substituted positions. Impressively, phosphorescence efficiency of p-BrAT in solid state can reach up to 9.7% with a long lifetime of 386 ms, which was one of the highest efficient UOP materials reported so far. Theoretical calculations further demonstrated that para-substitution exhibited the most effective radiative transition for triplet excitons. These results will provide an effective approach to achieving highly efficient UOP materials.     

Regioisomerism effect (RIE) on optimizing ultralong organic phosphorescence lifetimes

Organic phosphorescence materials demonstrate potential optoelectronic applications due to their remarkably ultralong organic phosphorescence (UOP) lifetime and abundant optical characteristics prior to the fluorescence materials. For a better insight into the intrinsic relationship among regioisomeric molecules, crystalline interactions, and phosphorescence properties, three crystalline dicarbazol-9-yl pyrazine-based regioisomers with para-, meta-, and ortho-convergent substitutions (p-DCzP, m-DCzP, and o-DCzP) were designed and presented gradually increased UOP lifetimes prolonging from 63.14, 127.93 to 350.46 ms, respectively, due to the regioisomerism effect (RIE) which would be an effective strategy for better understanding of structure-property of UOP materials.     

Subtle structure tailoring of metal-free triazine luminogens for highly efficient ultralong organic phosphorescence

Highly efficient ultralong organic phosphorescence (UOP) based on a series of metal-free triazine luminogens was achieved via subtly structural tailoring of bromine substituted positions.Impressively,p-BrAT in solid state displayed high phosphorescence efficiency up to 9.7% with a long lifetime of 386 ms,which was one of the highest efficient UOP materials reported so far in metal-free compounds.     

Dynamic Ultralong Organic Phosphorescence by Photoactivation

Smart materials with ultralong phosphorescence are rarely investigated and reported. Herein we report on a series of molecules with unique dynamic ultralong organic phosphorescence (UOP) features, enabled by manipulating intermolecular interactions through UV light irradiation. Our experimental data reveal that prolonged irradiation of single‐component organic phosphors of PCzT, BCzT, and FCzT under ambient conditions can activate UOP with emission lifetimes spanning from 1.8 to 1330 ms. These phosphors can also be deactivated back to their original states with short‐lived phosphorescence by UV irradiation for 3 h at room temperature or through thermal treatment. Additionally, the dynamic UOP was applied successfully for a visual anti‐counterfeiting application. These findings may provide unique insight into dynamic molecular motion for optical processing and expand the scope of smart‐response materials for broader applications.     

Manipulating the Stacking of Triplet Chromophores in the Crystal Form for Ultralong Organic Phosphorescence

Provided here is evidence showing that the stacking between triplet chromophores plays a critical role in ultralong organic phosphorescence (UOP) generation within a crystal. By varying the structure of a functional unit, and different on‐off UOP behavior was observed for each structure. Remarkably, 24CPhCz, having the strongest intermolecular interaction between carbazole units exhibited the most impressive UOP with a long lifetime of 1.06 s and a phosphorescence quantum yield of 2.5 %. 34CPhCz showed dual‐emission UOP and thermally activated delayed fluorescence (TADF) with a moderately decreased phosphorescence lifetime of 770 ms, while 35CPhCz only displayed TADF owing to the absence of strong electronic coupling between triplet chromophores. This study provides an explanation for UOP generation in crystal and new guidelines for obtaining UOP materials.     

Regioisomerism effect (RIE) on optimizing ultralong organic phosphorescence lifetimes

Regioisomerism effect was disclosed on optimizing ultralongorganic phosphorescence life times of three crystalline dicarbazol-9-yl pyrazine-based regioisomers (p-DCzP,m-DCzP,and o-DCzP) with para-,meta-, and ortho-convergent substitutions.It is revealed that regioisomerism effect could be an effective strategy for the deep understanding of UOP materials.     

Amorphous Ionic Polymers with Color‐Tunable Ultralong Organic Phosphorescence

Amorphous purely organic phosphorescence materials with long‐lived and color‐tunable emission are rare. Herein, we report a concise chemical ionization strategy to endow conventional poly(4‐vinylpyridine) (PVP) derivatives with ultralong organic phosphorescence (UOP) under ambient conditions. After the ionization of 1,4‐butanesultone, the resulting PVP‐S phosphor showed a UOP lifetime of 578.36 ms, which is 525 times longer than that of PVP polymer itself. Remarkably, multicolor UOP emission ranging from blue to red was observed with variation of the excitation wavelength, which has rarely been reported for organic luminescent materials. This finding not only provides a guideline for developing amorphous polymers with UOP properties, but also extends the scope of room‐temperature phosphorescence (RTP) materials for practical applications in photoelectric fields.     

Switchable and Highly Robust Ultralong Room-Temperature Phosphorescence from Polymer-Based Transparent Films with Three-Dimensional Covalent Networks for Erasable Light Printing

In this work, an efficient polymer-based organic afterglow system, which shows reversible photochromism, switchable ultralong organic phosphorescence (UOP), and prominent water and chemical resistance simultaneously, has been developed for the first time. By doping phenoxazine (PXZ) and 10-ethyl-10H-phenoxazine (PXZEt) into epoxy polymers, the resulting PXZ@EP-0.25 % and PXZEt@EP-0.25 % films show unique photoactivated UOP properties, with phosphorescence quantum yields and lifetimes up to 10.8 % and 845 ms, respectively. It is found that the steady-state luminescence and UOP of PXZ@EP-0.25 % are switchable by light irradiation and thermal annealing. Moreover, the doped films can still produce conspicuous UOP after soaking in water, strong acid and base, and organic solvents for more than two weeks, exhibiting outstanding water and chemical resistance. Inspired by these exciting results, the PXZ@EP-0.25 % has been successfully exploited as an erasable transparent film for light printing.     

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.     

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.     

New fluorous ponytailed 4‐[(2,2,2‐trifluoroethoxy)methyl]pyridinium halide salts

It is possible that fluorous compounds could be utilized as directing forces in crystal engineering for applications in materials chemistry or catalysis. Although numerous fluorous compounds have been used for various applications, their structures in the solid state remains a lively matter for debate. The reaction of 4‐[(2,2,2‐trifluoroethoxy)methyl]pyridine with HX (X = I or Cl) yielded new fluorous ponytailed pyridinium halide salts, namely 4‐[(2,2,2‐trifluoroethoxy)methyl]pyridinium iodide, C₈H₉F₃NO⁺·I⁻, (1), and 4‐[(2,2,2‐trifluoroethoxy)methyl]pyridinium chloride, C₈H₉F₃NO⁺·Cl⁻, (2), which were characterized by IR spectroscopy, multinuclei (¹H, ¹³C and ¹⁹F) NMR spectroscopy and single‐crystal X‐ray diffraction. Structure analysis showed that there are two types of hydrogen bonds, namely N—H…X and C—H…X. The iodide anion in salt (1) is hydrogen bonded to three 4‐[(2,2,2‐trifluoroethoxy)methyl]pyridinium cations in the crystal packing, while the chloride ion in salt (2) is involved in six hydrogen bonds to five 4‐[(2,2,2‐trifluoroethoxy)methyl]pyridinium cations, which is attributed to the smaller size and reduced polarizability of the chloride ion compared to the iodide ion. In the IR spectra, the pyridinium N—H stretching band for salt (1) exhibited a blue shift compared with that of salt (2).     

Utilizing d–pπ Bonds for Ultralong Organic Phosphorescence

Developing pure organic materials with ultralong lifetimes is attractive but challenging. Here we report a concise chemical approach to regulate the electronic configuration for phosphorescence enhancement. After the introduction of d–pπ bonds into a phenothiazine model system, a phosphorescence lifetime enhancement of up to 19 times was observed for DOPPMO, compared to the reference PPMO. A record phosphorescence lifetime of up to 876 ms was obtained in phosphorescent phenothiazine. Theoretical calculations and single‐crystal analysis reveal that the d–pπ bond not only reduces the (n, π*) proportion of the T₁ state, but also endows the rigid molecular environment with multiple intermolecular interactions, thus enabling long‐lived phosphorescence. This finding makes a valuable contribution to the prolongation of phosphorescence lifetimes and the extension of the scope of phosphorescent materials.     

Salts of maleic and fumaric acids with oxine: the role of isomeric acids in hydrogen‐bonding patterns

Both maleic and fumaric acid readily form adducts or complexes with other organic molecules. The 1:1 adduct formed by quinolin‐8‐ol (oxine) with maleic and fumaric acid are salts, namely 8‐hydroxyquinolinium hydrogen maleate, C₉H₈NO⁺·C₄H₃O₄⁻, (I), and 8‐hydroxyquinolinium hydrogen fumarate, C₉H₈NO⁺·C₄H₃O₄⁻, (II). The cations and anions of both salts are linked by ionic N⁺—H...O⁻ hydrogen bonds. The maleate salt crystallizes in the space group P2₁2₁2₁, while the fumarate salt crystallizes in P. The maleic and fumaric acids in their complex forms exist as semimaleate and semifumarate ions (mono‐ionized state), respectively. Classical N—H...O and O—H...O hydrogen bonds, together with short C—H...O contacts, generate an extensive hydrogen‐bonding network. The crystal structures of the maleate and fumarate salts of oxine have been elucidated to study the importance of noncovalent interactions in the aggregation and interaction patterns of biological molecules. The structures of the salts of the Z and E isomers of butenedioic acid (maleic and fumaric acid, respectively) with quinolin‐8‐ol are compared.     

Intrinsic persistent room temperature phosphorescence derived from 1H-benzo[f]indole itself as a guest

The influence of 1H-benzo[f]indole (Bd) and its derivatives on room temperature phosphorescence (RTP) has raised great concern since they were found to significantly affect RTP of the extensively studied carbazole (Cz) derivatives. However, the role of Bd itself existing in Cz-based or other doping systems was still unclear. In order to clarify its intrinsic phosphorescent property, Bd was introduced as a guest into different organic matrixes including substituted Cz derivatives and polymers. The phosphorescence located in 560–620 nm was confirmed to be derived from Bd itself, which can be detected whatever Bd was doped in the crystal or amorphous state of Cz derivatives. The suitable energy gap between Cz derivatives and Bd is the key to achieve ultralong RTP of Bd. Additionally, when doped in polymers with plenty of hydrogen bonds, RTP of Bd with lifetime over 280 ms was easily obtained. Among them, Bd@PHEMA (poly(hydroxyethyl methacrylate) exhibited superior phosphorescence, with yellow afterglow lasting for over 2.5 s. Therefore, this work demonstrated that a new organic RTP phosphor, Bd, is discovered, and ultralong RTP of Bd can be achieved not only doped in Cz derivatives but also in polymers as the hosts.     

New 1:1 and 2:1 salts in the `dl‐norvaline–maleic acid' system as an example of assembling various crystal structures from similar supramolecular building blocks

Molecular salts and cocrystals of amino acids have potential applications as molecular materials with nonlinear optical, ferroelectric, piezoelectric, and other various target physical properties. The wide choice of amino acids and coformers makes it possible to design various crystal structures. The amino acid–maleic acid system provides a perfect example of a rich variety of crystal structures with different stoichiometries, symmetries and packing motifs built from the molecular building blocks, which are either exactly the same, or differ merely by protonation or as optical isomers. The present paper reports the crystal structures of two new salts of the dl ‐norvaline–maleic acid system with 1:1 and 2:1 stoichiometries, namely dl ‐norvalinium hydrogen maleate, C₅H₁₂NO₂⁺·C₄H₃O₄⁻, (I), and dl ‐norvalinium hydrogen maleate–dl ‐norvaline, C₅H₁₂NO₂⁺·C₄H₃O₄⁻·C₅H₁₁NO₂, (II). These are the first examples of molecular salts of dl ‐norvaline with an organic anion. The crystal structure of (I) has the same C ₂²(12) structure‐forming motif which is common for hydrogen maleates of amino acids. The structure of (II) has dimeric cations. Of special interest is that the single crystals of (I) which are originally formed on crystallization from aqueous solution transform into single crystals of (II) if stored in the mother liquor for several hours.     

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.     

Two-Coordinate Copper(I)/NHC Complexes: Dual Emission Properties and Ultralong Room-Temperature Phosphorescence

As a kind of photoluminescent material, Cu^I complexes have many advantages such as adjustable emission, variable structures, and low cost, attracting attention in many fields. In this work, two novel two-coordinate Cu^I-N-heterocyclic carbene complexes were synthesized, and they exhibit unique dual emission properties, fluorescence and phosphorescence. The crystal structure, packing mode, and photophysical properties under different conditions were systematically studied, proving the emissive mechanism to be the locally excited state of the carbazole group. Based on this mechanism, ultralong room-temperature phosphorescence (RTP) with a lifetime of 140 ms is achieved by selective deuteration of the carbazole group. These results deepen the understanding of the luminescence mechanism and design strategy for two-coordinate Cu^I complexes, and prove their potential in applications as ultralong RTP materials.     

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.     

Metal Halide Regulated Photophysical Tuning of Zero-Dimensional Organic Metal Halide Hybrids: From Efficient Phosphorescence to Ultralong Afterglow

The photophysical tuning is reported for a series of tetraphenylphosphonium (TPP) metal halide hybrids containing distinct metal halides, TPP₂MX_n (MX_n=SbCl₅, MnCl₄, ZnCl₄, ZnCl₂Br₂, ZnBr₄), from efficient phosphorescence to ultralong afterglow. The afterglow properties of TPP⁺ cations could be suspended for the hybrids containing low band gap emissive metal halide species, such as SbCl₅²⁻ and MnCl₄²⁻, but significantly enhanced for the hybrids containing wide band gap non-emissive ZnCl₄²⁻. Structural and photophysical studies reveal that the enhanced afterglow is attributed to stronger π–π stacking and intermolecular electronic coupling between TPP⁺ cations in TPP₂ZnCl₄ than in the pristine organic ionic compound TPPCl. Moreover, the afterglow in TPP₂ZnX₄ can be tuned by controlling the halide composition, with the change from Cl to Br resulting in a shorter afterglow due to the heavy atom effect.