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Using Room Temperature Phosphorescence of Gold(I) Complexes for PAHs Sensing.

ABSTRACT: The synthesis of two new phosphane-gold(I)-napthalimide complexes has been performed and characterized. The compounds present luminescent properties with denoted room temperature phosphorescence (RTP) induced by the proximity of the gold(I) heavy atom that favors intersystem crossing and triplet state population. The emissive properties of the compounds together with the planarity of their chromophore were used to investigate their potential as hosts in the molecular recognition of different polycyclic aromatic hydrocarbons (PAHs). Naphthalene, anthracene, phenanthrene, and pyrene were chosen to evaluate how the size and electronic properties can affect the host:guest interactions. Stronger affinity has been detected through emission titrations for the PAHs with extended aromaticity (anthracene and pyrene) and the results have been supported by DFT calculation studies.

SUBMITTER: Rosental M

PROVIDER: S-EPMC8122727 | biostudies-literature |

REPOSITORIES: biostudies-literature

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Aggregation-Enhanced Room-Temperature Phosphorescence from Au(I) Complexes Bearing Mesogenic Biphenylethynyl Ligands.

Project description:Gold(I) complexes, enabling to form linear coordination geometry, are promising materials for manifesting both aggregation-induced emission (AIE) behavior due to strong intermolecular Au-Au (aurophilic) interactions and liquid crystalline (LC) nature depending on molecular geometry. In this study, we synthesized several gold(I) complexes with rod-like molecular skeletons where we employed a mesogenic biphenylethynyl ligand and an isocyanide ligand with flexible alkoxyl or alkyl chains. The AIE behavior and LC nature were investigated experimentally and computationally. All synthesized gold(I) complexes exhibited AIE properties and, in crystal, room-temperature phosphorescence (RTP) with a relatively high quantum yields of greater than 23% even in air. We have demonstrated that such strong RTP are drastically changed depending on the crystal-size and/or crystal growth process that changes quality of crystals as well as the aggregate structure, of e.g., Au-Au distance. Moreover, the complex with longer flexible chains showed LC nature where RTP can be observed. We expect these rod-like gold(I) complexes to have great potential in AIE-active LC phosphorescent applications such as linearly/circularly polarizing phosphorescence materials.

| S-EPMC8658970 | biostudies-literature

Modulating Room-Temperature Phosphorescence-To-Phosphorescence Mechanochromism by Halogen Exchange.

Project description:Modulating the stimulus-responsiveness of a luminescent crystal is challenging owing to the complex interdependent nature of its controlling factors, such as molecular structure, molecular conformation, crystal packing, optical properties, and amorphization behavior. Herein, we demonstrate a halogen-exchange approach that disentangles this problem, thereby realizing the modulation of room-temperature phosphorescence-to-phosphorescence mechanochromism. Replacing the bromine atoms in a brominated thienyl diketone with chlorine atoms afforded isostructural crystals; i.e., molecules with different halogen atoms exhibited the same molecular conformation and crystal packing. Consequently, amorphization behavior toward mechanical stimulation was also the same, and the phosphorescence of amorphous states originated from the same conformer of each diketone. In contrast, the phosphorescence properties of each conformer were modulated differently, which is ascribable to heavy atom effects, resulting in the modulation of the mechanochromism. Thus, halogen exchange is a promising approach for modulating the stimulus-responsive photofunctions of crystals involving spin-forbidden processes.

| S-EPMC8793743 | biostudies-literature

Purely Organic Microparticles Showing Ultralong Room Temperature Phosphorescence.

Project description:Currently, organic phosphorescent particles are heavily used in sensing and imaging. Up to now, most of these particles contain poisonous and/or expensive metal complexes. Environmentally friendly systems are therefore highly desired. A purely amorphous system consisting of poly(methyl methacrylate) particles with incorporated N,N,N',N'-tetrakis(4-carboxyphenyl)benzidine emitter molecules is presented in this work. Single particles with sizes between 400 and 840 nm show-depending on the environment-bright fluorescence and phosphorescence. The latter is observed when oxygen is not in the proximity of the emitting dye molecules. These particles can scavenge singlet oxygen, which is produced during the photoexcitation process, by incorporating it into the polymer matrix. This renders their use to be unharmful for the surrounding matter with possible application in marking schemes for living bodies.

| S-EPMC8158833 | biostudies-literature

A room temperature phosphorescence encoding [2]rotaxane molecular shuttle.

Project description:A novel bistable molecular shuttle, composed of a Pt(ii) porphyrin-containing dibenzo[24]crown-8 macrocycle threaded onto two different recognition sites (secondary dialkylammonium (NH2+) and 4,4'-bipyridinium (Bpym2+) units), and the anthracene (Anth) moiety as one terminal stopper, was synthesized by click chemistry. Its acid-base switchable shuttling could be addressed by both the room temperature phosphorescence (RTP) emission signals of the Pt(ii) porphyrin moiety and the fluorescence emission of the Anth unit, as well as their lifetime changes. When the macrocycle was switched to be located on the NH2+ site close to Anth, the Pt(ii) porphyrin moiety exhibited strong RTP emission, excited in the Anth band at 370 nm. This was due to the distance-dependent efficient singlet energy transfer between the Anth unit and the porphyrin moiety, followed by intersystem crossing from a singlet to a triplet state in Pt(ii) porphyrin, while its RTP emission dramatically decreased when located on the Bpym2+ site far from the Anth unit. When excited in the porphyrin band at 402 nm, the RTP emission lifetimes changed obviously. This is the first rotaxane-type molecular shuttle whose shuttling has been encoded by RTP signals.

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Red Phosphorescence from Benzo[2,1,3]thiadiazoles at Room Temperature.

Project description:We describe the red phosphorescence exhibited by a class of structurally simple benzo[2,1,3]thiadiazoles at room temperature. The photophysical properties of these molecules in deoxygenated cyclohexane, including their absorption spectra, steady-state photoluminescence and excitation spectra, and phosphorescence lifetimes, are presented. Time-dependent density functional theory calculations were carried out to better understand the electronic excited states of these benzo[2,1,3]thiadiazoles and why they are capable of phosphorescence.

| S-EPMC4892972 | biostudies-literature

Highly Efficient Aggregation-Induced Room-Temperature Phosphorescence with Extremely Large Stokes Shift Emitted from Trinuclear Gold(I) Complex Crystals.

Project description:Highly efficient (?75% quantum yield), aggregation-induced phosphorescence is reported. The phosphorescence is emitted at room temperature and in the presence of air from crystals of trinuclear Au(I) complexes, accompanied by an extremely large Stokes shift of 2.2 × 104 cm-1 (450 nm). The mechanism of the aggregation-induced room-temperature phosphorescence from the Au complex crystals was investigated in terms of the crystal packing structure and the primary structure of the molecules. It was found that two kinds of intermolecular interactions occurred in the crystals, and that these multiple dual-mode intermolecular interactions in the crystals play a crucial role in the in-air room-temperature phosphorescence of the trinuclear Au(I) complexes.

| S-EPMC6943708 | biostudies-literature

Mechano-induced persistent room-temperature phosphorescence from purely organic molecules.

Project description:The persistent room-temperature phosphorescence (RTP) of purely organic materials in the solid state has recently attracted much research interest and found promising, rapid and visual applications by the naked eye, after the removal of the excitation source. However, almost all reported organic persistent RTP processes are induced by using a UV-light irradiation source. In this report, persistent RTP with an emission lifetime as long as 0.15 s which can be induced not only by photoirradiation but also by mechanical action is presented, which merges mechano-induced luminescence and persistent RTP together. It is found that such persistent RTP is produced through intermolecular electronic coupling (IEC) of units with different excited state configurations. Interestingly, there are two different crystals with and without mechano-induced persistent RTP which can be grown from this organic material, as such a new type of mechano-luminescence (ML) is strongly dependent on their intermolecular interactions. Furthermore, the intensity of such mechano-induced persistent RTP can be increased by lowing the temperature as well, similar to that of photo-induced persistent RTP. Notably, these two crystals exhibit a ML enhancement and ML "turn on", respectively, with decreasing temperature. Therefore, such mechano-induced persistent RTP provides an example of new types of organic luminescent materials, which is a missing jigsaw piece of organic luminescence and important for both fundamental research and practical applications of both persistent RTP and ML of organic materials.

| S-EPMC5939606 | biostudies-literature

Engendering persistent organic room temperature phosphorescence by trace ingredient incorporation.

Project description:Pure organic persistent room temperature phosphorescence (RTP) has shown great potential in information encryption, optoelectronic devices, and bio-applications. However, trace impurities are generated in synthesis, causing unpredictable effects on the luminescence properties. Here, an impurity is isolated from a pure organic RTP system and structurally characterized that caused an unusual ultralong RTP in matrix even at 0.01 mole percent content. Inspired by this effect, a series of compounds are screened out to form the bicomponent RTP system by the trace ingredient incorporation method. The RTP quantum yields reach as high as 74.2%, and the lifetimes reach up to 430 ms. Flexible application of trace ingredients to construct RTP materials has become an eye-catching strategy with high efficiency, economy, and potential for applications as well as easy preparation.

| S-EPMC8104869 | biostudies-literature

Pure Boric Acid Does Not Show Room-Temperature Phosphorescence (RTP).

Project description:Boric acid (BA) has been used as a transparent glass matrix for optical materials for over 100 years. However, recently, apparent room-temperature phosphorescence (RTP) from BA (crystalline and powder states) was reported (Zheng et al., Angew. Chem. Int. Ed. 2021, 60, 9500) when irradiated at 280 nm under ambient conditions. We suspected that RTP from their BA sample was induced by an unidentified impurity. Our experimental results show that pure BA synthesized from B(OMe)3 does not luminesce in the solid state when irradiated at 250-400 nm, while commercial BA indeed (faintly) luminesces. Our theoretical calculations show that neither individual BA molecules nor aggregates would absorb light at >175 nm, and we observe no absorption of solid pure BA experimentally at >200 nm. Therefore, it is not possible for pure BA to be excited at >250 nm even in the solid state. Thus, pure BA does not display RTP, whereas trace impurities can induce RTP.

| S-EPMC9305524 | biostudies-literature

Multilevel Data Encryption Using Thermal-Treatment Controlled Room Temperature Phosphorescence of Carbon Dot/Polyvinylalcohol Composites.

Project description:Thermal-treatment controlled room temperature phosphorescence is realized by embedding either originally synthesized carbon dots (CDs) or 200 °C thermal-treated CDs into a polyvinylalcohol (PVA) matrix through post-synthetic thermal annealing at 200 or 150 °C. The thermal-treatment controlled phosphorescence is attributed to the transfer of photoexcitation from the excited singlet state to the triplet state through intersystem crossing, followed by radiative transition to the ground state, which is due to decrease of quenchers (oxygen) in the CDs and suppression of the vibrational dissipations through the chemical bonding of CDs in the PVA matrix. Multilevel fluorescence/phosphorescence data encryption is demonstrated based on the thermal-treatment controlled phosphorescence from CD@PVA composites.

| S-EPMC6145421 | biostudies-literature

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