Room-temperature Phosphorescence Molecules Research Articles

Insights on aggregation induced room temperature phosphorescence properties: A QM/MM study

Organic room temperature phosphorescence (RTP) molecules have attracted significant attention recently due to their promising application in security, bioimaging, sensing and organic light emitting diodes (OLEDs). Nevertheless, limited RTP molecules were reported until now and most of RTP phenomena were observed in crystal. Moreover, the underlying mechanisms of RTP still remain ambiguous. In this paper, excited-state properties of CZs-CN with RTP features in three crystals are theoretically studied using the combined quantum mechanics and molecular mechanics (QM/MM) method. Moreover, the photophysical properties of CZs-CN in solvent are also investigated by polarizable continuum model (PCM). The mechanism of aggregation induced RTP is revealed which is mainly contributed by the enhanced phosphorescence rates in aggregation, rather than the traditional restricted intramolecular motion mechanisms which usually bring decreased non-radiative decay rates. In addition, different crystal structures could induce different phosphorescence properties, and the emission spectra of the molecule in three crystals and THF are explained reasonable. Furthermore, dimers are confirmed to be involved in the emission when the intermolecular interaction is strong enough in aggregation. Our theoretical results provide inner perspective for aggregation induced RTP mechanism and could help one to better understand the different light-emitting properties in aggregation and solvent.

Room-Temperature Phosphorescence from a Series of 3-Pyridylcarbazole Derivatives.

Exploration of pure metal-free organic molecules that exhibit strong room-temperature phosphorescence (RTP) is an emerging research topic. In this regard, unveiling the design principles for an efficient RTP molecule is an essential, but challenging, task. A small molecule is an ideal platform to precisely understand the fundamental role of each functional component because the parent molecule can be easily derivatized. Here, the RTP behaviors of a series of 3-pyridylcarbazole derivatives are presented. Experimental studies in combination with theoretical calculations reveal the crucial role of the n orbital on the central pyridine ring in the dramatic enhancement of the intersystem crossing between the charge-transfer-excited singlet state and the locally excited triplet states. Single-crystal X-ray crystallographic studies apparently indicate that both the pyridine ring and fluorine atom contribute to the enhancement of the RTP because of the restricted motion owing to weak C-H⋅⋅⋅N and H⋅⋅⋅F hydrogen-bonding interactions. The single crystal of the fluorine-substituted derivative shows an ultra-long phosphorescent lifetime (τP ) of 1.1 s and a phosphorescence quantum yield (ΦP ) of 1.2 %, whereas the bromine-substituted derivative exhibits τP of 0.15 s with a ΦP of 7.9 %. We believe that this work provides a fundamental and universal guideline for the generation of pure organic molecules exhibiting strong RTP.

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

AbstractA 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 Tn. 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.

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 Tn . 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.

Long‐Lived Room‐Temperature Phosphorescence for Visual and Quantitative Detection of Oxygen

AbstractAn unconventional organic molecule (TBBU) showing obvious long‐lived room temperature phosphorescence (RTP) is reported. X‐ray single crystal analysis demonstrates that TBBU molecules are packed in a unique fashion with side‐by‐side arranged intermolecular aromatic rings, which is entirely different from the RTP molecules reported to date. Theoretical calculations verify that the extraordinary intermolecular interaction between neighboring molecules plays an important role in RTP of TBBU crystals. More importantly, the polymer film doped with TBBU inherits its distinctive RTP property, which is highly sensitive to oxygen. The color of the doped film changes and its RTP lifetime drops abruptly through a dynamic collisional quenching mechanism with increasing oxygen fraction, enabling visual and quantitative detection of oxygen. Through analyzing the grayscale of the phosphorescence images, a facile method is developed for rapid, visual, and quantitative detection of oxygen in the air.

Long-Lived Room-Temperature Phosphorescence for Visual and Quantitative Detection of Oxygen.

An unconventional organic molecule (TBBU) showing obvious long-lived room temperature phosphorescence (RTP) is reported. X-ray single crystal analysis demonstrates that TBBU molecules are packed in a unique fashion with side-by-side arranged intermolecular aromatic rings, which is entirely different from the RTP molecules reported to date. Theoretical calculations verify that the extraordinary intermolecular interaction between neighboring molecules plays an important role in RTP of TBBU crystals. More importantly, the polymer film doped with TBBU inherits its distinctive RTP property, which is highly sensitive to oxygen. The color of the doped film changes and its RTP lifetime drops abruptly through a dynamic collisional quenching mechanism with increasing oxygen fraction, enabling visual and quantitative detection of oxygen. Through analyzing the grayscale of the phosphorescence images, a facile method is developed for rapid, visual, and quantitative detection of oxygen in the air.

Impact of Methoxy Substituents on Thermally Activated Delayed Fluorescence and Room-Temperature Phosphorescence in All-Organic Donor-Acceptor Systems.

Thermally activated delayed fluorescence (TADF) and room-temperature phosphorescence (RTP) are known to occur in organic D-A-D and D-A systems where the donor group contains the phenothiazine unit and the acceptor is dibenzothiophene- S, S-dioxide. This study reports the synthesis and characterization of one new D-A and four new D-A-D systems with methoxy groups on the phenothiazine to examine their effect on emission properties in the zeonex matrix. X-ray analysis and highly specialized NMR techniques were used to characterize asymmetric methoxy-substituted derivative 3b, which is chiral at N because of an extremely high flipping barrier at the phenothiazine N atom. Based on hybrid-density functional theory computations, the methoxy substituents tune the relative stabilities of the axial conformers with respect to equatorial conformers of the phenothiazine units, depending on their substitution position. This conformational effect significantly influences both TADF and RTP contributions compared to the parent D-A-D system. It is also demonstrated that the equatorial forms of D-A-D and D-A systems in zeonex exhibit TADF. Additionally, the methoxy groups promote luminescence in D-A-D systems where only axial conformers exist. This work reveals further design opportunities for more efficient TADF and RTP molecules.

Room-Temperature Phosphorescence from Metal-Free Organic Materials in Solution: Origin and Molecular Design.

Metal-free organic materials with room-temperature phosphorescence (RTP) is hardly achieved in solution owing to the ambiguous underlying mechanism. By combining thermal vibration correlation function rate theory and a polarizable continuum model (PCM) coupled with the Tamm-Dancoff approximation method, concentrating on β-hydroxyvinylimine boron compounds C-BF2 and S-BF2, we showed that the increased intersystem crossing ( kisc) and radiative decay rates ( kp) are responsible for the strong RTP of S-BF2 in solution. From C-BF2 to S-BF2, the T2 state is increasingly dominated by the n → π* transition, largely enhancing the kisc of S1 → T2 (up to 3 orders of magnitude) and kp of T1 → S0. Impressively, the nonradiative decay rate of T1 → S0 is slightly increased by suppressing the out-of-plane twisting motions. This mechanism is also tenable for several designed RTP molecules through further experimental demonstration, which will pave a new way to design organic materials with single-molecule phosphorescence for applying to organic light-emitting diodes.

Intramolecular Charge Transfer Controls Switching Between Room Temperature Phosphorescence and Thermally Activated Delayed Fluorescence.

Chemical modification of phenothiazine-benzophenone derivatives tunes the emission behavior from triplet states by selecting the geometry of the intramolecular charge transfer (ICT) state. A fundamental principle of planar ICT (PICT) and twisted ICT (TICT) is demonstrated to obtain selectively either room temperature phosphorescence (RTP) or thermally activated delayed fluorescence (TADF), respectively. Time-resolved spectroscopy and time-dependent density functional theory (TD-DFT) investigations on polymorphic single crystals demonstrate the roles of PICT and TICT states in the underlying photophysics. This has resulted in a RTP molecule OPM, where the triplet states contribute with 89 % of the luminescence, and an isomeric TADF molecule OMP, where the triplet states contribute with 95 % of the luminescence.

Intramolecular Charge Transfer Controls Switching Between Room Temperature Phosphorescence and Thermally Activated Delayed Fluorescence

AbstractChemical modification of phenothiazine‐benzophenone derivatives tunes the emission behavior from triplet states by selecting the geometry of the intramolecular charge transfer (ICT) state. A fundamental principle of planar ICT (PICT) and twisted ICT (TICT) is demonstrated to obtain selectively either room temperature phosphorescence (RTP) or thermally activated delayed fluorescence (TADF), respectively. Time‐resolved spectroscopy and time‐dependent density functional theory (TD‐DFT) investigations on polymorphic single crystals demonstrate the roles of PICT and TICT states in the underlying photophysics. This has resulted in a RTP molecule OPM, where the triplet states contribute with 89 % of the luminescence, and an isomeric TADF molecule OMP, where the triplet states contribute with 95 % of the luminescence.

Proton-Activated "Off-On" Room-Temperature Phosphorescence from Purely Organic Thioethers.

Room-temperature phosphorescence (RTP)-based sensors have distinctive advantages over the fluorescence counterparts, such as larger Stokes shifts and longer lifetimes. Unfortunately, almost all RTP sensors are operated on quenching-based mechanisms given the sensitive nature of the emissive triplet state. Here we report a type of thioether RTP molecules that shows RTP "turn-on" when volatile acid vapors such as HCl are in contact. To elucidate the underlying mechanism, model thioethers containing different donor/acceptor combinations are investigated via fluorescence spectroscopy and theoretical calculations aided by molecular coordinates obtained from single-crystal X-ray diffraction. It is revealed that a charge-transfer character in the phosphorescence state is crucial. The "turn-on" design concept may significantly broaden the sensing application scope for organic RTP molecules.

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

AbstractPersistent 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.

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.