Dual Phosphorescence Research Articles

New Approach toward Dual-Emissive Organic-Inorganic Hybrids by Integrating Mn(II) and Cu(I) Emission Centers in Ionic Crystals.

Inorganic-organic hybrid luminescent materials have received great attention for their potential applications in a wide range of clean/renewable energy-related areas, including photovoltaics and solid-state lighting. Herein, we present a unique and general "Mn + Cu" approach by blending two earth-abundant luminogenic metals, manganese and copper, within a single ionic structure to construct a remarkable family of low-cost and multifunctional hybrid materials featuring dual emission, as well as triboluminescence and second-harmonic generation response. The novel hybrid materials are made of diphosphine dioxide-chelated [Mn(O∧O)3]2+ cations and various anionic [CuxIy](y-x)- clusters, ensuring manifestation of dual phosphorescence streamed from octahedral Mn2+ ions (605-648 nm) and iodocuprate anions (480-728 nm). Noteworthily, the relative ratio of the emission bands, and hence a resulting emission chromaticity, can be tuned in a wide range through modification of cluster [CuxIy](y-x)- modules. The structural diversity, enhanced robustness, and up to 100% luminescence quantum yield make the designed materials promising phosphors for lighting and sensing applications.

Anion-π-Induced Room Temperature Phosphorescence from Emissive Charge-Transfer States.

The burgeoning noncovalent interactions between π-acidic aromatic surfaces and anions have been recently shown to have unique functional relevance in anion transport, ion sensing, and organocatalysis. Despite its potential to instigate charge-transfer (CT) states, modulation of the emission features by toggling between the excited states using anion-π interactions is not yet explored. On the other hand, excited states with CT characteristics play an important role in the ambient triplet harvesting of organic chromophores. In this context, herein we propose an anion-π-based molecular design for the introduction of emissive singlet and triplet CT excited states, thereby expanding the functional scope of these weak supramolecular interactions. In the present study, we investigate the anion-π-induced emission from the singlet (1CT) and triplet (3CT) CT states of a dibromo dicationic pyromellitic diimide derivative. Remarkably, we accomplish dual room temperature phosphorescence emission from the anion-π-mediated 3CT state along with the locally excited triplet state (3LE) in solution phase using an organic-inorganic supramolecular scaffolding strategy. Comprehensive steady-state and time-resolved spectroscopy along with theoretical calculations provide detailed insights into the excited-state manifolds of phosphor. We envisage that the present study will expedite new molecular designs based on weak intermolecular interactions for the excited-state engineering of organic chromophores to facilitate ambient triplet harvesting and CT emission.

Aggregation-Induced Dual Phosphorescence from (o-Bromophenyl)-Bis(2,6-Dimethylphenyl)Borane at Room Temperature.

Designing highly efficient purely organic phosphors at room temperature remains a challenge because of fast non‐radiative processes and slow intersystem crossing (ISC) rates. The majority of them emit only single component phosphorescence. Herein, we have prepared 3 isomers (o, m, p‐bromophenyl)‐bis(2,6‐dimethylphenyl)boranes. Among the 3 isomers ( o ‐, m ‐ and p ‐BrTAB) synthesized, the ortho‐one is the only one which shows dual phosphorescence, with a short lifetime of 0.8 ms and a long lifetime of 234 ms in the crystalline state at room temperature. Based on theoretical calculations and crystal structure analysis of o ‐BrTAB, the short lifetime component is ascribed to the T1 M state of the monomer which emits the higher energy phosphorescence. The long‐lived, lower energy phosphorescence emission is attributed to the T1 A state of an aggregate, with multiple intermolecular interactions existing in crystalline o ‐BrTAB inhibiting nonradiative decay and stabilizing the triplet states efficiently.

Polarity-induced dual room-temperature phosphorescence involving the T2 states of pure organic phosphors

Polarity-induced room-temperature dual phosphorescence involving the T2 state of purely organic phosphors.

Hot-exciton harvesting via through-space single-molecule based white-light emission and optical waveguides.

Through-space donor–alkyl bridge–acceptor (D–σ–A) luminogens are developed as new organic single-molecule white light emitters (OSMWLEs) involving multiple higher lying singlet (Sn) and triplet (Tm) states (hot-excitons). Experimental and theoretical results confirm the origin of white light emission due to the co-existence of prompt fluorescence from locally excited states, thermally activated delayed fluorescence (TADF), and fast/slow dual phosphorescence color mixing simultaneously. Notably, the fast phosphorescence was observed due to trace amounts of isomeric impurities from commercial carbazole, while H-/J-aggregation resulted in slow phosphorescence. Crystal structure-packing-property analysis revealed that the alkyl chain length induced supramolecular self-assembly greatly influenced the solid-state optical properties. Remarkably, the 1D-microrod crystals of OSMWLEs demonstrated the first examples of triplet harvesting waveguides by self-guiding the generated phosphorescence through light propagation along their longitudinal axis. This work thus highlights an uncommon design strategy to achieve multi-functional OSMWLEs with in-depth mechanistic insights and optical waveguiding applications making them a potentially new class of white emissive materials.

White-light emission from organic aggregates: a review

White light, which contains polychromic visible components, affects the rhythm of organisms and has the potential for advanced applications of lighting, display, and communication. Compared with traditional incandescent bulbs and inorganic diodes, pure organic materials are superior in terms of better compatibility, flexibility, structural diversity, and environmental friendliness. In the past few years, polychromic emission has been obtained based on organic aggregates, which provides a platform to achieve white-light emission. Several white-light emitters are sporadically reported, but the underlying mechanistic picture is still not fully established. Based on these considerations, we will focus on the single-component and multicomponent strategies to achieve efficient white-light emission from pure organic aggregates. Thereinto, single-component strategy is introduced from four parts: dual fluorescence, fluorescence and phosphorescence, dual phosphorescence with anti-Kasha’s behavior, and clusteroluminescence. Meanwhile, doping, supramolecular assembly, and cocrystallization are summarized as strategies for multicomponent systems. Beyond the construction strategies of white-light emitters, their advanced representative applications, such as organic light-emitting diodes, white luminescent dyes, circularly polarized luminescence, and encryption, are also prospected. It is expected that this review will draw a comprehensive picture of white-light emission from organic aggregates as well as their emerging applications.

Multistimulus Response of Two Tautomeric Zn(II) Complexes and Their White-Light Emission Based on Different Mechanisms.

A triphenylamine (TPA)-based 2H-quinazoline Zn(II) complex (Q-TPA-Zn) exhibiting dual fluorescence and phosphorescence emission in the solid state was designed and prepared. It possesses mechanochromic luminescence and thermochromic luminescence properties. In the solid state, the white afterglow luminescence could be observed at 77 K (CIExy: 0.27, 0.33) while cyan luminescence could be observed at 297 K. After thermolysis at 300 °C, Q-TPA-Zn could be transformed into Schiff base complex S-TPA-Zn with white fluorescence in the powder state (CIExy: 0.32, 0.38), in methanol (CIExy: 0.32, 0.39), and in dimethylformamide (CIExy: 0.26, 0.32) at room temperature. This arises from dual emission of normal* emission and tautomeric* emission induced by excited-state intramolecular proton transfer (ESIPT) from the benzimidazole NH group to the Schiff base N atom. Q-TPA-Zn could also be transformed into its isomeric form, S-TPA-Zn, through photochemical ring-opening reaction upon irradiation under 365 nm in the solution, exhibiting high-contrast photochromic luminescence. Interestingly, S-TPA-Zn could further be transformed into its zwitterionic isomer after continuous irradiation. The same ring-opening reaction could also take place for the orgainc compound Q-TPA via heating or 365 nm irradiation. The ring-opening reaction mechanism and ESIPT emission were interpreted via theoretical calculation.

Surface Plasmon-Coupled Dual Emission Platform for Ultrafast Oxygen Monitoring after SARS-CoV-2 Infection

The outbreak of the COVID-19 pandemic has had a major impact on the health and well-being of people with its long-term effect on lung function and oxygen uptake. In this work, we present a unique approach to augment the phosphorescence signal from phosphorescent gold(III) complexes based on a surface plasmon-coupled emission platform and use it for designing a ratiometric sensor with high sensitivity and ultrafast response time for monitoring oxygen uptake in SARS-CoV-2-recovered patients. Two monocyclometalated Au(III) complexes, one having exclusively phosphorescence emission (λPL = 578 nm) and the other having dual emission, fluorescence (λPL = 417 nm) and phosphorescence (λPL = 579 nm), were studied using the surface plasmon-coupled dual emission (SPCDE) platform for the first time, which showed 27-fold and 17-fold enhancements, respectively. The latter complex having the dual emission was then used for the fabrication of a ratiometric sensor for studying the oxygen quenching of phosphorescence emission with the fluorescence emission acting as an internal standard. Low-cost poly (methyl methacrylate) (PMMA) and biodegradable wood were used to fabricate the microfluidic chips for oxygen monitoring. The sensor showed a high sensitivity with a limit of detection ∼ 0.1%. Furthermore, real-time oxygen sensing was carried out and the response time of the sensor was calculated to be ∼0.2 s. The sensor chip was used for monitoring the oxygen uptake in SARS-CoV-2-recovered study participants, to assess their lung function post the viral infection.

Dual-Emissive Tris-Heteroleptic Ruthenium Complexes: Tuning the DNA-Triggered Ratiometric Emission Response by Ancillary Ligands.

Three tris-heteroleptic mononuclear Ru(II) complexes with dual fluorescence and phosphorescence-[Ru(dpma)(bpy)(phen)]2+ (12+), [Ru(dpma)(bpy)(dppz)]2+ (22+), and [Ru(dpma)(phen)(dppz)]2+ (32+)-have been designed and used as ratiometric light-response probes for DNA, where dpma is di(pyrid-2-yl)(methyl)-amine, bpy is 2,2'-bipyridine, phen is 1,10-phenanthroline, and dppz is dipyridophenazine, respectively. Single crystals of complex 2(PF6)2 have been obtained and studied by X-ray analysis. The interactions of these complexes with different DNAs are investigated by means of spectroscopic methods, viscosity measurements, and molecular modeling. In the presence of calf thymus DNA, complexes 2(PF6)2 and 3(PF6)2 show the emergence of a new lower-energy phosphorescence emission band; meanwhile, the higher-energy fluorescence emission band is essentially unchanged, functioning as an intrinsic internal reference. These two complexes exhibit stronger preference for calf thymus DNA over single-strand DNA (d(A)16 and d(C)16). In contrast, no binding interaction between 1(PF6)2 and calf thymus DNA is observed. The intrinsic binding constants (Kb) of 2(PF6)2 and 3(PF6)2 with calf thymus DNA are determined to be (1.4 ± 0.4) × 105 and (9.5 ± 0.15) × 104 M-1, respectively. In addition, these spectroscopic results are compared with those of the prototype complex [Ru(bpy)2(dppz)]2+ (42+), and density functional theory and time-dependent density functional theory calculations are employed to elucidate these experimental findings.

Dihedral Angle Distribution of Thermally Activated Delayed Fluorescence Molecules in Solids Induces Dual Phosphorescence from Charge-Transfer and Local Triplet States

Dihedral Angle Distribution of Thermally Activated Delayed Fluorescence Molecules in Solids Induces Dual Phosphorescence from Charge-Transfer and Local Triplet States

Electronic and transport properties of the dual-emitter organometallic compound IrQ(ppy)2

The structure of the IrQ(ppy)2 organometallic dual phosphorescent compound was experimentally and theoretically investigated. The Metal-to-Ligand Charge Transfer toward the phenylpiridine and quinoline ligands explains its dual phosphorescence property. The IrQ(ppy)2 organometallic's electronic properties extend the absorption spectra toward the lower energies than Ir(ppy)3 due to the bandgap reduction induced by the quinoline ligand. The magneto-optical measurements reveal A-terms, which are produced by splitting the triplet states and B-terms, which arise when the electronic levels are mixed in the magnetic field. The IrQ(ppy)2 molecule's transport properties confirm an ambipolar character, consisting of a higher hole transport character induced by the phenyilpiridine ligands and a lower electron transport character induced by the quinoline ligand.

Bright and Robust Phosphorescence Achieved by Non-Covalent Clipping.

Phosphorescent materials with bright emission in versatile media are important for their practical applications, which require to lower the susceptibility of triplet excitons to surroundings. Herein a non-covalent clipping strategy has been developed to attain this objective, by designing a tweezer receptor to encapsulate PtII -based triplet emitters through two-fold π-stacking interactions. The PtII emitters display robust phosphorescence by virtue of synergistic rigidifying and shielding effects, which are hardly influenced by emitter concentration, oxygen content, and solvent polarity changes. The phosphorescent colors are elaborately modulated by varying ligand substitutes on PtII emitters. Circularly polarized phosphorescence is further amplified for chiral PtII emitters, by taking advantage of dual phosphorescence and chirality enhancement upon non-covalent tweezer complexation. Overall, the clipping approach paves the way for the development of high-performance phosphorescent materials with bright emission, environmental robustness, and facile color tunability.

Bright and Robust Phosphorescence Achieved by Non‐Covalent Clipping

AbstractPhosphorescent materials with bright emission in versatile media are important for their practical applications, which require to lower the susceptibility of triplet excitons to surroundings. Herein a non‐covalent clipping strategy has been developed to attain this objective, by designing a tweezer receptor to encapsulate PtII‐based triplet emitters through two‐fold π‐stacking interactions. The PtII emitters display robust phosphorescence by virtue of synergistic rigidifying and shielding effects, which are hardly influenced by emitter concentration, oxygen content, and solvent polarity changes. The phosphorescent colors are elaborately modulated by varying ligand substitutes on PtII emitters. Circularly polarized phosphorescence is further amplified for chiral PtII emitters, by taking advantage of dual phosphorescence and chirality enhancement upon non‐covalent tweezer complexation. Overall, the clipping approach paves the way for the development of high‐performance phosphorescent materials with bright emission, environmental robustness, and facile color tunability.

Metal-Free Organic Luminophores that Exhibit Dual Fluorescence and Phosphorescence Emission at Room Temperature.

Dual-fluorescent-phosphorescent compounds have attracted increasing attention in various fields, such as bio-imaging, data protection/encryption, ratiometric luminescence sensing, and white-light emission. Conventional dual-emissive compounds contain a phosphorescent organometallic complex of a precious metal, such as iridium or platinum. However, the use of precious metals in organic materials has several drawbacks. This Minireview focuses on precious-metal-free organic light-emitting materials that exhibit dual fluorescence and phosphorescence emission in the solid state at room temperature to produce bimodal steady-state emission spectra. The dual emitters presented herein are categorized into the following six compound classes: (1) difluoroboron diaroylmethanes, (2) diarylketones, (3) diarylsulfones, (4) triazines and pyrimidines, (5) fused phenazines, and (6) N-arylcarbazoles.

Thermochromic aggregation-induced dual phosphorescence via temperature-dependent sp3-linked donor-acceptor electronic coupling

Aggregation-induced emission (AIE) has proven to be a viable strategy to achieve highly efficient room temperature phosphorescence (RTP) in bulk by restricting molecular motions. Here, we show that by utilizing triphenylamine (TPA) as an electronic donor that connects to an acceptor via an sp3 linker, six TPA-based AIE-active RTP luminophores were obtained. Distinct dual phosphorescence bands emitting from largely localized donor and acceptor triplet emitting states could be recorded at lowered temperatures; at room temperature, only a merged RTP band is present. Theoretical investigations reveal that the two temperature-dependent phosphorescence bands both originate from local/global minima from the lowest triplet excited state (T1). The reported molecular construct serves as an intermediary case between a fully conjugated donor-acceptor system and a donor/acceptor binary mix, which may provide important clues on the design and control of high-freedom molecular systems with complex excited-state dynamics.

Diverse emission properties of transition metal complexes beyond exclusive single phosphorescence and their wide applications

• Intersystem crossing (ISC) rate of a metal complex is determined by not only SOC constant of the metal ion. • Various photophysical mechanisms are possible for transition metal complexes. • Emission properties other than single phosphorescence can be achieved by molecular design. • Uncommon emission properties open up novel applications in many areas. • Triplet excited state of earth-abundant metal complexes can be exploited for use by the novel mechanisms. Luminescence properties and excited state reactivities of photoactive transition metal complexes have been harnessed for various applications in the fields of electroluminescent devices, luminescent sensing and bio-imaging, and solar energy conversion as well as photo-redox catalysis in organic transformation. While, beyond the conventional phosphorescence from triplet excited sates that are populated through heavy metal atom induced intersystem crossing (ISC), the past decade has witnessed blooming reports on intriguing luminescence behaviors such as sole fluorescence, dual fluorescence/phosphorescence, thermally activated delayed fluorescence (TADF), and dual phosphorescence. All these findings reveal that the possible photophysical mechanisms of transition metal complexes remain relatively underexplored. On one hand, the intersystem crossing (ISC) rate that is crucial to the depopulation of the singlet excited state and thus the population efficiency of the triplet excited state has proven to be not simply dependent on the spin-orbit coupling constant of the metal atom. On the other hand, the decay paths for triplet excited state(s) through reverse ISC (T 1 → S 1 ) and direct radiation from higher triplet excited state have been opened by appropriate ligand design. Moreover, these novel emission properties of transition metal complexes have expanded their applications into the fields of ratiometric sensing/imaging, noble-metal-free high efficiency emitters and photocatalysts and beyond. This review is aimed to discuss the unconventional emission properties and applications of transition metal complexes that were reported mainly in the past decade by focusing on the structural factors that are at play in realizing the novel excited state properties. It is conceived to provide a better understanding of the excited state properties tuning and to direct the design of new emissive metal complexes with tailored functions.

Investigation of Luminescent Triplet States in Tetranuclear CuI Complexes: Thermochromism and Structural Characterization.

To develop new and flexible CuI containing luminescent substances, we extend our previous investigations on two metal‐centered species to four metal‐centered complexes. These complexes could be a basis for designing new organic light‐emitting diode (OLED) relevant species. Both the synthesis and in‐depth spectroscopic analysis, combined with high‐level theoretical calculations are presented on a series of tetranuclear CuI complexes with a halide containing Cu4X4 core (X=iodide, bromide or chloride) and two 2‐(diphenylphosphino)pyridine bridging ligands with a methyl group in para (4‐Me) or ortho (6‐Me) position of the pyridine ring. The structure of the electronic ground state is characterized by X‐ray diffraction, NMR, and IR spectroscopy with the support of theoretical calculations. In contrast to the para system, the complexes with ortho‐substituted bridging ligands show a remarkable and reversible temperature‐dependent dual phosphorescence. Here, we combine for the first time the luminescence thermochromism with time‐resolved FTIR spectroscopy. Thus, we receive experimental data on the structures of the two triplet states involved in the luminescence thermochromism. The transient IR spectra of the underlying triplet metal/halide‐to‐ligand charge transfer (3 m/XLCT) and cluster‐centered (3CC) states were obtained and interpreted by comparison with calculated vibrational spectra. The systematic and significant dependence of the bridging halides was analyzed.

Photophysics and reverse saturable absorption of cationic dinuclear iridium(III) complexes bearing fluorenyl-tethered 2-(quinolin-2-yl)quinoxaline ligands.

The synthesis, photophysics and reverse saturable absorption of two cationic dinuclear Ir(III) complexes bearing fluorenyl-tethered 2-(quinolin-2-yl)quinoxaline (quqo) ligands are reported in this paper. The two complexes possess intense and featureless diimine ligand localized 1ILCT (intraligand charge transfer)/1π,π* absorption bands at ca. 330 and 430 nm, and a weak 1,3MLCT (metal-to-ligand charge transfer)/1,3LLCT (ligand-to-ligand charge transfer) absorption band at >500 nm. Both complexes exhibit weak dual phosphorescence at ca. 590 nm and 710 nm, which are attributed to the 3ILCT/3π,π* and 3MLCT/3LLCT states, respectively. The low-energy 3MLCT/3LLCT state also gives rise to a moderately strong triplet excited-state absorption at 490-800 nm. Because of the stronger triplet excited-state absorption than the ground-state absorption of these complexes at 532 nm, both complexes manifest a moderate reverse saturable absorption (RSA) at 532 nm for ns laser pulses. Expansion of the π-conjugation of the fluorenyl-tethered diimine ligand in Ir-1 causes a slight red-shift of the 1ILCT/1π,π* absorption bands in its UV-vis absorption spectrum and the 3MLCT/3LLCT absorption band in the transient absorption spectrum and slightly enhances the RSA at 532 nm compared to that in Ir-2. This work represents the first report on dinuclear Ir(III) complexes that exhibit RSA at 532 nm.

Halogenation of a twisted non-polar π-system as a tool to modulate phosphorescence at room temperature.

Halogenation of a twisted three-fold symmetric hydrocarbon with F, Cl or Br leads to strong modulation of triplet–triplet annihilation and dual phosphorescence, one thermally activated and the other very persistent and visible by eye, with different relative contributions depending on the halide. The room temperature phosphorescence is highly unusual given the absence of lone-pair-contributing heteroatoms. The interplay between the spin–orbit coupling matrix elements and the spatial configuration of the triplet state induces efficient intersystem crossing and thus room temperature phosphorescence even without relying on heteroatomic electron lone pairs. A ninefold increase of the ISC rate after introduction of three bromine atoms is accompanied by a much higher 34-fold increase of phosphorescence rate.

Stereoselective Formation of Facial Tris-Cyclometalated PtIV Complexes: Dual Phosphorescence from Heteroleptic Derivatives.

A stereoselective synthetic route to homo- and heteroleptic facial tris-cyclometalated PtIV complexes is reported, involving the oxidative addition of 2-(2-pyridyl)- or 2-(1-isoquinolinyl)benzenediazonium salts to cis-[Pt(C^N)2 ] precursors, with C^N=cyclometalated 2-(p-tolyl)pyridine (tpy), 2-phenylquinoline (pq), 2-(2-thienyl)pyridine or 1-phenylisoquinoline (piq), to produce labile diazenide intermediates that undergo photochemical or thermal elimination of N2 . The method allows the preparation of derivatives bearing cyclometalated ligands of low π-π* transition energies. The new complexes exhibit phosphorescence in fluid solution at room temperature arising from triplet ligand-centered (3 LC) excited states, which, in the cases of the heteroleptic derivatives, involve the ligand with the lowest π-π* gap. The heteroleptic piq derivatives exhibit fluorescence and dual phosphorescence from different ligand-centered excited states in rigid media, demonstrating the potential of cyclometalated PtIV complexes as multi-emissive materials.