White Light Emission via Dual Thermally Activated Delayed Fluorescence from a Single-Component Phenothiazines-Diphenyl Quinoline Conjugate.

White light emission (WLE) via dual thermally activated delayed fluorescence (TADF) from a single-component-based organic system remains challenging as a result of the difficulty in design. Here, we introduce a conformational isomerization approach to achieve WLE from a twisted donor-acceptor (PTzQP1) that comprises two phenothiazines covalently attached to the 6,8-isomeric positions of 2,4-diphenyl quinoline via two C-N single bonds. Spectroscopic studies and quantum chemistry calculations revealed that PTzQP1 shows WLE via simultaneous blue TADF and orange TADF covering the visible range (420-800 nm) with a photoluminescence quantum yield of 45 ± 2% and Commission Internationale de l'Éclairage (CIE) coordinates of 0.30, 0.33. The dual TADF features with high rates of reverse intersystem crossing (kRISC1 = 1.38 × 107 ± 0.24 s-1 and kRISC2 = 5.04 × 106 ± 0.32 s-1) are realized as a result of the low singlet-triplet gaps (S1EQ-T1EQ = 0.04 eV and S1QA-T1QA = 0.05 eV) of the quasi-axial (QA) and quasi-equatorial (QE) conformers. This finding is expected to provide a new direction for designing high-energy-efficient WLE emitters.

Carbazole-Benzonitrile-Norbornadiene Conjugates for Photothermally Reversible Ambient Phosphorescence.

Organic photoswitches have attracted significant attention across various fields, such as sensing, bioimaging, photopharmacology, molecular machines, and solar energy storage. However, as a result of design complexities, achieving photothermally reversible ambient phosphorescence switching in the condensed state remains elusive. Herein, we explore the impact of norbornadiene (NBD)/quadricyclane (QC) substitution at position 5 of the benzonitrile acceptor covalently attached to the carbazole donor on photothermally reversible luminescence switching. Experimental investigations demonstrated that the CzN and TBCzN switches exhibited photothermally reversible fluorescence switching in solution. Moreover, in the condensed state, fluorescence and ambient phosphorescence switching were observed as a result of a low singlet-triplet (ΔEST) gap (CzN ⇆ CzQ, ΔESTCzN/CzQ = 0.05/0.28 eV; TBCzN ⇆ TBCzQ, ΔESTTBCzN/TBCzQ = 0.06/0.09 eV). Reversible ambient phosphorescence switching is primarily influenced by modulation of acceptor conjugation resulting from NBD ⇆ QC switching. This approach may provide important clues for the design of visible-light-absorbing photothermally reversible phosphorescent materials.

Conformational Effect of Catechol-Terephthalonitrile Emitters Leading to Ambient Violet Phosphorescence.

Organic ambient violet phosphorescent (AVP) materials are of great interest due to their involvement of high energy and longer-lived triplet excitons. Here, we show three fused ring functionalized donor-acceptor-donor (D-A-D/D-A-D') emitters (BPT1-BPT3), in which two catechol-based donors (3,4-dihydroxybenzophenone, catechol, or 3,5-ditert-butylcatechol) are covalently fused to the terephthalonitrile acceptor via four O-C single bonds. Spectroscopic analysis revealed that all the molecules show AVP (∼390-394 nm, τAVP = 73-101 µs) with phosphorescence quantum yields (ϕP) of 1.8-27.4% due to low singlet-triplet gaps (0.036-0.046 eV) and conformational effects. BPT3 with bulky tert-butyl groups increases AVP (ϕP = 27.4%). Quantum chemistry calculations reveal flat (F1) and twisted (F2) conformers (ground state) with a low energy difference (∼4-5 kcal/mol) for all molecules; the F1 conformer is responsible for efficient AVP, while weak blue thermally activated delayed fluorescence with longer-lived delayed components is realized from the F2 conformer. This approach may provide important clues for the design of high-energy organic phosphorescent materials.

Modulation of Delayed Fluorescence Guided by Conformational Effect-Mediated Thermally Enhanced Phosphorescence in Phenothiazines-Quinoline-Cl Conjugates.

Triplet energy harvesting via thermally activated delayed fluorescence (TADF) from pure organic systems has attracted great attention in organic light-emitting diodes, sensing, and photocatalysis. However, the realization of thermally enhanced phosphorescence (TEP)-guided efficient TADF with a high rate of reverse intersystem crossing (kRISC) still needs to be discovered. Herein, we report two phenothiazine-quinoline conjugates (P2QC, P2QMC) comprising two phenothiazine donors covalently attached to the chlorine-substituted quinolinyl acceptor. Spectroscopic analysis in conjunction with quantum chemistry calculations reveals that TEP in P2QC originated due to slow internal conversion from higher-lying triplet to lowest triplet (T2' → T1') of the quasi-axial (QA) conformer and TADF (kRISC = 1.44 × 108 s-1) originated from the quasi-equatorial (QE) conformer caused by a low singlet-triplet gap (ΔES1-T1 = 0.11 eV) and triplet energy transfer from QA to QE owing to the degenerate ground state of the conformers. In contrast, TADF (kRISC = 0.74 × 108 s-1) and dual phosphorescence under ambient conditions are observed in P2QMC. This study provides a sustainable guideline for developing efficient TADF emitters via conformation effects and energy transfer mechanisms.

Phenoxazine-Quinoline Conjugates: Impact of Halogenation on Charge Transfer Triplet Energy Harvesting via Aggregate Induced Phosphorescence.

Room-temperature phosphorescence (RTP) from organic compounds has attracted increasing attention in the field of data security, sensing, and bioimaging. However, realization of RTP with an aggregate induced phosphorescence (AIP) feature via harvesting supersensitive excited charge transfer triplet (3CT) energy under visible light excitation (VLE) in single-component organic systems at ambient conditions remains unfulfilled. Organic donor-acceptor (D-A) based orthogonal structures can therefore be used to harvest the energy of the 3CT state at ambient conditions under VLE. Here we report three phenoxazine-quinoline conjugates (PQ, PQCl, PQBr), in which D and A parts are held in orthogonal orientation around the C-N single bond; PQCl and PQBr are substituted with halogens (Cl, Br) while PQ has no halogen atom. Spectroscopic studies and quantum chemistry calculations combining reference compounds (Phx, QPP) reveal that all the compounds in film at ambient conditions show fluorescence and green-RTP due to (i) radiative decay of both singlet charge transfer (1CT) and triplet CT (3CT) states under VLE, (ii) energetic nondegeneracy of 1CT and 3CT states (1CT- 3CT, 0.17-0.21 eV), and (iii) spatial separation of highest and lowest unoccupied molecular orbitals. Further, we found in a tetrahydrofuran-water mixture (f w = 90%, v/v) that both PQCl (10-5 M) and PQBr (10-5 M) show concentration-dependent AIP with phosphorescence quantum yields (ϕP) of ∼25% and ∼28%, respectively, whereas aggregate induced quenching (ACQ) was observed in PQ. The phosphorescence lifetimes (τP) of the PQCl and PQBr aggregates were shown to be ∼22-62 µs and ∼22-59 µs, respectively. The ϕP of the powder samples is found to be 0.03% (PQ), 15.6% (PQCl), and 13.0% (PQBr), which are significantly lower than that of the aggregates (10-5 M, f w = 90%, v/v). Film (Zeonex, 0.1 wt %) studies revealed that ϕP of PQ (7.1%) is relatively high, while PQCl and PQBr exhibit relatively low ϕP values (PQCl, 9.7%; PQBr, 8.8%), as compared with that of powder samples. In addition, we found in single-crystal X-ray analysis that multiple noncovalent interactions along with halogen···halogen (Cl···Cl) interactions between the neighboring molecules play an important role to stabilize the 3CT caused by increased rigidity of the molecular backbone. This design principle reveals a method to understand nondegeneracy of 1CT and 3CT states, and RTP with a concentration-dependent AIP effect using halogen substituted twisted donor-acceptor conjugates.

Molecular-Level Understanding of Dual-RTP via Host-Sensitized Multiple Triplet-to-Triplet Energy Transfers and Data Security Application.

Dual-room-temperature phosphorescence (DRTP) from organic molecules is of utmost importance in chemical physics. The Dexter-type triplet-to-triplet energy transfer mechanism can therefore be used to achieve DRTP at ambient conditions. Here, we report two donor-acceptor (D-A)-based guests (CQN1, CQN2) in which the donor (D) and acceptor (A) parts are held in angular orientation around the C-N single bond. Spectroscopic analysis along with computational calculations revealed that both guests are incapable of emitting either thermally activated delayed fluorescence (TADF) or RTP at ambient conditions due to large singlet-triplet gaps, which are presented to show host (benzophenone, BP)-sensitized DRTP via multiple intermolecular triplet-to-triplet energy transfer (TTET) channels that originate from the triplet state (T1 BP) of BP to the triplet states (T1 D, T1 A) of the D and A parts (TTET-I:T1 BP → T1 D; TTET-II:T1 BP → T1 A). In addition, an intramolecular TTET channel that occurs from the T1 D to T1 A states of the D and A parts of CQN2 is also activated due to the low triplet (T1 D)-triplet (T1 A) gap at ambient conditions. The efficiency of TTET processes was found to be 100%. The phosphorescence quantum yields (ϕP) and lifetimes (τP) were shown to be 13-20% and 0.48-0.55 s, respectively. Given the high lifetime of the DRTP feature of both host-guest systems (1000:1 molar ratio), a data security application is achieved. This design principle provides the first solid proof that DRTP via radiative decay of the dark triplet states of the D and A parts of D-A-based non-TADF systems is possible, revealing a method to increase the efficiency and lifetime of DRTP.

Effect of π···π Interactions of Donor Rings on Persistent Room-Temperature Phosphorescence in D4-A Conjugates and Data Security Application.

Organic room-temperature phosphorescence (RTP) materials with persistent RTP (PRTP) have attracted huge interest in inks, bioimaging, and photodynamic therapy. However, the design principle to increase the lifetime of organic molecules is underdeveloped. Herein, we show donor(D4)-acceptor(A) molecules (TOEPh, TOCPh, TOMPh, TOF and TOPh) with similar orientation of donor rings in aggregates that cause a large number of noncovalent interactions. We observed that TOEPh, TOCPh, TOMPh and TOF showed PRTP, whereas TOPh showed only phosphorescence emission (ΦP = ∼11%) with no PRTP property at ambient conditions. The spectroscopic and single-crystal X-ray analyses confirm the molecular assembly via J-aggregation with a face-to-face orientation of the donor rings. The crystal structure analysis (TOEPh, TOCPh, TOMPh, TOF) reveals that moderate π···π interactions (3.706 to 4.065 Å) between the donor rings cause the enhancement of the phosphorescence lifetime (26 to 245 ms), whereas the short phosphorescence lifetime (12 ms) of TOPh was observed because of the absence of π···π interactions. We found that TOEPh shows a long lifetime (245 ms) as compared to other derivatives because of the presence of ethoxy (-OEt) groups that enables spin-orbit coupling caused by strong lone pair (O)···π interactions present in the molecule. Utilizing the PRTP feature of TOEPh and the fluorescence emission of TOPh, we have shown data security applications in poly(methyl methacrylate).

Thermally activated delayed fluorescence and room-temperature phosphorescence in naphthyl appended carbazole-quinoline conjugates, and their mechanical regulation.

The influences of naphthyl and/or phenyl rings at the 2,4-positions of the quinolinyl fragments in carbazole-quinoline conjugates are studied. The centric phase of one of the conjugates (ß-CQNN) revealed both thermally activated delayed fluorescence (TADF) and room-temperature phosphorescence (RTP), while prompt fluorescence and RTP were observed in the non-centric phase (α-CQNN) that can regenerate the emission features of ß-CQNNvia mechanical grinding. This unique observation is explained by the modulation of the higher-lying triplet (T2) energy level caused by conformational change.

Biluminescence via Fluorescence and Persistent Phosphorescence in Amorphous Organic Donor(D4)-Acceptor(A) Conjugates and Application in Data Security Protection.

Purely organic biluminescent materials are of great interest due to the involvement of both singlet and long-lived triplet emissions, which have been rarely reported in bioimaging and organic light-emitting diodes. We show two molecules 3,4,5,6-tetraphenyloxy-phthalonitrile (POP) and 3,4,5,6-tetrakis- p-tolyloxy-phthalonitrile (TOP), in which POP was found to exhibit fluorescence and persistent room-temperature green phosphorescence (pRTGP) in the amorphous powder and crystal states. Both POP and TOP show aggregation-induced emission in a tetrahydrofuran-water mixture. We found in single-crystal X-ray analysis that intra- and intermolecular lp(O)···π interactions along with π(C = C)···π(C≡N), hydrogen bond (H-B), and C-H···π interactions induce a head-to-tail slipped-stack arrangement in POP. In addition, the X-ray structure of TOP with a slipped-stack arrangement induced by only π(C═C)···π(C≡N) and H-B interactions shows dim afterglow only in crystals. These indicate that more noncovalent interactions found in POP may reinforce relatively efficient intersystem crossing that leads to pRTGP. Given the unique green afterglow feature in amorphous powder of POP, document security protection application is achievable.

Dual Emission through Thermally Activated Delayed Fluorescence and Room-Temperature Phosphorescence, and Their Thermal Enhancement via Solid-State Structural Change in a Carbazole-Quinoline Conjugate.

The emergence of single-component organic dual light emitters holds great promise for white light-emitting diodes (WLEDs) and biological detection due to the involvement of broad emission covering visible spectrum. Here we show experimental studies on dual emission of carbazole-quinoline conjugate (CQ) that exhibits both thermally activated delayed fluorescence (TADF) via reverse intersystem crossing (r ISC) from the higher-lying triplet state ( T2) to the singlet state ( S1) and room-temperature phosphorescence (RTP) from the lowest triplet state ( T1) due to low energy gap between T2 and S1, and energetic proximity of T1 with T2. We found in thermal effect that the intensity of the dual features is enhanced with increasing temperatures up to 100 °C, which can be explained by a thermal-induced structural change (TISC) mechanism that compensates the emission losses due to nonradiative transitions at elevated temperatures. This property, in addition to its enhanced TADF and phosphorescence decay rates (∼107 s-1and 101 s-1) at 100 °C, would have great promise for high-efficiency LEDs.

Conformational switching via an intramolecular H-bond modulates the fluorescence lifetime in a novel coumarin-imidazole conjugate.

Achieving synthetic control over light-driven molecular dynamics is essential for designing complex molecule-based devices. Here we design a novel coumarin-imidazole conjugate (1) whose excited state structural dynamics are primarily controlled by a distant intramolecular H-bonding interaction within the backbone. The coumarin conjugate is based on a 1,2,4,5-aryl substituted imidazole framework (aryl = -Ph and -PhOH) covalently connected to the coumarin moiety via a C-N bond. A carefully positioned OH group in the aryl part of the imidazole fragment resulted in achieving two dissimilar O-HN and O-HO distal intramolecular hydrogen bonding interactions. NMR studies in conjunction with density functional theory (DFT) at the B3LYP/6-311G(d,p) level of theory show the existence of two ground state conformers with a rotational barrier of 6.12 kcal mol-1. Due to the presence of conformational isomers of 1, the local excited state dynamics of the parent coumarin get biased towards a long-lived fluorescence state with diminished non-radiative decay channels. Time-resolved emission studies show an ∼4-5 times increase in the excited state lifetime in 1 when compared to coumarin-imidazole conjugates, 2 and 3, without the OH group. Solvent dependent studies show that solvent polarity, the H-bond donating ability and viscosity dictate the conformational distribution in the ground state and the dynamical evolution to the final emissive state. Our studies highlight the importance of rotamerism around the C1-C4 single bond, which leads to rigidification along the coumarin-imidazole backbone through a combination of distal H-bonding and solvent interactions. The concept of new emission signaling pathways caused by conformational switching between two states offers a new paradigm to introduce functional allostery in macromolecular backbones.

Regulating signal enhancement with coordination-coupled deprotonation of a hydrazone switch.

Proton relay plays an important role in many biocatalytic pathways. In order to mimic such processes in the context of molecular switches, we developed coordination-coupled deprotonation (CCD) driven signaling and signal enhancement sequences. This was accomplished by using the zinc(ii)-initiated CCD of a hydrazone switch to instigate an acid catalyzed imine bond hydrolysis that separates a quencher from a fluorophore thus leading to emission amplification. Because CCD is a reversible process, we were able to show that the catalysis can be regulated and turned "on" and "off" using a metalation/demetalation cycle.

A switching cascade of hydrazone-based rotary switches through coordination-coupled proton relays.

Imidazole, a subunit of histidine, plays a crucial role in proton-relay processes that are important for various biological activities, such as metal efflux, viral replication and photosynthesis. We show here how an imidazolyl ring incorporated into a rotary switch based on a hydrazone enables a switching cascade that involves proton relay between two different switches. The switching process starts with a single input, zinc(II), that initiates an E/Z isomerization in the hydrazone system through a coordination-coupled proton transfer. The resulting imidazolium ring is unusually acidic and, through proton relay, activates the E/Z isomerization of a non-coordinating pyridine-containing hydrazone switch. We hypothesize that the reduction in the acid dissociation constant of the imidazolium ring results from a combination of electrostatic and conformational effects, the study of which might help elucidate the proton-coupled electron-transfer mechanism in photosynthetic bacteria.

Effect of hydrogen-bonding on the excited-state reactivity of fullerene derivatives and its impact on the control of the emission polarisation from photopolic single crystals.

The kinetics of the irreversible photoinduced switch in polarisation (p) observed in single crystals of a fullerene derivative possessing hydrogen-bonding barbiturate units were investigated using confocal fluorescence microscopy. In the samples investigated, it was found that the maximum luminescence polarisation (p = 0.78) is obtained for an orientation of ca. 60° from the long axis of the crystal. Upon irradiation at 385 nm, the maximum luminescence polarisation undergoes a rotation of ca. 70° with respect to the initial orientation and reaches a new value of p = 0.40. The results indicate that the process is not dependent on the orientation of the incident polarised excitation beam and that it is not accompanied by a noticeable change in the photophysical properties of the crystal. Based on these observations, a mechanism is proposed in which photoinduced dimerisation occurs from the lowest energy emissive excimer-like state that acts as a sink for the excitation energy.

Direct formation of fullerene monolayers using [4+2] Diels-Alder cycloaddition.

The formation of covalent C(60) monolayers through [4+2] Diels-Alder cycloaddition between C(60) and anthracene monolayers grafted onto a silicon oxide surface was investigated by ellipsometry, fluorescence and by atomic force microscopy.

Self-assembly of supramolecular fullerene ribbons via hydrogen-bonding interactions and their impact on fullerene electronic interactions and charge carrier mobility.

The anisotropy of the electronic interactions between fullerenes in crystalline solids was examined using a confocal fluorescence microscope by probing the polarization of the fluorescence emission arising from fullerene excimer-like emitting states. Crystals of C(60) obtained by vacuum-sublimation or from chloroform solution exhibited no or little polarization (p = 0 or 0.11, respectively), as expected from the high symmetry of the C(60) fcc lattice or the low degree of anisotropy induced by included solvent molecules. The use of hydrogen-bonding to supramolecularly control interfullerene electronic interactions was explored using a fullerene derivative (1) combining a solubilizing 3,4-di-tert-butylbenzene group and a barbituric acid hydrogen-bonding (H-B) moiety. The crystal structure of 1 establishes the existence of fullerene H-B tapes along which interfullerene electronic interactions are expected to be large. In agreement with this, we observe very strong polarization of the fullerene excimer-like emission (p = 0.78), indicative of a high degree of anisotropy in the fullerene interactions. The charge-carrier mobility of 1 as determined from OFET devices was found to be lower than that of C(60) (1.2 x 10(-4) vs 1.2 x 10(-2) cm(2)/s V), which is rationalized on the basis of the reduced dimensionality of 1 as a wire-like semiconductor and variations in the morphology of the device active layer revealed by AFM measurements.

Ag(I) induced emission with azines having donor-acceptor-donor chromophore.

Two azine molecules, [3-{4-(dimethylamino)phenyl}prop-2-en-1-ylidene]hydrazone (HL) and [4-(dimethylamino)benzylidene]hydrazone (LL) synthesized via Schiff base condensation, show an absorption band due to intra-ligand charge transfer (ILCT). Both ligands show weak emission in the absence of a metal ion as input. When Ag(+) ions are added to either compound in THF, the metal ion gets bonded to the azine moiety resulting in a high intensity emission (approximately 400 fold). While Cu(+) shows a slight enhancement of emission, other first-row transition, alkali or alkaline-earth metal ions do not show any emission allowing Ag(+) ions to be detected in the presence of these metal ions. Both the Ag(+) complexes were characterised by X-ray crystallography and show solid-state spectra similar to their solution spectra. Time-resolved fluorescence measurements done on the complexes show two excited-state lifetimes.

A coumarin-derived fluorescence probe selective for magnesium.

Two different coumarin derivatives have been connected via an imine linkage to obtain a new fluorescence signaling system. This compound itself does not show any emission due to rapid isomerization around the C[double bond]N bond. However, in the presence of a Mg(II) ion, this isomerization is stopped because of bonding to the metal ion resulting in high-intensity (approximately 550-fold) emission. Other metal ions like Li(I), Ca(II), and Zn(II) show very little emission, while biologically relevant transition-metal ions do not show any emission. In this way, the Mg(II) ion can be detected in the presence of these ions.