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.

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).

Formation of spherical and core-shell polymeric microparticles from glycopolymers.

6-O-methacryloyl-α-d-glucoside 2 and 4-bromophenyl-6-O-methacryloyl-d-glucothioside 7, obtained by enzyme-catalyzed synthesis, have been homo-polymerized and copolymerized with styrene by a free radical process, yielding polymer materials with sugar moieties, attached to the polymer backbone via ester linkages. The results demonstrated that modifying the structural features of the monomers greatly affected the thermal and rheological properties of the polymers. The polymer materials obtained have been characterized by NMR, MALDI-MS, DSC, AFM, and EWC (equilibrium water content). The AFM images indicated the formation of spherical and core-shell polymeric microparticles.

Metal-free direct amination/aromatization of 2-cyclohexenones to iodo-N-arylanilines and N-arylanilines promoted by iodine.

An iodine mediated aromatization leading to a one-pot synthesis of iodo-N-arylanilines and N-arylanilines is reported. This highly regioselective aliphatic-aromatic transformation can be performed with various combinations of 2-cyclohexenones and anilines. The presence of a directing group is crucial for achieving high yields.

Linear or cross-shaped di(cyclopentadienyltitanium) compounds with aryl or heteroaryl spacers.

The preparation of hexamethylated and hexabenzylated arylene or heteroarylene bridged dinuclear di(cyclopentadienyltitanium) compounds from the reaction of the corresponding hexachlorides with methyllithium or benzylmagnesium chloride is described. The spacers between the cyclopentadienyl rings consist of one, two or three phenylene groups, a dioctyloxyphenylene group or a 2,2'-bithienylene group. The corresponding hexachlorides and hexaisopropoxides have also been prepared.