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···πinteractions (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···πinteractions. 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)···πinteractions 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). © 2021 The Authors. Published by American Chemical Society.

Debdas Ray

Chemistry

(SoNS) School of Natural Sciences

Bhatia H.

Dey S.

Fulltext

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Shiv Nadar University

ACS Omega

Pure organic white light emitters with an afterglow (AG) feature have unique advantages and various potential applications. However, the studies of single-component organic white light emitters with AG and visible light excitation (VLE)-dependent efficient room-temperature phosphorescence (RTP) features remain a challenging area of research in photophysics. Herein, we synthesize three terephthalonitriles in which 2,3,5,6-positions are covalently attached to 2-fluoro-phenoxy (TOF), 2-chloro-phenoxy (TOC), and 2-methoxy-phenoxy groups (TOM) to give twisted geometries. We observed that powder samples of both TOC and TOM show white light emission with CIE coordinates of (0.32, 0.38) and (0.26, 0.33), respectively, while TOM gives VLE-dependent efficient RTP under ambient conditions. In addition, both TOC and TOF exhibit a dim AG feature. Spectroscopic studies reveal that dual emission of these chromophores originates via radiative decay of monomeric excited states (singlet, triplet), dimer-like excited states (DLES) (singlet, triplet), and aggregated triplet states. Detailed spectroscopic and X-ray analyses reveal the signature of DLES that is formed via conformational reorganization of the phenoxy donors in the excited states. Single-crystal X-ray diffraction analysis shows that the multiple lp(O)···π(CN)/C=C, Cl/F···π, and hydrogen-bonding interactions in the X-ray structures play a significant role in facilitating intersystem crossing, stabilizing multiple triplet states, and suppressing nonradiative decay, thereby triggering dim afterglow under ambient conditions. We found that TOC and TOF exhibit persistent RTP (PRTP) with lifetimes of 139 and 736 ms, respectively, when they are embedded in the polyvinyl alcohol matrix. Given the PRTP feature, invisible security ink application is developed. These results provide a guidance to design white light-emitting materials with afterglow and visible light-activated efficient RTP features. Copyright © 2019 American Chemical Society.

Journal of Physical Chemistry C

Use of Dimeric Excited States of the Donors in D4-A Systems for Accessing White Light Emission, Afterglow, and Invisible Security Ink

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 (β-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 β-CQNNvia mechanical grinding. This unique observation is explained by the modulation of the higher-lying triplet (T2) energy level caused by conformational change. © The Royal Society of Chemistry.

Chemical Communications

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

Achieving red phosphorescence from purely organic system is a challenging feat due to the predominant thermal nonradiative decay pathways of the excited electrons. Here, we design single-component charge-transfer (CT) complexes based on phenoxazine-quinoline conjugates (PQ1-PQ3), in which the phenoxazine ring is covalently attached to the quinolinyl fragment via a C-N bond. These conjugates in concentration-dependent absorption studies show a new low-energy CT absorption band along with the parent Ï€-Ï€∗ band with binding constants of up to 102 M-1 due to self-association via intermolecular CT (I2CT). Steady-state emission and phosphorescence decay transient measurements of all of the conjugates in solutions, thin films, and crystals reveal the signature of I2CT that leads to orange-red phosphorescence (ORP) at ambient conditions. Theoretical calculations show the existence of dimer with stronger I2CT characteristics and reduced energy gap between the lowest singlet (S1) and triplet (T1) states (Î"EST = 0.05-0.14 eV), which is in line with emission measurements. These conjugates are used for solid-state dichloromethane vapor sensors, and PQ3 can be transformed into oxygen sensor. These studies give an insight into the ORP properties and provide a rational strategy for the design of single-component self-CT complexes with ORP feature at ambient conditions. © 2018 American Chemical Society.

Roomerature Orange-Red Phosphorescence by Way of Intermolecular Charge Transfer in Single-Component Phenoxazine-Quinoline Conjugates and Chemical Sensing

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. Copyright © 2018 American Chemical Society.

Journal of Physical Chemistry Letters

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