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

Overview

Journal ACS Omega

Publisher American Chemical Society

Specialty Chemistry

Date 2022 Feb 7

PMID 35128280

Authors

Nirmalya Acharya

Suvendu Dey

Raktim Deka

Debdas Ray

Affiliations

Soon will be listed here.

Abstract

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 (, ) 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 multiple intermolecular triplet-to-triplet energy transfer (TTET) channels that originate from the triplet state (T ) of BP to the triplet states (T , T ) of the D and A parts (TTET-I:T → T ; TTET-II:T → T ). In addition, an intramolecular TTET channel that occurs from the T to T states of the D and A parts of is also activated due to the low triplet (T )-triplet (T ) gap at ambient conditions. The efficiency of TTET processes was found to be 100%. The phosphorescence quantum yields (ϕ) and lifetimes (τ) 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 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.

Citing Articles

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

Karmakar S, Dey S, Upadhyay M, Ray D ACS Omega. 2022; 7(19):16827-16836.

PMID: 35601330 PMC: 9118413. DOI: 10.1021/acsomega.2c01909.

References

Bhattacharjee I, Hirata S . Highly Efficient Persistent Room-Temperature Phosphorescence from Heavy Atom-Free Molecules Triggered by Hidden Long Phosphorescent Antenna. Adv Mater. 2020; 32(31):e2001348. DOI: 10.1002/adma.202001348. View

Bhatia H, Dey S, Ray D . Effect of π···π Interactions of Donor Rings on Persistent Room-Temperature Phosphorescence in D-A Conjugates and Data Security Application. ACS Omega. 2021; 6(5):3858-3865. PMC: 7876834. DOI: 10.1021/acsomega.0c05666. View

Chai Z, Wang C, Wang J, Liu F, Xie Y, Zhang Y . Abnormal room temperature phosphorescence of purely organic boron-containing compounds: the relationship between the emissive behaviorand the molecular packing, and the potential related applications. Chem Sci. 2018; 8(12):8336-8344. PMC: 5858747. DOI: 10.1039/c7sc04098a. View

Alam P, Leung N, Liu J, Cheung T, Zhang X, He Z . Two Are Better Than One: A Design Principle for Ultralong-Persistent Luminescence of Pure Organics. Adv Mater. 2020; 32(22):e2001026. DOI: 10.1002/adma.202001026. View

Paul L, Chakrabarti S, Ruud K . Anomalous Phosphorescence from an Organometallic White-Light Phosphor. J Phys Chem Lett. 2017; 8(19):4893-4897. DOI: 10.1021/acs.jpclett.7b02148. View

Bhattacharjee I, Hayashi K, Hirata S . Key of Suppressed Triplet Nonradiative Transition-Dependent Chemical Backbone for Spatial Self-Tunable Afterglow. JACS Au. 2021; 1(7):945-954. PMC: 8395709. DOI: 10.1021/jacsau.1c00132. View

Qiu W, Cai X, Li M, Chen Z, Wang L, Xie W . Achieving Purely Organic Room-Temperature Phosphorescence Mediated by a Host-Guest Charge Transfer State. J Phys Chem Lett. 2021; 12(19):4600-4608. DOI: 10.1021/acs.jpclett.1c01095. View

Gan N, Wang X, Ma H, Lv A, Wang H, Wang Q . Manipulating the Stacking of Triplet Chromophores in the Crystal Form for Ultralong Organic Phosphorescence. Angew Chem Int Ed Engl. 2019; 58(40):14140-14145. DOI: 10.1002/anie.201907572. View

Yang J, Zhen X, Wang B, Gao X, Ren Z, Wang J . The influence of the molecular packing on the room temperature phosphorescence of purely organic luminogens. Nat Commun. 2018; 9(1):840. PMC: 5826932. DOI: 10.1038/s41467-018-03236-6. View

10.

Yang J, Zhang Y, Wu X, Dai W, Chen D, Shi J . Rational design of pyrrole derivatives with aggregation-induced phosphorescence characteristics for time-resolved and two-photon luminescence imaging. Nat Commun. 2021; 12(1):4883. PMC: 8361132. DOI: 10.1038/s41467-021-25174-6. View

11.

Paul L, Moitra T, Ruud K, Chakrabarti S . Strong Duschinsky Mixing Induced Breakdown of Kasha's Rule in an Organic Phosphor. J Phys Chem Lett. 2019; 10(3):369-374. DOI: 10.1021/acs.jpclett.8b03624. View

12.

Bhattacharjee I, Acharya N, Ray D . Thermally activated delayed fluorescence and room-temperature phosphorescence in naphthyl appended carbazole-quinoline conjugates, and their mechanical regulation. Chem Commun (Camb). 2019; 55(13):1899-1902. DOI: 10.1039/c8cc09220f. View

13.

Luo X, Han Y, Chen Z, Li Y, Liang G, Liu X . Mechanisms of triplet energy transfer across the inorganic nanocrystal/organic molecule interface. Nat Commun. 2020; 11(1):28. PMC: 6946700. DOI: 10.1038/s41467-019-13951-3. View

14.

Xie Z, Zhang X, Wang H, Huang C, Sun H, Dong M . Wide-range lifetime-tunable and responsive ultralong organic phosphorescent multi-host/guest system. Nat Commun. 2021; 12(1):3522. PMC: 8192513. DOI: 10.1038/s41467-021-23742-4. View

15.

Bolton O, Lee K, Kim H, Lin K, Kim J . Activating efficient phosphorescence from purely organic materials by crystal design. Nat Chem. 2011; 3(3):205-10. DOI: 10.1038/nchem.984. View

16.

Grosskopf J, Kratz T, Rigotti T, Bach T . Enantioselective Photochemical Reactions Enabled by Triplet Energy Transfer. Chem Rev. 2021; 122(2):1626-1653. DOI: 10.1021/acs.chemrev.1c00272. View

17.

He G, Du L, Gong Y, Liu Y, Yu C, Wei C . Crystallization-Induced Red Phosphorescence and Grinding-Induced Blue-Shifted Emission of a Benzobis(1,2,5-thiadiazole)-Thiophene Conjugate. ACS Omega. 2019; 4(1):344-351. PMC: 6648371. DOI: 10.1021/acsomega.8b02805. View

18.

Yoshii R, Hirose A, Tanaka K, Chujo Y . Functionalization of boron diiminates with unique optical properties: multicolor tuning of crystallization-induced emission and introduction into the main chain of conjugated polymers. J Am Chem Soc. 2014; 136(52):18131-9. DOI: 10.1021/ja510985v. View

19.

He Z, Zhao W, Lam J, Peng Q, Ma H, Liang G . White light emission from a single organic molecule with dual phosphorescence at room temperature. Nat Commun. 2017; 8(1):416. PMC: 5583377. DOI: 10.1038/s41467-017-00362-5. View

20.

Itoh T . Fluorescence and phosphorescence from higher excited states of organic molecules. Chem Rev. 2012; 112(8):4541-68. DOI: 10.1021/cr200166m. View