Highly Efficient Color-tunable Organic Co-crystals Unveiling Polymorphism, Isomerism, Delayed Fluorescence for Optical Waveguides and Cell-imaging

Overview

Journal Nat Commun

Specialty Biology

Date 2023 Oct 20

PMID 37863932

Authors

Debasish Barman

Mari Annadhasan

Anil Parsram Bidkar

Pachaiyappan Rajamalli

Debika Barman

Siddhartha Sankar Ghosh

Rajadurai Chandrasekar

Parameswar Krishnan Iyer

Affiliations

Soon will be listed here.

Abstract

Photofunctional co-crystal engineering strategies based on donor-acceptor π-conjugated system facilitates expedient molecular packing, consistent morphology, and switchable optical properties, conferring synergic 'structure-property relationship' for optoelectronic and biological functions. In this work, a series of organic co-crystals were formulated using a twisted aromatic hydrocarbon (TAH) donor and three diverse planar acceptors, resulting in color-tunable solid and aggregated state emission via variable packing and through-space charge-transfer interactions. While, adjusting the strength of acceptors, a structural transformation into hybrid stacking modes ultimately results in color-specific polymorphs, a configurational cis-isomer with very high photoluminescence quantum yield. The cis-isomeric co-crystal exhibits triplet-harvesting thermally activated delayed fluorescence (TADF) characteristics, presenting a key discovery in hydrocarbon-based multicomponent systems. Further, 1D-microrod-shaped co-crystal acts as an efficient photon-transducing optical waveguides, and their excellent dispersibility in water endows efficient cellular internalization with bright cell imaging performances. These salient approaches may open more avenues for the design and applications of TAH based co-crystals.

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References

Lei Y, Jin Y, Zhou D, Gu W, Shi X, Liao L . White-light emitting microtubes of mixed organic charge-transfer complexes. Adv Mater. 2012; 24(39):5345-51. DOI: 10.1002/adma.201201493. View

Barman D, Annadhasan M, Chandrasekar R, Iyer P . Hot-exciton harvesting through-space single-molecule based white-light emission and optical waveguides. Chem Sci. 2022; 13(31):9004-9015. PMC: 9365089. DOI: 10.1039/d2sc02172b. View

Zhai C, Yin X, Niu S, Yao M, Hu S, Dong J . Molecular insertion regulates the donor-acceptor interactions in cocrystals for the design of piezochromic luminescent materials. Nat Commun. 2021; 12(1):4084. PMC: 8253821. DOI: 10.1038/s41467-021-24381-5. View

Karothu D, Dushaq G, Ahmed E, Catalano L, Polavaram S, Ferreira R . Mechanically robust amino acid crystals as fiber-optic transducers and wide bandpass filters for optical communication in the near-infrared. Nat Commun. 2021; 12(1):1326. PMC: 7910442. DOI: 10.1038/s41467-021-21324-y. View

Rajamalli P, Rizzi F, Li W, Jinks M, Gupta A, Laidlaw B . Using the Mechanical Bond to Tune the Performance of a Thermally Activated Delayed Fluorescence Emitter*. Angew Chem Int Ed Engl. 2021; 60(21):12066-12073. PMC: 8251797. DOI: 10.1002/anie.202101870. View

Garain S, Ansari S, Kongasseri A, Chandra Garain B, Pati S, George S . Room temperature charge-transfer phosphorescence from organic donor-acceptor Co-crystals. Chem Sci. 2022; 13(34):10011-10019. PMC: 9430718. DOI: 10.1039/d2sc03343g. View

Huang Y, Xing J, Gong Q, Chen L, Liu G, Yao C . Reducing aggregation caused quenching effect through co-assembly of PAH chromophores and molecular barriers. Nat Commun. 2019; 10(1):169. PMC: 6329816. DOI: 10.1038/s41467-018-08092-y. View

Wang Y, Sun L, Wang C, Yang F, Ren X, Zhang X . Organic crystalline materials in flexible electronics. Chem Soc Rev. 2018; 48(6):1492-1530. DOI: 10.1039/c8cs00406d. View

Boterashvili M, Lahav M, Shankar S, Facchetti A, van der Boom M . On-surface solvent-free crystal-to-co-crystal conversion by non-covalent interactions. J Am Chem Soc. 2014; 136(34):11926-9. DOI: 10.1021/ja5066587. View

10.

Yan D, Delori A, Lloyd G, Friscic T, Day G, Jones W . A cocrystal strategy to tune the luminescent properties of stilbene-type organic solid-state materials. Angew Chem Int Ed Engl. 2011; 50(52):12483-6. DOI: 10.1002/anie.201106391. View

11.

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

12.

Cui L, Ruan S, Bencheikh F, Nagata R, Zhang L, Inada K . Long-lived efficient delayed fluorescence organic light-emitting diodes using n-type hosts. Nat Commun. 2017; 8(1):2250. PMC: 5740151. DOI: 10.1038/s41467-017-02419-x. View

13.

Harada J, Ohtani M, Takahashi Y, Inabe T . Molecular motion, dielectric response, and phase transition of charge-transfer crystals: acquired dynamic and dielectric properties of polar molecules in crystals. J Am Chem Soc. 2015; 137(13):4477-86. DOI: 10.1021/jacs.5b00412. View

14.

Qin Z, Gao H, Dong H, Hu W . Organic Light-Emitting Transistors Entering a New Development Stage. Adv Mater. 2021; 33(31):e2007149. DOI: 10.1002/adma.202007149. View

15.

Samanta P, Kim D, Coropceanu V, Bredas J . Up-Conversion Intersystem Crossing Rates in Organic Emitters for Thermally Activated Delayed Fluorescence: Impact of the Nature of Singlet vs Triplet Excited States. J Am Chem Soc. 2017; 139(11):4042-4051. DOI: 10.1021/jacs.6b12124. View

16.

Rajamalli P, Senthilkumar N, Huang P, Ren-Wu C, Lin H, Cheng C . New Molecular Design Concurrently Providing Superior Pure Blue, Thermally Activated Delayed Fluorescence and Optical Out-Coupling Efficiencies. J Am Chem Soc. 2017; 139(32):10948-10951. DOI: 10.1021/jacs.7b03848. View

17.

Etherington M, Gibson J, Higginbotham H, Penfold T, Monkman A . Revealing the spin-vibronic coupling mechanism of thermally activated delayed fluorescence. Nat Commun. 2016; 7:13680. PMC: 5141373. DOI: 10.1038/ncomms13680. View

18.

Bidkar A, Sanpui P, Ghosh S . Red Blood Cell-Membrane-Coated Poly(Lactic--glycolic Acid) Nanoparticles for Enhanced Chemo- and Hypoxia-Activated Therapy. ACS Appl Bio Mater. 2022; 2(9):4077-4086. DOI: 10.1021/acsabm.9b00584. View

19.

Goetz K, Fonari A, Vermeulen D, Hu P, Jiang H, Diemer P . Freezing-in orientational disorder induces crossover from thermally-activated to temperature-independent transport in organic semiconductors. Nat Commun. 2014; 5:5642. DOI: 10.1038/ncomms6642. View

20.

Ma Y, Xiao G, Fang X, Chen T, Yan D . Leveraging Crystalline and Amorphous States of a Metal-Organic Complex for Transformation of the Photosalient Effect and Positive-Negative Photochromism. Angew Chem Int Ed Engl. 2022; 62(11):e202217054. DOI: 10.1002/anie.202217054. View