A Cross-shaped Organic Framework: a Multi-functional Template Arranging Chromophores

Overview

Journal Org Chem Front

Date 2024 Dec 26

PMID 39722802

Authors

Camiel C E Kroonen

Adriano DAddio

Allesandro Prescimone

Daniel Haussinger

Marcel Mayor

Affiliations

Soon will be listed here.

Abstract

This work explores the use of a cross-shaped organic framework that is used as a template for the investigation of multi-functionalized chromophores. We report the design and synthesis of a universal cross-shaped building block bearing two bromines and two iodines on its peripheral positions. The template can be synthesized on a gram scale in a five-step reaction comprising an oxidative homo-coupling macro-cyclization. The formed scaffold was selectively functionalized Suzuki cross-coupling reactions with methoxynaphthalene, naphthalimide and BODIPY derivatives, yielding a library of cross-shaped and chromophore-decorated model compounds, all of which were fully characterized. The formed racemic bis- and tetra-substituted crosses were resolved chiral stationary phase HPLC, and assignment of the enantiomers was done comparison of experimental and simulated electronic circular dichroism spectra as well as enantiomer single-crystal analysis. Additionally, the hybrid naphthalimide/BODIPY chromophore was found to be acting as an intramolecular Förster energy resonance transfer pair, which was investigated in more detail. With this easy-to-functionalize universal building block, we believe it might prove to be useful in the study of different sets of chromophores.

References

Benkhaya S, Mrabet S, El Harfi A . Classifications, properties, recent synthesis and applications of azo dyes. Heliyon. 2020; 6(1):e03271. PMC: 7002841. DOI: 10.1016/j.heliyon.2020.e03271. View

Saravanan V, Ganesan S, Rajakumar P . Synthesis and DSSC application of BODIPY decorated triazole bridged and benzene nucleus cored conjugated dendrimers. RSC Adv. 2022; 10(31):18390-18399. PMC: 9053714. DOI: 10.1039/d0ra01672a. View

Kroonen C, Hinaut A, DAddio A, Prescimone A, Haussinger D, Navarro-Marin G . Toward Molecular Textiles: Synthesis and Characterization of Molecular Patches. Chemistry. 2024; 30(69):e202402866. PMC: 11632409. DOI: 10.1002/chem.202402866. View

Xu M, Han J, Zhang Y, Yang X, Zang L . A selective fluorescence turn-on sensor for trace vapor detection of hydrogen peroxide. Chem Commun (Camb). 2013; 49(100):11779-81. DOI: 10.1039/c3cc47631f. View

Nitti A, Pasini D . Aggregation-Induced Circularly Polarized Luminescence: Chiral Organic Materials for Emerging Optical Technologies. Adv Mater. 2020; 32(41):e1908021. DOI: 10.1002/adma.201908021. View

Josse P, Favereau L, Shen C, Dabos-Seignon S, Blanchard P, Cabanetos C . Enantiopure versus Racemic Naphthalimide End-Capped Helicenic Non-fullerene Electron Acceptors: Impact on Organic Photovoltaics Performance. Chemistry. 2017; 23(26):6277-6281. DOI: 10.1002/chem.201701066. View

Zhai J, Pan T, Zhu J, Xu Y, Chen J, Xie Y . Boronic acid functionalized boron dipyrromethene fluorescent probes: preparation, characterization, and saccharides sensing applications. Anal Chem. 2012; 84(23):10214-20. DOI: 10.1021/ac301456s. View

Luo Q, Li L, Ma H, Lv C, Jiang X, Gu X . Deep-red fluorescence from isolated dimers: a highly bright excimer and imaging . Chem Sci. 2021; 11(23):6020-6025. PMC: 8159302. DOI: 10.1039/d0sc01873b. View

Sidler E, Malincik J, Prescimone A, Mayor M . Induced axial chirality by a tight belt: naphthalene chromophores fixed in a 2,5-substituted cofacial -phenylene-ethynylene framework. J Mater Chem C Mater. 2021; 9(45):16199-16207. PMC: 8614465. DOI: 10.1039/d1tc02180j. View

10.

Hestand N, Spano F . Expanded Theory of H- and J-Molecular Aggregates: The Effects of Vibronic Coupling and Intermolecular Charge Transfer. Chem Rev. 2018; 118(15):7069-7163. DOI: 10.1021/acs.chemrev.7b00581. View

11.

Telfer S, McLean T, Waterland M . Exciton coupling in coordination compounds. Dalton Trans. 2011; 40(13):3097-108. DOI: 10.1039/c0dt01226b. View

12.

Martinez L, Scaiano J . Characterization of the transient intermediates generated from the photoexcitation of nabumetone: a comparison with naproxen. Photochem Photobiol. 1998; 68(5):646-51. View

13.

Shrestha D, Jenei A, Nagy P, Vereb G, Szollosi J . Understanding FRET as a research tool for cellular studies. Int J Mol Sci. 2015; 16(4):6718-56. PMC: 4424985. DOI: 10.3390/ijms16046718. View

14.

Rodriguez-Muniz G, Gomez-Mendoza M, Nuin E, Andreu I, Marin M, Miranda M . "Snorkelling" vs. "diving" in mixed micelles probed by means of a molecular bathymeter. Org Biomol Chem. 2017; 15(48):10281-10288. DOI: 10.1039/c7ob02595e. View

15.

Dhbaibi K, Favereau L, Srebro-Hooper M, Jean M, Vanthuyne N, Zinna F . Exciton coupling in diketopyrrolopyrrole-helicene derivatives leads to red and near-infrared circularly polarized luminescence. Chem Sci. 2018; 9(3):735-742. PMC: 5872492. DOI: 10.1039/c7sc04312k. View

16.

Li J, Zhuang Z, Lou X, Zhao Z, Tang B . Molecular Design and Biomedical Application of AIEgens with Photochemical Activity. Chem Biomed Imaging. 2024; 1(9):785-795. PMC: 11504000. DOI: 10.1021/cbmi.3c00038. View

17.

DAddio A, Malincik J, Fuhr O, Fenske D, Haussinger D, Mayor M . Geländer Molecules with Orthogonal Joints: Synthesis of Macrocyclic Dimers. Chemistry. 2022; 28(56):e202201678. PMC: 9804589. DOI: 10.1002/chem.202201678. View

18.

Bozzi I, Machado L, Diogo E, Delolo F, Barros L, Graca G . Electrochemical Diselenation of BODIPY Fluorophores for Bioimaging Applications and Sensitization of O. Chemistry. 2023; 30(11):e202303883. DOI: 10.1002/chem.202303883. View

19.

Dhbaibi K, Matozzo P, Abella L, Jean M, Vanthuyne N, Autschbach J . Exciton coupling chirality in helicene-porphyrin conjugates. Chem Commun (Camb). 2021; 57(82):10743-10746. DOI: 10.1039/d1cc03314j. View

20.

Langhals H, Hofer A, Bernhard S, Siegel J, Mayer P . Axially chiral bichromophoric fluorescent dyes. J Org Chem. 2011; 76(3):990-2. DOI: 10.1021/jo102254a. View