Synthesis and Characterization of a Fluorescent Dianthraceno­indacene

Conerd K. Frederickson; Joshua E. Barker; Justin J. Dressler; Zheng Zhou; Evan R. Hanks; Jeremy P. Bard; Lev N. Zakharov; Marina A. Petrukhina; Michael M. Haley

doi:10.1055/s-0037-1610280

Synlett, Table of Contents

Synlett 2018; 29(19): 2562-2566
DOI: 10.1055/s-0037-1610280

cluster

Synthesis and Characterization of a Fluorescent Dianthracenoindacene

Authors

Conerd K. Frederickson

^aDepartment of Chemistry & Biochemistry and Materials Science Institute, University of Oregon, Eugene, Oregon 97403-1253, USA Email: haley@uoregon.edu
Joshua E. Barker

^aDepartment of Chemistry & Biochemistry and Materials Science Institute, University of Oregon, Eugene, Oregon 97403-1253, USA Email: haley@uoregon.edu
Justin J. Dressler

^aDepartment of Chemistry & Biochemistry and Materials Science Institute, University of Oregon, Eugene, Oregon 97403-1253, USA Email: haley@uoregon.edu
Zheng Zhou

^bDepartment of Chemistry, University of Albany, State University of New York, Albany, NY 12222-0100, USA
Evan R. Hanks

^aDepartment of Chemistry & Biochemistry and Materials Science Institute, University of Oregon, Eugene, Oregon 97403-1253, USA Email: haley@uoregon.edu
Jeremy P. Bard

^aDepartment of Chemistry & Biochemistry and Materials Science Institute, University of Oregon, Eugene, Oregon 97403-1253, USA Email: haley@uoregon.edu
Lev N. Zakharov

^cCAMCOR, University of Oregon, Eugene, Oregon 97403-1433, USA
Marina A. Petrukhina

^bDepartment of Chemistry, University of Albany, State University of New York, Albany, NY 12222-0100, USA
Michael M. Haley *

^aDepartment of Chemistry & Biochemistry and Materials Science Institute, University of Oregon, Eugene, Oregon 97403-1253, USA Email: haley@uoregon.edu

Abstract

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Published as part of the Cluster Synthesis of Materials

Abstract

A freely soluble dianthracenoindacene derivative has been synthesized using an ‘inside-out’ Friedel–Crafts alkylation method and is the first fluorescent diacenoindacene reported. Linear fusion of the anthracenes is confirmed by X-ray diffraction studies on the neutral molecule as well as its dianion. Based on predictions from our previous studies, this is also the least antiaromatic diacenoindacene derivative yet to be prepared, which is reflected in its highly negative and irreversible reduction. With its paratropicity essentially eliminated, we posit that the molecule is no longer deactivated by a conical intersection, typical of antiaromatic molecules, and therefore fluorescence is restored. This follows the trend shown in the related dianthracenopentalenes, with the reappearance of fluorescence when the outer acene groups are extended to linearly-fused anthracene moieties.

Key words

antiaromaticity - aromaticity - fluorescence - indacene - indenofluorene

Full Text

References

References and Notes
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38 Synthesis of Compound 1 Toluene (50 mL) was added to a degassed flask containing DDQ (60 mg, 0.26 mmol) and 4 (236 mg, 0.167 mmol). The reaction was heated at 80 °C for 2.5 h monitoring by TLC for disappearance of the fluorescent starting material spot. Once 4 was consumed, the cooled reaction mixture was passed through a SiO₂ plug using 3:2 hexanes/CH₂Cl₂ as eluent and then the solvent was removed in vacuo. The resulting crude solid was triturated with warm (ca. 70 °C) EtOH and filtered, which upon cooling resulted in a dark purple crystalline solid (191 mg, 80%). ¹H NMR (600 MHz, CDCl₃): δ = 8.85 (s, 2 H), 8.48 (ddt, J = 9.8, 7.2, 3.1 Hz, 4 H), 8.04 (s, 2 H), 7.53 (dt, J = 6.6, 3.3 Hz, 4 H), 7.19 (s, 2 H), 7.04 (s, 4 H), 1.27–1.17 (br s, 42 H), 1.11–1.06 (br s, 42 H). ¹³C NMR (151 MHz, CDCl₃): δ = 143.30, 142.86, 140.15, 140.12, 137.38, 137.04, 136.28, 133.87, 132.69, 132.59, 132.09, 129.56, 128.49, 127.37, 127.33, 127.12, 126.90, 119.84, 119.35, 119.24, 119.04, 115.56, 105.01, 104.72, 103.67, 103.63, 21.37, 20.45, 18.92, 18.81, 11.75, 11.52. UV-vis (cyclohexane): λ_max (ε) 651 (37900), 615 (93300), 570 (67550), 447 (102350), 426 (109000) nm. Fluorescence (cyclohexane): λ_max (Φ) 664 nm (0.01). HRMS (ESI): m/z calcd for C₉₈H₁₂₀Si₄ [M + H]⁺: 1409.8545; found: 1409.8503.

Supplementary Material

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Synthesis and Characterization of a Fluorescent Dianthraceno­indacene

Authors

Synthesis and Characterization of a Fluorescent Dianthracenoindacene