We report the first synthesis of norbornyl-bridged acene dimers (2 and 3) with well-defined and controlled spatial relationships between the acene chromophore subunits. We employ a modular 2-D strategy wherein the central module, common to all our compounds, is a norbornyl moiety. The acenes are attached to this module using the Diels-Alder reaction, which also forms one of the acene rings. Manipulation of the Diels-Alder adducts provides the desired geometrically defined bis-acenes. The modular nature of this synthesis affords flexibility and allows for the preparation of a variety of acene dimers, including functionalized tetracene dimers.
Download full-text PDF |
Source |
|---|---|
| http://dx.doi.org/10.1021/acs.joc.7b00602 | DOI Listing |
Publication Analysis
Top Keywords
Similar Publications
Insight into the Excited States in Monomers and π-Stacked Dimers of Azulene-Fused Acenes: ADC(2) and TD-DFT Studies.
J Phys Chem A
January 2025
Department of Chemistry, Indian Institute of Technology, Guwahati 781039, India.
Charge transfer (CT) states in polycyclic aromatic hydrocarbons play crucial roles in determining their electronic properties and their potential applications in organic electronics. In this work, we investigate the nature of the excited states in monomers and π-stacked dimers of azulene-fused naphthalene and anthracene systems, focusing on the interplay between structure and excited-state properties. Four different isomers for azulene-fused naphthalene (, , , and ) and anthracene (, , , and ) are considered.
View Article and Find Full Text PDFThe Acetylene Bridge in Intramolecular Singlet Fission: A Boon or A Nuisance?
Angew Chem Int Ed Engl
December 2024
Solid State and Structural Chemistry Unit, Indian Institute of Science, Bangalore, 560012, India.
Various analogues of the alkylsilylacetylene group are frequently used as auxiliary groups to enhance the solubility and stability of the acene dimer core, widely used as platforms to investigate intramolecular singlet fission (iSF) mechanisms. However, while in the 2,2'-linked dimers they are primarily auxiliary groups, these are essential fragments of the bridging units in 6,6'/5,5'-linked dimers, the two preferred choices for dimerization. The starkly different iSF dynamics observed in the two variants raise the question of what role the acetylene bridges play.
View Article and Find Full Text PDFAn aza-Diels-Alder approach to nitrogen-containing tetrabenzoacene derivatives.
RSC Adv
September 2024
Department of Materials Science and Engineering, University of California, Irvine Irvine CA 92697 USA
Acenes and -heteroacenes have been synthesized and studied for over a century because of their fundamentally interesting materials properties and promise for device applications. Within this context, our laboratory has previously synthesized nitrogen-containing tetrabenzo[,,,]pentacenes an aza-Diels-Alder reaction-based approach, and herein, we expand our methodology to obtain substituted, expanded, functionalized, and dimeric tetrabenzoacenes. Overall, our study adds to the limited number of tetrabenzoacene derivatives reported to date and may open further opportunities for these materials in organic optoelectronics applications.
View Article and Find Full Text PDFComputational Studies of Dimerization of []-Cyclacenes.
J Phys Chem A
August 2024
Institut für Organische Chemie, Eberhard Karls Universität Tübingen, Auf der Morgenstelle 18, Tübingen 72076, Germany.
Cyclacenes, CH, consist of linearly fused benzene rings that are arranged to result in a closed nanohoop structure. Cyclacenes are thus the cyclic versions of acenes and have so far escaped synthesis. In order to estimate the tendency of []-cyclacenes (6 ≤ ≤ 20) to undergo dimerization, which is assumed to be a major pathway of degradation under oxygen-free conditions, we here report the energy of dimerization as computed by density functional theory using spin-restricted, spin-unrestricted, and thermally assisted-occupation (TAO) formalisms.
View Article and Find Full Text PDFNear-IR Emissive B-N Lewis Pair-Functionalized Anthracenes via Selective LUMO Extension in Conjugated Dimer and Polymer.
Angew Chem Int Ed Engl
November 2024
Department of Chemistry, Rutgers, The State University-Newark, 73 Warren Street, Newark, NJ 07102, USA.
Acenes are attractive as building blocks for low gap organic materials with applications, for example, in organic light emitting diodes, solar cells, bioimaging and diagnostics. Previously, we have shown that modification of dipyridylanthracene via B-N Lewis pair fusion (BDPA) strongly redshifts the emission, while facilitating self-sensitized reactivity toward O to reversibly generate the corresponding endoperoxides. Herein, we report on the further expansion of the π-system of BDPA to a vinyl-substituted monomer, vinylene-bridged dimer, and a polymer with an average of 20 chromophores.
View Article and Find Full Text PDFWant AI Summaries of new PubMed Abstracts delivered to your In-box?
Enter search terms and have AI summaries delivered each week - change queries or unsubscribe any time!