Rigid Core Anthracene and Anthraquinone Linked Nitronyl and Iminoyl Nitroxide Biradicals

Akpinar, Handan; Schlueter, John A.; Allão Cassaro, Rafael A.; Friedman, Jonathan R.; Lahti, Paul M.

doi:10.1021/acs.cgd.6b00588

Rigid Core Anthracene and Anthraquinone Linked Nitronyl and Iminoyl Nitroxide Biradicals

Journal Article · Thu May 26 00:00:00 EDT 2016 · Crystal Growth and Design

DOI:https://doi.org/10.1021/acs.cgd.6b00588· OSTI ID:1345415

Akpinar, Handan ^[1]; Schlueter, John A. ^[2]; Allão Cassaro, Rafael A. ^[3]; Friedman, Jonathan R. ^[4]; Lahti, Paul M. ^[1]

Univ. of Massachusetts, Amherst, MA (United States)
National Science Foundation, Arlington, VA (United States)
Univ. Federal do Rio de Janeiro (Brazil)
Amherst College, MA (United States)

The first syntheses of bis(nitronyl nitroxide) and bis(iminoyl nitroxide) (diNN, diIN) biradicals linked through rigid acene core conjugating anthracene (A) and anthraquinone (AQ) units are reported. Computational modeling predicts weak intramolecular exchange in AQ-linked systems, but A-linked biradicals to have ground state multiplicities consistent with the Borden-Davidson disjointness model. Solution electron spin resonance spectra showed inter-radical exchange-coupled triplet states, except for 2,6-AQ biradicals showing isolated spin spectra. Crystallography of the A-linked biradicals shows a key role for inter-radical contacts for molecular packing. DiINs showed lower-dimensional dyad packing with disorder at the radical units: the conformationally more symmetrical diNNs gave staircase one-dimensional or brickwork two-dimensional lattices. Core anthracene unit stacking was only seen in two systems with bromine on the central anthracene ring: the (large) bromine occupies alternate side placement in dyad stacks for the diIN, chain stacks for the diNN. Magnetism of 2,7-A-linked systems showed predominant ferromagnetic intramolecular triplet-singlet splitting of 24–28 K for diNNs and 8 K for diINs, plus weak antiferromagnetic (AFM) interactions from intermolecular contacts. Furthermore, the 2,6-A-linked biradicals showed AFM exchange between spins. Both A and AQ cores offer possibilities for electronic material development, with a combination of multiple radical spins and π-electron-rich acene cores.

View Accepted Manuscript (DOE)

Research Organization:: Argonne National Laboratory (ANL), Argonne, IL (United States)

Sponsoring Organization:: National Science Foundation; USDOE

Grant/Contract Number:: AC02-06CH11357

OSTI ID:: 1345415

Journal Information:: Crystal Growth and Design, Journal Name: Crystal Growth and Design Journal Issue: 7 Vol. 16; ISSN 1528-7483

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: ENGLISH

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CCDC 1435874: Experimental Crystal Structure Determination Akpinar, Handan; Schlueter, John A.; Cassaro, Rafael A. Allão https://doi.org/10.5517/ccdc.csd.cc1k64jf The current record is supplemented by this dataset	dataset	January 2016
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Rigid Core Anthracene and Anthraquinone Linked Nitronyl and Iminoyl Nitroxide Biradicals

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