New Polymorphs of Perylene-Tetracyanoquinodimethane Charge Transfer Cocrystals

J. Henderson, M. Masino, L. E. Hatcher, G. Kociok-Köhn, T. Salzillo, A. Brillante, P. R. Raithby, A. Girlando, E. Da Como

Research output: Contribution to journalArticle

8 Citations (Scopus)

Abstract

We report two hitherto unknown polymorphs of the charge transfer (CT) cocrystal perylene:tetracyanoquinodimethane (TCNQ) grown by physical vapor transport (PVT) in argon atmosphere. One of the polymorphs, named β, has stoichiometry 1:1 and adds to the three known structures with stoichiometry 1:1 (α), 2:1, and 3:1. Interestingly, below (280 ± 10) K the β structure undergoes a phase transition to what we refer to as the γ polymorph, with halving of the unit cell and reduction of symmetry from monoclinic to triclinic. Both new crystal structures present two alternating stacks with different intermolecular and intramolecular geometries. In stack S-I the perylene molecules show substantial deviations from planarity, with the angle between the naphthalene intramolecular moieties of 6.69°, and with the perylene and TCNQ molecular centroids shifted by 1.95 Å. In the second stack, S-II, the perylene is planar, and the centroids almost coincident. Structural investigations on bond length complemented by vibrational IR spectroscopy indicate that in the new polymorphs the degree of charge transfer, ρ, can be 0 or 0.12. The higher value of ionicity to be due to donor-acceptor pairs in the S-II, while molecules in S-I are closer to neutrality. Thus, the ionicity of the donor-acceptor pair depends on the stack and is comparable to that of the α polymorph which we redetermined as ρ = 0.15 ± 0.05.

LanguageEnglish
Pages2003-2009
Number of pages7
JournalCrystal Growth and Design
Volume18
Issue number4
DOIs
StatusPublished - 4 Apr 2018

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Perylene
Polymorphism
Charge transfer
charge transfer
centroids
stoichiometry
Stoichiometry
Vibrational spectroscopy
naphthalene
Molecules
Argon
Crystal symmetry
Bond length
molecules
Naphthalene
argon
vapors
Infrared spectroscopy
deviation
atmospheres

ASJC Scopus subject areas

  • Chemistry(all)
  • Materials Science(all)
  • Condensed Matter Physics

Cite this

New Polymorphs of Perylene-Tetracyanoquinodimethane Charge Transfer Cocrystals. / Henderson, J.; Masino, M.; Hatcher, L. E.; Kociok-Köhn, G.; Salzillo, T.; Brillante, A.; Raithby, P. R.; Girlando, A.; Da Como, E.

In: Crystal Growth and Design, Vol. 18, No. 4, 04.04.2018, p. 2003-2009.

Research output: Contribution to journalArticle

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AB - We report two hitherto unknown polymorphs of the charge transfer (CT) cocrystal perylene:tetracyanoquinodimethane (TCNQ) grown by physical vapor transport (PVT) in argon atmosphere. One of the polymorphs, named β, has stoichiometry 1:1 and adds to the three known structures with stoichiometry 1:1 (α), 2:1, and 3:1. Interestingly, below (280 ± 10) K the β structure undergoes a phase transition to what we refer to as the γ polymorph, with halving of the unit cell and reduction of symmetry from monoclinic to triclinic. Both new crystal structures present two alternating stacks with different intermolecular and intramolecular geometries. In stack S-I the perylene molecules show substantial deviations from planarity, with the angle between the naphthalene intramolecular moieties of 6.69°, and with the perylene and TCNQ molecular centroids shifted by 1.95 Å. In the second stack, S-II, the perylene is planar, and the centroids almost coincident. Structural investigations on bond length complemented by vibrational IR spectroscopy indicate that in the new polymorphs the degree of charge transfer, ρ, can be 0 or 0.12. The higher value of ionicity to be due to donor-acceptor pairs in the S-II, while molecules in S-I are closer to neutrality. Thus, the ionicity of the donor-acceptor pair depends on the stack and is comparable to that of the α polymorph which we redetermined as ρ = 0.15 ± 0.05.

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