What is syncrystallization? States of the pH indicator methyl red in crystals of phthalic acid

Jason B. Benedict, Dawn E. Cohen, Scott Lovell, Andrew L. Rohl, Bart Kahr

Research output: Contribution to journalArticle

Abstract

The concept of syncrystallization was reinvestigated by focusing on phthalic acid (PA) grown with methyl red (MR). Crystals are alternately red and yellow in adjacent growth sectors. X-ray structures of MR and its cocrystals, revealing MR in the neutral, zwitterionic, and protonated states, as well as measurements of linear birefringence and linear dichroism of mixed crystals, were used to investigate mechanisms of PA coloring. These experiments were complemented by force field calculations of the lowest energy stable surfaces of expressed facets and energies of MR on and in crystals, as well as molecular orbital calculations of MR. Two MR species were detected in PA having distinct energies, polarizations, and face selectivities. Assignments of structures to these MRs, previously thought to be neutral and protonated, required a nuanced analysis of hydrogen bonds. The essential difference between yellow and red species is whether the MR carboxylic acid proton is inter- or intramolecularly hydrogen bound. Inferences about mixed crystal structure drawn from an examination of cocrystals of PA and MR are inconsistent with polarization spectroscopy signaling caution when using stoichiometric compounds as models of dilute solid solutions. Upon heating mixed crystals, linear dichroism diminishes and oriented, elongated pools of MR separate and pass through the bulk in directions perpendicular to the direction of elongation. These bâtonnets subsequently crystallize leaving macroscopic oriented crystals of a MR-rich phase within PA. No evidence was found for the simultaneous crystallization of MR and PA; however, the MR reorientation on heating as well as the separation and recrystallization of a MR-rich phase are distinct processes that could be embraced by the literal meaning of syncrystallization.

Original languageEnglish (US)
Pages (from-to)5548-5559
Number of pages12
JournalJournal of the American Chemical Society
Volume128
Issue number16
DOIs
StatePublished - Apr 26 2006

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Crystals
Acids
Dichroism
Crystallization
Polarization
Heating
Orbital calculations
Molecular orbitals
Coloring
Birefringence
Carboxylic acids
phthalic acid
methyl red
Elongation
Solid solutions
Hydrogen bonds
Protons
Hydrogen
Crystal structure
Spectroscopy

ASJC Scopus subject areas

  • Chemistry(all)

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What is syncrystallization? States of the pH indicator methyl red in crystals of phthalic acid. / Benedict, Jason B.; Cohen, Dawn E.; Lovell, Scott; Rohl, Andrew L.; Kahr, Bart.

In: Journal of the American Chemical Society, Vol. 128, No. 16, 26.04.2006, p. 5548-5559.

Research output: Contribution to journalArticle

Benedict, Jason B. ; Cohen, Dawn E. ; Lovell, Scott ; Rohl, Andrew L. ; Kahr, Bart. / What is syncrystallization? States of the pH indicator methyl red in crystals of phthalic acid. In: Journal of the American Chemical Society. 2006 ; Vol. 128, No. 16. pp. 5548-5559.
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