Rationalization of the color properties of fluorescein in the solid state: a combined computational and experimental study
Authors
Eddleston, Mark D
Day, Graeme M
Bučar, Dejan-Krešimir
Publication Date
2016-06-15Journal Title
Chemistry - A European Journal
ISSN
0947-6539
Publisher
Wiley
Volume
22
Pages
10065-10073
Language
English
Type
Article
This Version
VoR
Metadata
Show full item recordCitation
Arhangelskis, M., Eddleston, M. D., Reid, D., Day, G. M., Bučar, D., Morris, A., & Jones, B. (2016). Rationalization of the color properties of fluorescein in the solid state: a combined computational and experimental study. Chemistry - A European Journal, 22 10065-10073. https://doi.org/10.1002/chem.201601340
Abstract
Fluorescein is known to exist in three tautomeric forms defined as quinoid, zwitterionic and lactoid. In the solid state, the quinoid and zwitterionic forms give rise to red and yellow materials respectively. The lactoid form has not been crystallized pure, although its cocrystal and solvate forms exhibit colors ranging from yellow to green. An explanation for the observed colors of the crystals is found using a combination of UV/Vis spectroscopy and plane-wave DFT calculations. In addition, the role of cocrystal coformers in modifying crystal color is established. Several new crystal structures are determined using a combination of X-ray and electron diffraction, solid-state NMR and crystal structure prediction (CSP). The protocol presented herein may be used to predict color properties of materials prior to their synthesis.
Keywords
optical spectroscopy, plane-wave DFT, color, tautomerism, surface
Sponsorship
M.A. thanks EPSRC for a PhD studentship. M.D.E. acknowledges support from the Interreg V “2 Mers Seas Zeeën” cross-border cooperation program. D.G.R. acknowledges financial support from the MRC. D.K.B. acknowledges University College London for an UCL Excellence Fellowship. A.J.M. acknowledges the support from the Winton Program for the Physics of Sustainability. G.M.D. thanks the Royal Society for funding. This work was performed using the Darwin Supercomputer of the University of Cambridge High Performance Computing Service (http://www.hpc.cam.ac.uk/), provided by Dell Inc. using Strategic Research Infrastructure Funding from the Higher Education Funding Council for England and funding from the Science and Technology Facilities Council.
Funder references
Isaac Newton Trust (1238(j))
Royal Society (nf100747)
MRC (MR/J007692/1)
EPSRC (1127438)
European Regional Development Fund (ERDF) (via Lille University of Science and Technology) (unknown)
Embargo Lift Date
2100-01-01
Identifiers
External DOI: https://doi.org/10.1002/chem.201601340
This record's URL: https://www.repository.cam.ac.uk/handle/1810/255953
Rights
Attribution 4.0 International, Attribution 4.0 International, Attribution 4.0 International