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6000 Broken Sound Parkway, NW6000 Broken Sound Parkway, NW BojidarkBao jIivdaanrokvaa Ivanova
Suite 300, Boca Raton, FL 33487 Suite 300, Boca Raton, FL 33487
711 Third Avenue 711 Third Avenue
an informa business Neawn Yionfrok,r mNaY b 1u0si0n1es7s New York, NY 10017
2 Park Square, Milton Park 2 Park Square, Milton Park Tsonko TKsoolnekvo Kolev
Abingdon, Oxon OX14 4RN, UK Abingdon, Oxon OX14 4RN, UK
Linearly
Polarized IR
Spectroscopy
Theory and Applications for Structural Analysis
Linearly
Polarized IR
Spectroscopy
Theory and Applications for Structural Analysis
BBoojjiiddaarrkkaa IIvvaannoovvaa
TTssoonnkkoo KKoolleevv
Boca Raton London New York
CRC Press is an imprint of the
Taylor & Francis Group, an informa business
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Library of Congress Cataloging‑in‑Publication Data
Koleva, Bojidarka.
Linearly polarized IR spectroscopy : theory and applications for structural analysis /
authors, Bojidarka Koleva, Tsonko Kolev.
p. cm.
“A CRC title.”
Includes bibliographical references and index.
ISBN 978-1-4398-2559-4 (hardcover : alk. paper)
1. Infrared spectroscopy. 2. Polarization spectroscopy. 3. Materials--Analysis. 4.
Chemical structure. I. Kolev, Tsonko. II. Title.
QD96.I5.K65 2010
541’.22--dc22 2009049465
Visit the Taylor & Francis Web site at
http://www.taylorandfrancis.com
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Contents
Preface......................................................................................................................vii
Acknowledgments......................................................................................................ix
Authors.......................................................................................................................xi
Introduction.............................................................................................................xiii
Chapter 1 Linear-Dichroic.Infrared.(IR-LD).Spectroscopy:.Background............1
1.1. Theoretical.Prerequisites............................................................3
1.2. Symmetry.Analysis.of.Normal.Vibrations.and.Dipole.
Moments.of.Transition.Generated.Therefrom............................8
1.2.1. Elements.and.Operations.of.Symmetry........................8
1.2.2. Symmetry.Analysis.of.the.Dipole.Moments.of.
Transition.....................................................................12
1.3. Orientation.of.the.Samples.......................................................13
1.3.1. Orientation.in.Liquid.Crystal.Solutions......................14
1.3.2. Orientation.as.Suspension.in.Liquid.Crystals.............17
1.4. Photometrization.and.Processing.of.IR-LD.Spectra:.
Reducing.Differential.Procedure.............................................18
1.5. Effects.in.the.Infrared.Spectra.of.Crystals...............................23
Chapter 2 The.Background.of.the.Orientation.Method.of.Colloid.
Suspensions.in.a.Nematic.Host...........................................................29
2.1. Orientation.Procedure..............................................................29
2.2 Validation.of.the.Orientation.Procedure..................................36
2.2.1 Accuracy.and.Repeatability........................................42
2.2.2 The.Quantitative.Ratio.of.Liquid.Crystals.and.
Solid.Samples..............................................................42
2.2.3 Preliminary.Rubbing.Out.of.the.KBr.Plates...............43
2.2.4 Peak.Function.Type.for.the.Curve-Fitting.
Procedure....................................................................43
2.2.5 Number.of.Scans.in.the.Measurements.......................43
2.3 Experimental.Design................................................................43
2.4 Mathematical.Tools.for.the.Interpretation.of.the.
IR Spectroscopic.Patterns........................................................46
2.4.1 IR.Spectra.Subtraction................................................46
2.4.2 The.Smoothing.Procedure..........................................46
2.4.2.1 Limits.of.Detection.and.Smoothing.
Procedure.Validation...................................46
2.4.3 Accuracy.and.Precision...............................................48
2.4.4 Deconvolution.............................................................48
v
vi Contents
2.4.5 Curve-Fitting.Procedure.(CFP)...................................49
2.4.6 Baseline.Correction.(BLC).........................................52
2.5 Reducing-Difference.Procedure.(RDP).for.IR-LD.
Spectra.Interpretation...............................................................53
Chapter 3 Structural.Elucidation.of.Inorganic.Compounds.and.Glasses............63
3.1. Inorganic.Compounds..............................................................63
3.2. IR.Spectroscopic.Elucidation.of.Glasses..................................69
Chapter 4 Structural.Elucidation.of.Organic.Compounds...................................73
4.1. Analysis.of.Heterocyclic.Compounds......................................73
4.2. Small.Biologically.Active.Molecules.....................................104
Chapter 5 Application.in.Pharmaceutical.Analysis...........................................123
5.1. Analysis.of.Morphine.Alkaloids............................................143
Chapter 6 Application.in.the.Chemistry.of.Dyes...............................................151
6.1. Stilbazolium.Salts...................................................................151
6.2. Dicyanoisophorone.Derivatives..............................................176
Appendix: List of Acronyms................................................................................187
References..............................................................................................................189
Preface
The.potential.of.polarized.spectroscopy.as.a.tool.for.experimental.study.of.oriented.
compounds.has.been.demonstrated.for.almost.120.years..The.development.of.this.
method.began.as.early.as.1888.by.Ambronn.[1],.who.published.the.results.obtained.
from.the.first.linear-dichroic.study.on.membranes..Since.then,.prominent.publi-
cations,.review.articles,.and.books.devoted.to.this.spectacular.research.area.have.
appeared..These.investigations.include.wide-scope.studies.on.polarized.u.ltraviolet.
and.vibrational.(infrared.[IR].and.Raman).spectroscopy.of.oriented.polymers,.
embedded.compounds.in.stretched.polymers,.oriented.single.crystals,.dissolved.mol-
ecules.in.nematic.liquid.crystal.hosts,.polycrystalline.samples.oriented.by.melting,.
and.membrane.techniques..The.fundamental.work.on.IR.spectroscopy.of.polymers.
by.Zbinden.[2],.Frushour.[3],.Jasse.and.Köning.[4],.Thulstrup.and.Eggers.[5],.Michl.
and.Thulstrup.[6,7],.Shrader.[8],.and.Siesler.[9].has.significantly.contributed.to.the.
development.of.this.research.field..The.studies.of.a.number.of.other.scientists.should.
also.be.mentioned,.including:.Laurent.[10].and.Samori.[11,12].on.the.linear.dichro-
ism.of.solute.molecules.within.micelles.and.liquid.crystalline.catalysis;.Vogt.[13].
on..oriented.thin.films;.and.the.series.of.fundamental.works.of.Jordanov.[14–24].on.
oriented.molecules.in.liquid.crystal.solutions.(homogenic.systems)..The.investiga-
tions.of.the.latter.have.been.continued.by.Arnaudov,.Andreev,.Tsankov,.Kolev,.and.
Rogojerov.[17,25–31]..The.theoretical.background.of.polarization.IR.spectroscopy.
has.been.summarized.in.many.of.these.fundamental.contributions..Therefore,.the.
polarization.IR.spectroscopic.method.is.undergoing.continued.development,.particu-
larly.with.respect.to.the.search.for.both.new.orientation.approaches.and.theoretical.
generalizations..These.contributions.result.in.growing.possibilities.for.the..application.
of.an.inherently.“classical”.method.such.as.IR.spectroscopy.for.the.instrumental.
structural.characterization.of.compounds.
Colloid.suspensions.(heterogeneous.systems).in nematic.liquid.crystal.(CS-NLC).
hosts.were.first.employed.in.2004.by.Ivanova and.her.coworkers [32].as.a.tool.for.
the.partial.orientation.of.solids.to.be.examined.by.linear-dichroic.infrared.spectros-
copy..The.authors.of.this.book.have.found.that.it.is.possible.to.perform.spectroscopic.
and.structural.elucidation.of.the.embedded.compounds,.independent.of.their.melting.
point,.crystalline.or.amorphous.states,.and.the.quality.of.single.crystals.or.polycrys-
talline.samples..The.method.can.be.used.for.structural.elucidation.of.inorganic.and.
organic.compounds,.including.organic.salts,.metal.complexes,.and.glasses..The.vast.
research.of.Ivanova.and.her.coworkers.has.also.covered.a.number.of.important.top-
ics,.such.as.the.theoretical.background.of.the.orientation.method,.validation.for.accu-
racy,.influence.of.the.host.on.peak.positions,.integral.absorbance.of.guest.molecule.
bands,.optimization.of.experimental.conditions,.morphology.of.suspended.particles,.
the.influence.of.the.physical.and.chemical.properties.of.the.liquid.crystal.medium.
on.the.degree.of.orientation.of.suspended.particles,.studies.on.the.velocity.of.shear-
ing.the.suspension,.effects.of.the.extent.of.roughening.KBr-plates.on.the.degree.of.
orientation,.the.influence.of.the.space.group.on.the.orientation.parameters,.effects.
vii
viii Preface
of.nature.and.balance.of.the.forces.acting.on.suspended.particles.and.their.degree.of.
orientation,.and.the.building.of.corresponding.mathematical.models.[33–35].
Today,.the.application.of.the.CS-NLC.method.is.associated.with.more.than.350.
compounds.as.analytical.objects,.including.a.small.number.of.inorganic.compounds;.
a.large.number.of.organic.compounds.such.as.all.essential.amino.acids,.their.salts,.
and.amides;.a.series.of.aliphatic.and.aromatic.small.homo-.and.heteropeptides,.their.
salts,.and.metal.complexes;.heterocyclic.compounds,.such.as.substituted.pyridines,.
quinolines,.benzimidazoles,.benzotriazoles,.and.their.salts.and.metal.complexes;.
aromatic.amines;.pharmaceutical.products;.alkaloids;.and.organic.dyes..The.method.
has.also.been.successfully.employed.for.obtaining.local.information.on.the.struc-
tures.of.tellurite,.vanadate,.and.borate.glasses.
This.book.is.the.first.to.be.devoted.to.both.the.theory.and.practical.application.of.
partially.oriented.colloidal.systems.in.nematic.liquid.crystals.for.IR.spectroscopic.
and.structural.elucidation.of.an.embedded.chemical.in.the.solid.state..The.main.
goal.of.this.work.is.to.indicate.the.possibilities.of.application.of.this.new.orientation.
technique.for.structural.characterization.of.various.compounds..More.specifically,.
this.book.is.intended.to.show.the.ways.of.obtaining.important.information.about.
the.structure.and.spectral.properties.of.oriented.compounds..The.examples.included.
serve.to.demonstrate.both.the.advantages.of.this.technique.and.its.limitations.associ-
ated.with.some.specific.systems..Although,.unlike.the.single-crystal.X-ray.diffrac-
tion,.IR.spectroscopy.cannot.be.regarded.as.an.“absolute”.instrumental.method.for.
structural.analysis,.particular.emphasis.is.placed.on.the.application.of.the.method.
for.systems.providing.reliable.and.complete.information.compared.to.those.requir-
ing.caution.in.structural.evaluation.without.the.support.of.additional.instrumental.
methods.
This.book.is.divided.into.two.parts,.including.the.theoretical.basis.of.linear-
.dichroic.infrared.(IR-LD).spectroscopy.(Chapter.1),.the.orientation.method.as.colloid.
suspension.in.nematic.hosts.(Chapter.2),.and.practical.aspects.(Chapters.3.through.6).
associated.with.the.use.of.the.method.for.the.characterization.of.inorganic.chemicals.
and.glasses.as.well.as.various.classes.of.organic.compounds..In.all.of.the.examples,.
the.scope.and.limitation.of.the.method.are.discussed.and.summarized..Therefore,.
this.text.can.serve.as.a.useful.source.of.information.not.only.for.specialists.in.IR.
spectroscopy.but.also.for.other.scientists.as.well.as.Ph.D..students.working.in.the.
field.of.structural.analysis..It.can.also.be.successfully.used.by.B.Sc..and.M.Sc..stu-
dents.who.attend.courses.for.advanced.physical.methods.of.analysis.
Acknowledgments
We.would.like.to.express.our.sincere.gratitude.to.the.Alexander.von.Humboldt.
Foundation.(Germany).for.its.continuous.support.of.our.research..We.are.thank-
ful.for.the.research.fellowships.granted,.which.provided.us.with.the.unique.oppor-
tunity.to.work.with.prominent.scientists.at.recognized.educational.and.research.
institutions.including.the.University.of.Dortmund—Department.of.Organic.and.
Structural.Chemistry,.and.Professor.Paul.Bleckmann.(fellowship.granted.to.Tsonko.
Kolev,.1988–1989.and.1991–1992);.and.Ruhr.University.Bochum—Department.of.
Analytical.Chemistry,.and.Profesor.William.S..Sheldrick.(fellowship.granted.to.
Bojidarka.Koleva,.2003,.2007–2009).
We.also.gratefully.acknowledge.the.kind.assistance.of.Dr..Michael.Spiteller,.
Managing.Director.of.the.Institute.of.Environmental.Research,.Technical.University.
Dortmund.(Germany),.for.the.successful.long-time.collaboration,.including.the.valu-
able.discussions.and.excellent.conditions.for.research.and.a.creative.atmosphere.within.
the.framework.of.several.research.projects.supported.by.the.Bundesministerium.für.
Bildung.und.Forschung.(BMBF,.Germany),.Deutscher.Akademischer.Austausch.
Dienst.(DAAD,.Germany),.and.Deutsche.Forschungsgemeinschaft.(DFG,.Germany).
We.greatly.appreciate.the.kind.assistance.of.Dr..William.S..Sheldrick,.head.of.the.
Department.of.Analytical.Chemistry.at.Ruhr.University.Bochum.(Germany),.for.our.
fruitful.collaboration.and.creative.discussions.
ix
