ElectronicSpectroscopy

Ultravioletandvisible

Whereinthespectrumarethese
transitions?

Whyshouldwelearnthisstuff?
Afterall,nobodysolvesstructures
withUVanylonger!
ManyorganicmoleculeshavechromophoresthatabsorbUV
UVabsorbanceisabout1000xeasiertodetectpermolethanNMR
Stillusedinfollowingreactionswherethechromophorechanges.Useful
becausetimescaleissofast,andsensitivitysohigh.Kinetics,esp.in
biochemistry,enzymology.
MostquantitativeAnalyticalchemistryinorganicchemistryisconductedusing
HPLCwithUVdetectors
Onewavelengthmaynotbethebestforallcompoundinamixture.
AffectsquantitativeinterpretationofHPLCpeakheights

UsesforUV,continued
KnowingUVcanhelpyouknowwhentobeskepticalofquantresults.Need
tocalibrateresponsefactors
AssessingpurityofamajorpeakinHPLCisimprovedbydiodearraydata,
takingUVspectraattimepointsacrossapeak.Anydifferencescouldsuggest
aunresolvedcomponent.PeakHomogeneityiskeyforpurityanalysis.
SensitivitymakesHPLCsensitive
e.g.validationofcleaningprocedureforaproductionvessel
Butyouwouldneedtoknowwhatcompoundscouldandcouldnotbedetected
byUVdetector!(Structure!!!)
Oneofthebestwaysforidentifyingthepresenceofacidicorbasicgroups,due
tobigshiftsinforachromophorecontainingaphenol,carboxylicacid,etc.

hypsochromicshift

bathochromicshift

TheUVAbsorptionprocess
*and*transitions:highenergy,
accessibleinvacuumUV(max<150nm).Notusually
observedinmolecularUVVis.
n*and*transitions:nonbondingelectrons
(lonepairs),wavelength(max)inthe150250nmregion.

n*and*transitions:mostcommon
transitionsobservedinorganicmolecularUVVis,
observedincompoundswithlonepairsandmultiple
bondswithmax=200600nm.
Anyoftheserequirethatincomingphotonsmatchin
energythegapcorrrespondingtoatransitionfrom
groundtoexcitedstate.

Energiescorrespondtoa1photonof300nmlightare

Whatarethe
natureofthese
absorptions?

*
*
*
n

*; =218
=11,000
max

*
*
*
n

*
Example
fora
*
simple
*
enone
n

n*; =320
=100
max

Example:*transitionsresponsibleforethyleneUVabsorptionat~170nm
calculatedwithZINDOsemiempiricalexcitedstatesmethods(Gaussian03W):

h170nmphoton

HOMO u bonding molecular orbital

g antibonding molecular orbital

LUMO

HowDoUVspectrometerswork?
Rotates,to
achievescan

Matchedquartzcuvettes
Sampleinsolutionatca.105M.
SystemprotectsPMtubefrom
straylight
D2lampUV
TungstenlampVis
DoubleBeammakesita
differencetechnique

Twophotomultiplier
inputs,differential
voltagedrivesamplifier.

DiodeArrayDetectors
Diodearray
alternativeputs
grating,arrayof
photosens.
Semiconductorsafter
thelightgoesthrough
thesample.
Advantage,speed,
sensitivity,
TheMultiplex
advantage

ModelfromAgilentliterature.Imagine
replacingcellwithamicroflowcellfor
HPLC!

Disadvantage,
resolutionis1nm,vs
0.1nmfornormal
UV

Experimentaldetails
WhatcompoundsshowUVspectra?
Generallythinkofanyunsaturatedcompoundsasgood
candidates.Conjugateddoublebondsarestrongabsorbers
JustheteroatomsarenotenoughbutC=Oarereliable
Mostcompoundshaveendabsorbanceatlowerfrequency.
Unfortunatelysolventcutoffsprecludeobservation.
YouwillfindmolarabsorbtivitiesinLcm/mol,tabulated.
Transitionmetalcomplexes,inorganics
SolventmustbeUVgrade(greatsensitivitytoimpuritieswith
doublebonds)
TheNISTdatabaseshaveUVspectraformanycompounds

AnElectronicSpectrum

Makesolutionof
concentrationlowenough
thatA1
(EnsuresLinearBeers
lawbehavior)

1.0

maxwithcertain
extinction

UV

Visible

Eventhoughadualbeam
goesthroughasolvent
blank,choosesolvents
thatareUVtransparent.

Absorbance

Canextractthevalueif
conc.(M)andb(cm)are
known
UVbandsaremuch
broaderthanthephotonic
transitionevent.Thisis
becausevibrationlevels
aresuperimposedonUV.

0.0
200

400

Wavelength,,generallyinnanometers(nm)

800

SolventsforUV(showinghigh
energycutoffs)
Water

205

THF

CH3CN

210

CH2Cl2 235

C6H12

210

CHCl3

245

Ether

210

CCl4

265

EtOH

210

benzene

280

Hexane

210

Acetone

300

MeOH

210

Variousbuffersfor
HPLC,checkbefore

using.

Dioxane

220

220

Organiccompounds(manyof
them)haveUVspectra
Onethingisclear

Uvscanbeverynonspecific
Itshardtointerpretexceptata
cursorylevel,andtosaythatthe
spectrumisconsistentwiththe
structure
Eachbandcanbea
superpositionofmany
transitions
Generallywedontassignthe
particulartransitions.

FromSkoogandWestetal.Ch14

AnExamplePulegone
Frequently
plottedas
logof
molar
extinction

Soat240nm,
pulegonehas
amolar
extinctionof
7.24x103
Antilogof3.86

CanwecalculateUVs?
Molar Absorptivity (l/mol-cm)

Electronic Spectra

50243

40194

30146

20097

10049
nacindolA
0
220

230

240

250

260

270

280

290

300

Wavelength

Electronic Spectra

Molar Absorptivity (l/mol-cm)

51972

41578

Semiempirical(MOPAC)at
AM1,thenZINDOfor
config.interactionlevel14
Bandwidthsetto3200cm

31183

20789

10394

0
220

230

Nacetylindo

240

250

260

270

280

290

300

Wavelength

Theorbitalsinvolved

Electronic Spectra

Molar Absorptivity (l/mol-cm)

55487

44390

33292

22195

11097

0
200

210

220

230

240

250

260

270

280

290

Showing
atomswhose
MOs
contribute
Nacetylindolmosttothe
Wavelength (nm) bands
300

TheQuantitativePicture
Transmittance:
T=P/P0

Absorbance:
A=log10T=log10P0/P

P0
(powerin)

P
(powerout)

B(path through sample)

TheBeerLambertLaw(a.k.a.BeersLaw):
A=bc
WheretheabsorbanceAhasnounits,sinceA=log10P0/P
isthemolarabsorbtivitywithunitsofLmol1cm1
bisthepathlengthofthesampleincm
cistheconcentrationofthecompoundinsolution,expressedinmolL1(orM,molarity)

BeerLambertLaw
Linearabsorbancewithincreasedconcentrationdirectly
proportional
MakesUVusefulforquantitativeanalysisandinHPLC
detectors
Aboveacertainconcentrationthelinearitycurvesdown,
losesdirectproportionalityDuetomolecularassociations
athigherconcentrations.Mustdemonstratelinearityin
validatingresponseinananalyticalprocedure.

Polyenes,andUnsaturated
Carbonylgroups;
anEmpiricaltriumph

R.B.Woodward,L.F.Fieserandothers

Predictmaxfor*inextendedconjugation
systemstowithinca.23nm.

Homoannular,base253nm

Acyclic,base217nm

heteroannular,base214nm

Attachedgroup

increment,nm

Extendconjugation

+30

AddnexocyclicDB

+5

Alkyl

+5

OAcyl

Salkyl

+30

Oalkyl

+6

NR2

+60

Cl,Br

+5

X=H207

SimilarforEnones

227

202
215
BaseValues,addtheseincrements

239

ExtndC=C

+30

AddexocyclicC=C

+5

Homoannulardiene

+39

alkyl

+10

+12

Withsolventcorrection
of..

OH

+35

+30

Water+8

OAcyl

+6

+6

+6

+6

EtOH0

Oalkyl

+35

+30

+17

+31

CHCl31

NR2

Dioxane5

Salkyl

Et2O7

Cl/Br

+15/+25

+12/+30

X=R215
X=OH193
X=OR193

Hydrcrbn11

+18

+18
+50

SomeWorkedExamples

Basevalue
2xalkylsubst.
exoDB
total
Obs.

217
10
5
232
237

Basevalue
3xalkylsubst.
exoDB
total
Obs.

214
30
5
234
235

Basevalue
2alkylsubst.
total
Obs.

215
24
239
237

DistinguishIsomers!
Basevalue
4xalkylsubst.
exoDB
total
Obs.

214
20
5
239
238

Basevalue
4xalkylsubst.
total
Obs.

253
20
273
273

HO2C

HO2C

Generally,extendingconjugation
leadstoredshift
particleinaboxQMtheory;biggerbox
Substituentsattachedtoachromophorethatcausearedshift
arecalledauxochromes
Strainhasaneffect

max 253239

256

248

InterpretationofUVVisibleSpectra
Transitionmetal
complexes;d,f
electrons.
Lanthanidecomplexes
sharplinescaused
byscreeningofthe
felectronsbyother
orbitals
Oneadvantageofthis
istheuseofholmium
oxidefilters(sharp
lines)forwavelength
calibrationofUV
spectrometers.

See Shriver et al. Inorganic Chemistry, 2nd Ed. Ch. 14

Benzenoid
aromatics
UVof
Benzenein
heptane

FromCrewes,Rodriguez,Jaspars,OrganicStructureAnalysis

Group

Kband()

Bband()

Rband

Alkyl

208(7800)

260(220)

OH

211(6200)

270(1450)

236(9400)

287(2600)

OCH3

217(6400)

269(1500)

NH2

230(8600)

280(1400)

204(6200)

254(900)

Cl

210(7500)

257(170)

Br

210(7500)

257(170)

207(7000)

258/285(610/180
)

NH3+

203(7500)

254(160)

C=CH2

248(15000)

282(740)

CCH

248(17000)

278(6500

C6H6

250(14000)

C(=O)H

242(14000)

280(1400)

328(55)

C(=O)R

238(13000)

276(800)

320(40)

CO2H

226(9800)

272(850)

CO2

224(8700)

268(800)

CN

224(13000)

271(1000)

NO

252(10000)

280(1000)

330(140)

Substituenteffectsdontreallyaddup
Canttellanythingaboutsubstitutiongeometry
Exceptiontothisiswhenadjacentsubstituents
caninteract,e.ghydrogenbonding.
E.gthesecondarybenzenebandat254shiftsto
303insalicylicacid
Inphydroxybenzoicacid,itisatthephenolor
benzoicacidfrequency

Heterocycles
Nitrogenheterocyclesareprettysimilartothebenzenoid
anaologsthatareisoelectronic.
Canstudyprotonation,complexformation(charge
transferbands)

Quantitative
analysis
Greatfornon
aqueoustitrations
Examplehere
givesdetnof
endpointfor
bromcresolgreen

Isosbesticpoints
Singleclearpoint,canexclude
intermediatestate,excludelight
scatteringandBeerslawapplies

Bindingstudies
FormItoformII

Bindingofalanthanidecomplexto
anoligonucleotide

MoreComplexElectronicProcesses

Fluorescence:absorptionof
radiationtoanexcitedstate,
followedbyemissionofradiationto
alowerstateofthesame
multiplicity
Phosphorescence:absorptionof
radiationtoanexcitedstate,
followedbyemissionofradiationto
alowerstateofdifferentmultiplicity
Singletstate:spinsarepaired,no
netangularmomentum(andnonet
magneticfield)
Tripletstate:spinsareunpaired,net
angularmomentum(andnet
magneticfield)