Chapter 1 Ultraviolet/Visible Spectroscopy

Introduction f S I t d ti of Spectroscopy t
• The structure of new compounds that are isolated from natural sources or prepared in the p p lab must be determined (and/or verified).
– Chemical analysis (Classical methods) y ( ) – Spectroscopy (Modern techniques)

• Spectroscopic techniques are non-destructive and generally require small amounts of sample sample.

Types of Energy in Each Region of the yp gy g Electromagnetic Spectrum
Region of Spectrum
X-rays Ultraviolet/Visible Infrared Microwave Radiofrequencies

Energy Transitions
Bond Breaking Electronic Vibrational Rotational Nuclear Spin (Nuclear Magnetic Resonance) Electron Spin (Electron Spin Resonance)

3

μ μ 部分电磁波的波段分布示意图 .

Four common spectroscopic techniques used to determine structure: – Ult i l t S Ultraviolet Spectroscopy t – Infrared Spectroscopy (IR) – Nuclear Magnetic Resonance Spectroscopy (NMR) – Mass Spectrometry (MS or Mass Spec) .

• Ult i l t S Ultraviolet Spectroscopy t – Observes electronic transitions • Provides information on the electronic bonding in a molecule .

• Infrared spectroscopy: – Used to determine the functional groups present in a molecule • Mass spectrometry – B k molecule i t Breaks l l into fragments • Analysis of the masses of the fragments gives f th f t i MW and clues to the structure of the molecule .

• N l Nuclear M Magnetic R ti Resonance S Spectroscopy t – Observes the chemical environment of the hydrogen (or carbon) atoms in the molecule • Helps provide evidence for the structure of the carbon skeleton and/or the alkyl groups present k l t d/ th lk l t 1H NMR of CH3CH2OH 13C NMR of CH3CH2OH .

9 .1.1 1 1 Principle of UV Light Absorption Ultraviolet light: wavelengths between 190 and 400 nm Visible light: wavelengths between 400 and 800 nm Ultraviolet/visible spectroscopy involves the absorption of ultraviolet light by a molecule causing the promotion of an electron from a ground electronic state to an excited electronic state.

Principle of UV p 10 .

and halogen it lf dh l compounds) n to π∗ ( b (carbonyl compounds) l d) 11 . azo b l d lk compounds) n to σ∗ ( (oxygen. sulfur. alkynes. carbonyl compounds. nitrogen.There are several types of electronic transitions available to a molecule including: σ to σ∗ (alkenes) π to π∗ ( lk (alkenes.

Instrument frame 12 .

Spectrometer Multichannel photodiode array .

Ultraviolet/Visible Spectroscopy Hewlett-Packard 8452a Diode Array Spectrophotometer .

2 Electronic Excitations 15 .1.

Vibrational levels Electronic excited state Vibrational levels Electronic ground state 16 .

1.3 1 3 The Origin of UV Band Structure A UV Absorption Band at Room Temperature (A) and at Lowered Temperature (B) 17 .

4 the absorption law—the Beer-Lambert Law I log = ε . ε is known as the molar extinction cofficient 10 0 18 .1.l.c I 0 10 Io = the intensities of the incident light I = the intensities of the transmitted light l = the path length of the absorbing in centimetres c = the concentration in moles per litre log ( I / I ) is called the absorbance or optical density.

1 2.2 3. max log ε = 4.5 Presentation of Spectra λ = 230nm.9 272 282 Ultraviolet Spectrum of Benzoic A id i C l h Ult i l t S t fB i Acid in Cyclohexane 19 .1.

nm ll 190 191 195 201 203 204 215 220 237 257 20 .1.6 C Choice of S f Solvents So e so ve s Some solvents used in ultraviolet spectroscopy u v o e spec oscopy Solvent Acetonitrile Water Cyclohexane Hexane Methanol Ethanol Ether Methylene dichloride Chloroform Carbon tetrachloride Minimum wavelength for 1 cm cell.

and n-hexane. 21 . Usually solvents which do not contain conjugated systems are most suitable f thi purpose. 95% ethanol. although t t it bl for this lth h they vary as to the shortest wavelength at which they th remain t i transparent t ultraviolet radiation. t to lt i l t di ti The solvents most commonly used are water.The first criterion for solvent A good solvent should not absorb ultraviolet radiation in the same region as the substance whose spectrum is being determined determined.

A second criterion ( the effect of a solvent on the fine structure of an absorption band) Ultraviolet Spectra of Phenol in Ethanol and in Isooctane 22 .

Large energy lowering caused by g y solvent interaction The effect of a polar solvent on a transition 23 .

A third property of a solvent The ability of a solvent to influence the wavelength of ultraviolet light which will be absorbed. a polar solvent would shift an absorption to longer wavelength. Polar solvents may not form hydrogen bonds as readily with excited states as with ground states of polar solvents. in some cases the excited states may form stronger hydrogen bonds than the corresponding ground state. since the energy of the electronic transition would be decreased. In such cases. Transitions of the π → π * type are shifted to longer wavelengths by polar solvents. Transitions of the n → π * type are shifted to shorter wavelengths by polar solvents. On the other hand. 24 .

5 CH3OH C2H5OH CHCl3 270 272 277 C6H14 279 λ .Solvent Shifts on the Transition in Acetone n →π * Solvent Sl t H2O 264. nm max 25 .

B. CH3(CH=CH)nCH3 . n=4.1. C. n=5 26 . A. n=3.7 the Effect of Conjugation Ultraviolet Spectra of Dimethylpolyenes.

Conjugation of two chromophores not only results in a bathochromic shift.3. but it also increases the intensity of the b th absorption.5-Hexatriene β Carotene β-Carotene (11 double bonds) Ketones Acetone π→π* n →π* 3-Buten-2-one π→π* n →π* π λmax (nm) 175 217 258 465 ε 15.000 35. 189 280 213 320 900 12 7.100 27 27 .000 125.000 . ti The Effect of Conjugation on Electronic Transitions Alkenes Ethylene 1.000 15 000 21.3-Butadiene 1.

28 .

8 the Effect of Conjugation on Alkenes Formation of the Molecular Orbitals for Ethylene 29 .1.

Fig.3Butadiene Conjugation makes the energy lower j g gy 30 . 1-13 Comparison of th Fi 1 13 A C i f the Molecular Orbital Energy Levels and Energy of the π→π* Transitions in Eth lene and 1 3 Ethylene 1.

31 .A Comparison of the π→π* Energy Gap π→π in a Series of Polyenes of Increasing Chain Length The longer the conjugated system. g wavelength of the absorption maximum. the longer the g j g y .

the Appearance of the Spectra of some Polyenes 32 .

-OR. or –NH2 OH OR X NH Δ E1 > Δ E2 Energy Relationships of the New Molecular Orbitals and the Interacting π System and its Auxochrome 33 . -X.An extension of the length of the conjugated system B = -OH.

34 .Overlap of the electrons Hyperconjugation Quasi-resonance structures The net effect is an extension of the πsystem .

transitions may become allowed — called “cis band”.9 the Effect of conformation and Geometry on Polyene Spectra • • • All-trans polyenes show only the Ψ2 → Ψ3* transition In polyenes with one or more cis double bonds the Ψ2 → Ψ4* bonds. even when possessing several cis d bl b d will not show th cis i l i double bonds.1. Any molecule which retains a center of symmetry. ill t h the i band. 35 .

36 .Spectra of isomeric β-carotenes. showing the development of the cis band.

Empirical rules for caluclating UV/Vis Absorptions Woodward-Fieser Rules for Dienes A. Benzoyl Derivatives 37 . Woodward's Rules for Conjugated Carbonyl Compounds B. Mono-Substituted Benzene Derivatives C. Di-Substituted Benzene Derivatives D.

alkyl substitution p hyperchromic effects. With certain patterns of alkyl substitution. increases but the intensity decreases. y produces bathochromic shifts and Generally. decreases 38 .1.000 λ =217 to 245nm Butadiene and many simple conjugated dienes exist in a planar sB t di d i l j t d di i ti l trans conformation. y.000 to 26. the wavelength increases.10 the Woodward-Fieser Rules for Dienes conjugated di j t d dienes π→π* transition ε=20.

000 λ shorter (234nm) The actual rules for predicting the absorption of open chain and sixmembered ring diene were first made by Woodward in 1941.000 intense 5 000 15 000 λ longer (273nm) Heteroannular Diene (s(s-trans) more intense. 39 . ε= 12.000 – 28. ε= 5.000 –15. Since that time they have been modified by Fieser and Scott as a result of experience with a very large number of dienes and trienes.Cyclic dienes The central bond is a part of the ring system. the diene chromophore is usually held rigidly in either the s trans or the s cis conformation s-trans s-cis Homoannular Diene (s(s-cis) less intense.

Rules for diene and triene absorption Value i d t V l assigned to parent heteroannular or open diene th t l di Value assigned to parent homoannular diene Increment for (a) each alkyl substituent or ring residue (b) the exocyclic double bond (c) a double-bond extension (d) auxochrome ―OCOCH3 ―OR ―SR ―Cl. ―Br ―NR2 λcalc Total H H C H C H C C H H 214 nm 253 nm 5 nm 5 nm 30 nm 0 nm 6 nm 30 nm 5 nm 60 nm H C C H H H 3C H 3C C H 3C C transoid: observed: b d 214 nm 217 nm transoid: alkyl groups: observed: 214 nm 3 × 5 = 15 229nm 228 nm 40 .

CH3 a A a B a CH3 Exocyclic Double Bond CH CH C 3C 2O transoid: 214 nm ring residues: 3 × 5 = 15 exocyclic double bond: 5 234 nm observed: 235 nm CH3 observed: 240 nm 241 nm CH3 CH CH3 CH3 cisoid: 253 nm ring residues: 3 × 5 = 15 exocyclic double bond: 5 273 nm observed: 275 nm observed: 278 nm 275 nm 41 .

j g 42 .CH3 CH3 cisoid: 253 nm ring residues: 5× 5= 25 double bonds extending g conjugation: 2 × 30 = 60 exocyclic double bonds: 3 × 5 = 15 CH3COO–: COO : 0 353 nm observed: 355 nm CH3COO The Woodward-Fieser rules work well for polyenes with from one to four conjugated double bonds.

2 × 104 Lycopene. ε=15. 13 Double Bonds (11 Conjugated) y p .11 1 11 the Fieser-Kuhn Rules for polyenes β-Carotene.1. ε=18.6 × 104 43 . ( j g ) λmax= 474 nm(hexane). β Carotene 11 Double Bonds λmax= 452 nm(hexane).

0 − 1. β-Carotene: M = 10 n = 11 Rendo = 2 Therefore: λmax= 453.Empirical Rules for Polyens E ii lR l f P l λ (hexane) = 114 + 5M + n(48.7 n) − 16.3 εmax= 19.5R − 10 R ε (hexane) = 1.1 ×104 44 Rexo = 0 .74 × 10 n max endo d 4 max exo where: M n Rendo Rexo = = = = the number of alkyl substituents the number of conjugated double bonds the number of rings with endocyclic double bonds the number of rings with exocyclic double bonds g y For example.

as in amides. or –X.12 1 12 carbonyl compounds. or acid chlorides. – OH. such as –NR2.1. acids. esters. gives a pronounced hypsochromic effect on the n→π* transition and lesser bathochromic effect on the π→π* transition. –NH2. (resonance interaction) 45 . enones b l d Two i i l T principal uv transition: ii forbidden 280-290 280 290 nm allowed 190 nm π* n π Substitution by an auxochrome with a lone pair of electrons. –OR.

They withdraw electrons from the carbonyl carbon. . or halogen atoms. g y y causing the lone pair of electrons on oxygen to be held more firmly than 46 would be the case in the absence of an inductive effect.the Hypsocromic Effect of Lone Pair Auxochromes on the n→π* Transition of a Carbonyl Group λ max O CH3 C O H ε max Solvent S l t 293 nm 279 235 214 204 12 15 53 60 Hexane Hexane Hexane Water Water CH 3 C O CH 3 CH 3 CH3 C O C Cl NH2 O CH 3 C OCH2CH3 This shift is due primarily to the inductive effect of the oxygen. nitrogen.

both h b h the n→π* and the π→π* b d are shifted to longer wavelengths. * d h * bands hif d l l h The energy of the n→π* transition does not decreased as rapidly as that of the π→π* band. which is more intense. If the conjugated chain becomes long enough. .the Spectra of a Series of Polyene Aldehydes If the carbonyl group is a part of a conjugated system of double bonds. the n→π* band becomes 47 “buried” under the more intense π→π* band.

the Orbitals of an Enone System Compared to those of the Noninteracting Chromophores 48 .

at 310 ~ 330 nm much less intense (ε nm. not predictable 49 .000 8 000 to 20. predictable n→π n→π*.13 Woodward’s Rules for Enones Conjugation of a double bond with a carbonyl group leads to absorption (ε = 8. π→π*.000). = 50 to 100).1. at 220 ~ 250 nm.

O H 3C C H 3C C O C CH 3 CH3 OCOCH3 CH 3 acyclic enone: α -CH3: β -CH3: CH observed: CH3 215nm 10 24 249nm 249nm 6 membered 6-membered enone: double bond extending conjugation: homocyclic diene δ-ring residue: observed: b d O CH3 215nm 30 39 18 302nm 300nm 300 O Br 5-membered enone: β-ring residue: 2× 12= exocyclic double bond: observed: 202nm 24 5 231nm 226nm 5-membered enone: α-Br: B β-ring residue: 2× 12= exocyclic double bond: observed: 202nm 25 24 5 256nm 251nm .

14 1 14 Solvent Shifts – a more detailed examination 1.1. In most π→π* transitions ( (bathochromic shift. lower energy) gy) π* E N E R G Y π* } Large energy lowering caused by solvent interaction π Non-Polar Solvent Polar Solvent π the Effect of a Polar Solvent on a Transition 51 .

g g g the th ground state d t t the π electron density equally distributed.The ground state of the molecule is relatively non-polar. when a polar solvent is used. the C becomes electron deficient The excited state interacts more strongly with polar or hydrogen bonding solvents 52 . As a result. and the excited state is often more polar than the ground state. it interacts more strongly with the excited state than with the ground state. the nuclei of C are shielded the π* excited state the electron is promoted. and the transition is shifted to longer wavelength.

2 In most n→π* transitions n→π (hypsochromic shift. •Hydrogen bonding solvents interact more strongly with unshared electron pairs in the ground state molecule 53 .2. higher energy) π* E N E R G Y becomes electron deficient n π Non-Polar Solvent Polar Solvent π * C* O } n π Large solvent stabilization due to hydrogen bonding C O H O H the Eff h Effect of a Polar Solvent on an n→π* T f P l S l * Transition ii •The ground state is more polar than the excited state.

1.15 1 15 Aromatic Compounds

Molecular Orbitals and E M l l O bit l d Energy St t f Benzene States for B

184 and 202 nm 255nm

primary bands secondary bands (fine-structure)
54

The second primary band (184 nm, ε=47,000) in vacuum ultraviolet region The 202 nm band is much less intense (ε=7,400), it corresponds to a forbidden transition The secondary band is the least intense of the benzene bands (ε=230) (ε 230). It corresponds to a symmetry forbidden electronic transition. Ultraviolet Spectrum of Benzene
55

A. A Substitutents with Unshared Electrons
Y Y Y Y

• The non-bonding electrons can increase the length of g g the π system though resonance. • The more available these n-electrons are for interaction with the π system of the aromatic ring, the greater the shifts will be. (-NH2, -OH, -OCH3, -X) • Interactions of this type between the n and π electrons usually cause shifts in the primary and secondary benzene absorption bands to longer y p g wavelength. • In addition, the presence of n-electrons in these compounds gives the possibility of n→π* transition.
56

This causes a separation of charge in the molecule.If an n-electron is excited into the extended π* chromophore. The extra electron in the ring is actually in a π* orbital. while the π system of the aromatic ring acquires an extra electron. the atom from which it was removed becomes electrondeficient. * Y * Y Y * Y * A charge transfer or an electron transfer excited state With compounds which are acids or bases. p . pH changes can have a very significant effect on the positions of the primary and secondary bands. 57 .

S b i B Substituents capable of π-conjugation bl f j i C O R C O R C O R C O R Interaction of the benzene ring electrons and the π electrons of the substituent can also produce a new electron transfer band.B. This new band may be so intense as to obscure the secondary band of the benzene system. The effect of acidity or basicity of the solution on such a chromophoric substituent group 58 . the ring becomes electron deficient. Notice that the opposite polarity is induced.

One is electron-releasing while the other is electronwithdrawing.) O H2N N+ O H2N O N+ O resonance interactions 59 .C. 2. wo poss b es: 1. Both groups are electron-releasing or electronwithdrawing. two possiblities: . For para-. enhanced shifting (the magnitude of the shift of the primary band is greater than the sum of the shifts due to the individual group. o pa a . similar to monosubstituted benzenes. Disubstituted benzene Derivatives A.

mppo-.mpo-.mp- 246 250 230 3 10 7 25 11 20 78 0 10 2 15 13 58 20 45 73 20 85 -Cl -Br -NH 2 -NHCOCH 3 -NHCH 3 NHCH -N(CH 3 ) 2 60 .-OCH 3 .mpo-.mo.Empirical Rules for Benzoyl Derivatives O C R Parent chromophore: y g R = Alkyl or ring residue R=H R = OH or OAlkyl Increment for each substituent: Alkyl -Alkyl or ring residue -OH.mpoo mpo-.m. po-.mpo-.or –OAlkyl -O O o-.

Br O HO O HO OH C OH parent chromophore: 246nm o-ring residue: i id 3 m-Br: 2 251nm observed: 253nm parent chromophore: 230nm m-OH: 2× 7 = 14 p-OH: 25 269nm observed: 270nm 61 .

To obtain the information of conjugation.Qualification 2 Qualification analysis 3.Application of UV 1. ε 2.Quantitative analysis: A=εbc .

Example spectra .

Example spectra .

 N. C=N. or –CONH2 65 . or unconjugated. N=N.‐COOR. ‐NO2. 360nm with no major absorption at shorter wavelengths (200­250nm) n→π* A simple.A practical guide: Exercises What do you look for in an ultraviolet  spectrum?   A single band of low intensity (10 to 100) in the region 250­ 360nm. chromophore (contains an O.or S):  A i l j d h h ( i O N S) C=O. ‐COOH.

•For dienes using the Woodwood fieser rules dienes. •Substituent on the aromatic rings will increase the molar absorptivity above 10.000). both with (ε 1. the longer the observed wavelength will be.000 to 20. 10 000 •In polynuclear aromatic substances.Two bands of medium intensity (ε=1. above 210 nm unsaturated ketone or a diene or polyene an α.000). a third band will appear near 200 nm.β- •The longer the length of the conjugated system. Bands of high intensity (ε=10. using Fiese-Kuhn rules 66 . Woodwood-fieser •More than four double bonds.000.000 λmax above 200 nm an aromatic system •A good d l of fine structure in the longer wavelength band (in non-polar A d deal f fi t t i th l l th b d (i l solvents only).000 to 10.

. amides.β-unsaturated esters and acids. and other compounds p . p containing both π system and unshared electron pairs. . esters.Simple ketones. high intensity) •With conjugation (enones).000. Woodward’s rules ε above 10. 67 . bury the weaker n→π* transition y •α. π→π* at shorter wavelength (<250nm. will show two absorptions: n→π* at longer wavelength (>300nm low intensity) (>300nm. acids. the λmax of the π→π* band moves to linger wavelengths . Nielsen’s rules Compounds which are highly colored are likely to contain a long-chain conjugated system (4~5) or a polycyclic aromatic chromophore. .

Homework and Course Requirements • Comprehend the rationale Ultraviolet and visible spectra t • Master the fundamental type of electronic transition • Master the major component parts and the demand of every part of visible ultraviolet spectrophotometer • Finish Homework .

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