Photochemical processes

2nd singlet excited state

Chap. 12 Photochemistry
Jablonski diagram
3rd triplet excited state 2nd triplet excited state

1st singlet excited state

1st triplet excited state Ground state

1. 2. 3. 4. 5. 6. 7. 8. 9. 10.

Light absorption: S0 S1, S0 S2 k~1015 Vibrational Relaxation: k~1012/s, from high to low Internal Conversion: to lower electronic state of same multiplicity (k>1010/s ) Radiationless Decay: S1S0, no emission, k<106/s Intersystem Crossing: k 106~1010 /s, depends on molecules. (carbonyl fast; alkene slow) Fluorescence: S1 S0, with emission. k 106 -109. Phosphorescene: T1 S0 with emission. k 10-2 104 Triplet Triplet Absorption Singlet Singlet Absorption Singlet Triplet Absorption

Photophysical Processes
S0(ground st.) of H2C=O : [(1SO)2(1SC)2(2SO)2(C-H)2 (C-H)2 (C-O)2](C-O)2 (nO)2 S1(1st exc.state): [(1SO)2(1SC)2(2SO)2(C-H)2 (C-H)2 (C-O)2](C-O)2 (nO)(*C-O) S2(2nd exc.state): [(1SO)2(1SC)2(2SO)2(C-H)2 (C-H)2 (C-O)2](C-O) (nO)2(*C-O)
H H
*c-o n c-o n * *

UV Absorption and Emission

Factors determining radiative transition:
1. Symmetry of electronic state (ini. final state) 2. Multiplicity of the spin
Spin-orbit interaction (allows different spin transition mixing due to the mixing of magnetic moment of e- and the magnetic moment of the nucleus) Heavy atom effect: higher rate of intersystem crossing Greater mixing if S and T are closer in energy, example carbonyl cpds. Vertical transition

3. Frank-Condon term,
determined by overlap of nuclear coordinate of init. and final state
Internuclear distance

 At the instant of excitation, only electrons are reorganized, the heavier nuclei retain the ground state geometry The excited state has similar molecular geometry as ground state

Frank-Condon Principle
(1): Vib. energy diff. of S0 (2): (0,0) transition (3): Vib energy diff. of S1
(2) (1)

(3)

Anthrcene

geometry quite different from ground state geometry => large Stokes shift (anti-Stokes shift: the fluorescence is at shorter wavelength)

Fluorescence The excited state

Stokes shift

hv
planar geometry

 Beer-Lambert Law: logI It =A (absorbance) I0: incident light It: transmitted light : extinction coefficient c: concentration d: light path length

Measurement of Absorption
=c d

Quantum yield of emission:

# of photon emitted from S 1 f = # of photon absorbed

Phosphorescence

OH Br

Much reduced due to diffusional quenching with ground state species or O2 Observed in fixed matrix, such as liquid N2 temperature or surrounded by a host

In aqueous solution with -CD

Concentration Dependent Fluorescence

Excimer formation Excimer: A complex formed between an excited molecule with a ground state molecule of same compound

In heptane A*A AA*

Geometric Requirement of Excimer Formation

The molecular plane can stack together with interplanar distance less than 3.5 .
CH2(CH2)nCH2

n=0 no overlap of ring n=1 excimer formation n=2 strain of chain

CH2CH2CH2

CH2CH2 CH2

Excimer formation Partial overlap of ring plane

 Exciplex: complex formed between an excited molecule with a ground state molecule of dissimilar molecule A*B AB* can give exciplex emission or quench emission
N(CH2CH3)2

aromatics / amine aromatics/conjugate olefin

CH3 N HC CH3

Fluorescence quencher
CH3

quench by Geometric requirement less stringent

1)

Radiative energy transfer D* D+ hv A+hv A* The rate depends on The quantum yield of emission by D* (De) The concentration of (the # of) A in light path The light absorbing ability of A (extinction coefficient) The overlap of emission spectrum of D* and absorption of A (spectral overlap integral)

Energy Transfer and Electron Transfer Pathways D*+A D+A*

2)

Frster energy transfer Long range (D*-A distance up to 100 ) No radiation involved The dipole-dipole interaction of D* and A
inte
Cou lom b rac tion

An interaction at a distance via electromagnetic field, induce a dipole oscillation in A by D*. Efficient transfer requires a good overlap of emission of D* with absorption of A.

3) Collisional energy transfer (Dexter energy transfer): exchange of electron between the donor and acceptor
electron exchange

The exchange of electron via overlap of electron clouds require physical contact between the interacting partners. Spectral overlap integral also required This process allows triplet state to be generated D* + A0 D0 + A* A short-ranged interaction

Electron Transfer
The photo excited state is a better donor (lower oxid. potential) as well as a better acceptor (lower reductive potential) relative to ground state

Acidity and Basicity in Excited States

O-

OH

A-H hv [A-H]*

A - + H+ [A-]* + H+

 H*+hv = H+hv H*-H = +hv - hv G*-G (if S* S for ionization) G = 2.303RTpK hv" hv ' G * - G pK*-pK=
2.303RT

2.303RT

(1) (2) (3)

(1):more acidic (2):less acidic (3):more acidic

When photochem. excited, electron from HOMO LUMO, and change the e- density

LUMO
OH

HOMO

LUMO

COOH

HOMO

HOMO
H3C N CH3

LUMO

N+ H3C

n
H

C
H

Bond angle, Dipole moments of Excited state * hv

H

LUMO
H
H

HOMO
H

C
H

O
H

O H

(allowed, strong)

(forbidden, Weak)

S0 S1 (n-*) excited state less polar than the ground state

hypsochromic (blue) shift with polar solvent

S0 S2 (- *) excited state more polar than the ground state

bathochromic (red) shift with polar solvent

Photochemical Reactions of Carbonyl Compounds

O

hv
*
O
1

diradical character

Satd Ketone
3

n *
* or

C O

C O

Norrish Type I Cleavage (- cleavage)

O R R

hv

O R R

*
R

O C + R

R
R

+ CO

CH3(CH2)2CH=CH2+CO
O

disproportionation

hv
gas phase

CO

more energetic lose CO readily

H2C = CH2+H3CCH = CH2+CO

fragmentation

S1 T1 at vibrationally excited state of T1

hv
solution

H 2 C = C H (C H 2 ) 3 C H O

O
C

O H

Ketene
H C O

ROH
OR

H2O Less energetic; no CO loss

O C OH
acid

Hydrogen Abstraction Reaction

O

hv

O C

H-A

H O

Ph
O

OH hv

Ph
Photoreduction of benzophenone in iPA
Ph

Ph HO Ph

Ph Ph

H 3C H 3C

OH +

OH

Ph

Ph

OH

O
Ph

Ph

OH
Ph

H 3C HO H 3C

Stable radical

Norrish Type II Cleavage(-Cleavage)

O R H CH2 hv CH2 CH2

H O R

CH2 CH CH2 2
R

CH2 CH2

6-membered ring (T.S.)

O R CH3

OH CH2 R

HO
If the S.M. is retrieved, the carbon may loose stereochem. (if chiral), so not exactly the same original S.M.

R
O CH3 R
- unsaturated ketone

H O
hv

H O
O

Absorb at longer wave length

Photo-driven

De-conjugated absorb at shorter wave length

Oxetene Formation (Paterno-Buchi Reaction)

*O
O O

hv
O

H HO H

hv
H Ar

Ar O H

Ar

Photochemical Reactions of Alkene and Dienes

Isomerization

1.

C C

hv
*
265 nm

< 200nm 2. max

higher

C C

Cis

trans lower

Trans compound has longer absorption wavelength Both cis and trans give the same excited state species => twisted geometry with 90o rotation of p-orbital relative to each other

R1 R2

C C

R3 R4

hv

R1 R2

R3 R4

hv R1

R4 R3

R2
3

A photostationary state will be reached from either side (cis photostationary state; trans photostationary state)

[C ] pss [T ] pss

t kc c kt

kc=formation constant of cis from the excited twisted state kt =formation constant of trans from the excited twisted state

(CH2)n

hv xylene -H+

*
(CH2)n ROH + H OR ROH, -H+ (CH2)n -H+ H (CH2)n H
strained

For n=4,5,6

(CH2)n

OH hv
H+-catalyzed hydration

+
OH

89%

2%

OH

H+-catalyzed hydration
OH

For cyclopentene, the cis-trans isomerization doesnt occur.

CH3OH

CH2OH + + 2

hv

by H abstraction of the diradical species

The photochemically allowed reaction by symmetry rule may be only one of many reaction pathways

H
193nm

hv

thermally allowed other mechanism

Symmetry-allowed dis. rot. product