ADVANCED PHOTOCHEMISTRY

& RADIATION CHEMISTRY

COURSE CODE: CHEM-743

DR. ABDUR RAUF

Department of Chemistry
University of Sahiwal
FLUORESCENCE

SPECTRA
 Fluorescence Spectrum of
Azulene
• Azulene is an aromatic hydrocarbon that contains no six-membered

rings. It is an isomer of naphthalene and has a similar odor, but

instead of white, its crystals are dark blue and is known for six

centuries.
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• According to Kasha ’ s rule, fluorescence from organic compounds

usually originates from the lowest vibrational level of the lowest

excited singlet state (S1 ).

• An exception occurs in case of hydrocarbon azulene, which shows

fluorescence from S2. This behaviour may be explained by

considering that the azulene molecule has a relatively large S2 – S1

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gap, which is responsible for slowing down the normally rapid S2

to S1 internal conversion such that the fluorescence of azulene is

due to the S2 → S0 transition.

• The fluorescence emission spectrum of azulene is an approximate

mirror image of the S0 → S2 absorption spectrum.

…continued
Fluorescence Quantum Yield:

• The fluorescence quantum yield of a compound may be determined

by comparing the area under its fluorescence spectrum with the area

under the fluorescence spectrum of a reference compound whose

fluorescence quantum yield is known. The spectra of both

compounds must be determined under the same conditions in very

dilute solution.
…continued

• Because of Kasha’ s rule, the probability of an excited molecule

ending up in the lowest vibrational energy level of S1 is very high,

irrespective of the energy of the exciting light used. Thus the

fluorescence quantum yield is independent of the wavelength of the

exciting light ( Vavilov’ s rule ).

 … continued

• A molecule in S1(v = 0) can undergo fluorescence, intersystem

crossing or internal conversion, which have rate quantum yields φf ,

φisc and φic , respectively and:

• If the only process occurring from S1(v = 0) is fluorescence then φf

will be equal to 1, whereas if no fluorescence occurs from S1(v = 0)

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then φf will be equal to 0. Thus the fluorescence quantum yield

has values between 0 and 1.

• In general, because of the relatively large energy gap between S0

and S1 , φic is much smaller than φf and φisc , which implies that

φf + φisc ≈ 1

• This is called Ermolev ’ s rule.

 Factors Effecting Fluorescence
Spectrum
1) The Nature of S1

• Molecules in which S1 is (π, π*) tend to have a high fluorescence

quantum yield. In general, S1 (π, π*) states have much shorter

lifetimes (of the order of ns) than S1 (n, π*) states (of the order of

μs) and so S1 (π, π*) states are more likely to undergo fluorescence

emission before intersystem crossing can occur.

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• Fluorescence from S1 (n, π*) is generally weak because not only is

the excited state lifetime longer but the rate of intersystem crossing

is faster. This faster rate of intersystem crossing is due to the fact

that the singlet – triplet energy gap, E(S–T), is smaller for S1(n,π*)

than for S1 (π, π*).

• The net result is that for molecules in which S1 is (π, π*), both
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fluorescence and phosphorescence emission will be observed

provided φf < 1, but if S1 is (n, π*) then the quantum yield of

phosphorescence will very likely be much greater than φf .

2. Molecular Rigidity

• Molecular rigidity can be increased either by increasing the structural

rigidity of the molecule (by preventing rotation or bending of bonds)

or by increasing the rigidity of the medium (for example, by

replacing a fluid solution at room temperature with a rigid glass

made by freezing the fluid solution). Molecular rigidity favors

efficient fluorescence emission

…continued
…continued

• The fluorescence quantum yield of trans-stilbene is 0.75 when

measured in a rigid glass at 77 K, showing that the rigid medium

results in more efficient fluorescence.

3. The Effect of Substituent Groups

• Substituent groups have a marked effect on the fl uorescence

quantum yield of many compounds. Electron - donating groups such

…continued

as –OH, –NH2 and –NR2 enhance the fluorescence efficiency,

whereas electron withdrawing groups such as –CHO, –COOH and

–NO2 reduce the fluorescence quantum yield.

4. The Heavy Atom Effect

• The presence of so - called heavy atoms such as bromine or iodine in

either the parent molecule (internal heavy atom effect) or the solvent

(external heavy atom effect) increases the probability of intersystem

crossing by increasing the magnitude of the spin – orbit coupling.

…continued
 Molecular Fluorescence in
Analytical Chemistry
• Measurement of fluorescence intensity can be used for quantitative

analysis of fluorescent compounds where the intensity of

fluorescence is proportional to the concentration of the compound.

• Because of their high sensitivity and selectivity, analytical

techniques based on fluorescence detection are commonly used. If a

target compound is fluorescent then direct detection of the

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fluorescence is possible using a fluorimeter.

• For example, the urine of patients with kidney disorders contains

abnormally high levels of the hormones adrenaline, noradrenaline

and dopamine. The three compounds of interest can be separated by

HPLC followed by fluorescence intensity measurement at 310 nm

with the excitation wavelength 286 nm.

…continued

• Derivatization methods can be used where the substance of interest

is not fluorescent but may be converted into a fluorescent derivative

by reaction with a suitable (nonfluorescent) reagent.

• For example, 8-hydroxyquinoline is not fluorescent, because its

non-bonded electrons give rise to an (n, π*) excited state on

irradiation. However, when these electrons bind to Al3+ ions the

…continued

complex formed is fluorescent due to:

• Formation of a ring, which increases the rigidity of the molecule.

8 - hydroxyquinoline Complex
…continued

• By building scale models of aircraft equipped with many pressure

sensors it is possible to investigate the effects of pressure variations

across the model surface when high - speed wind tunnel trials are

carried out.

• This method is very time - consuming and costly, so an alternative

strategy involves the use of a paint containing an oxygen-sensitive

…continued

fluorescent compound. The fluorescent lifetime of the pressure-

sensitive paint becomes shorter as the oxygen pressure increases.

• In regions of high pressure, dissolved oxygen concentration in the

paint increases and the fluorescence from the paint is quenched.

Thus pressure images can be collected and related to previously

collected pressure – calibration data.