Chem 312 L11a Photoluminescence Spectros

An Introduction to Fluorescence Spectroscopy Spectroscopy Definition of fluorescence Photoluminescence: An Introduction to Fluorescence Spectroscopy
Spin states Jablonski diagram Comparison to phosphorescence Quantum yield Emission, lifetime, and quantum yield spectroscopy Broadband internet applications Bioapplications Quantum cutters
Chem 312, Spring 2007
Lanthanide chemistry Special topic: Lanthanide-based Fluorescence
February 15, 2007
February 15, 2007
An Introduction to Fluorescence Spectroscopy

Photoluminescence occurs when an external source of energy, in the form of electromagnetic radiation, is absorbed by a atom or molecule, resulting in the emission of photons. Normally the absorbed light is at a higher energy level (frequency) than the emitted energy.
- First
part of talk part of talk
- Second
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February 15, 2007

Photoluminescence occurs when an external source of energy, in the form of electromagnetic radiation, is absorbed by a atom or molecule, resulting in the emission of photons. Not always seen at room temperature excitation/ emission spectroscopy

At room temperature most molecules occupy the lowest vibrational level of the ground electronic state, and on absorption of light they are elevated to produce excited states. The simplified diagram below shows absorption by molecules to produce either the first, S1, or second S2, excited state.
February 15, 2007
February 15, 2007

What is the difference between fluorescence and phosphorescence? Electron Spin States
Fluorescence requires that the spin state of the electron remains the same during the transition from the lowest excited singlet state, S1, to the singlet ground state, S0. Phosphorescence requires that the spin state of the electron changes during the transition from the lowest excited triplet state, T1, to the singlet ground state, S0.
Phosphorescence decay is similar to fluorescence, except the electron undergoes a spin conversion into a "forbidden" triplet state (T(1)) instead of the lowest singlet excited state, a process known as intersystem crossing. Emission from the triplet state occurs with lower energy relative to fluorescence, hence emitted photons have longer wavelengths.
February 15, 2007
February 15, 2007

What is a Quantum efficiency?
To account adequately for the processes of absorption and emission of light, it is necessary to assume that radiant energy can only be absorbed in definite units, or quanta. The energy, E, carried by any one quantum is proportional to its frequency of oscillation, that is E = h!/ ! = hc ergs f where ! is the frequency, ! the related wavelength and h = Planck's constant (6.624 x 10-27 ergs/seconds). The energy of a single quantum is too small for convenience and it is usual to talk of the energy associated with N quanta (where N = 6.023 x 1023 the number of single molecules in a gram molecule), which is called an einstein. Thus, if in a photochemical reaction one molecule reacts for each quantum absorbed, then the absorption of one einstein is sufficient energy for the reaction of one gram mole. Since the amount of energy per einstein is proportional to the frequency of the radiation, it varies enormously over the range of the electromagnetic spectrum.
So how do we measure the efficiency of the emission process? By calculating the Quantum Efficiency (also known as a Quantum Yield, ")
Or in other words:
" = photons emitted photons absorbed and the maximum value attainable is 1 (100% efficiency).
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February 15, 2007
An Introduction to Fluorescence Spectroscopy So what affects the quantum yields of fluorophores?

Typically there are three main factors that affect luminescent output (i.e.: ") of fluorphores: Internal conversion (IC) Intersystem crossing (ISC) Vibrational relaxation

Typically there are three main factors that affect luminescent output (i.e.: ") of fluorphores: Internal conversion (IC)
radiationless transition between energy states of the same spin state
February 15, 2007
February 15, 2007

Typically there are three main factors that affect luminescent output (i.e.: ") of fluorphores: Internal conversion (IC) Intersystem crossing (ISC)
radiationless transition between different spin states

Typically there are three main factors that affect luminescent output (i.e.: ") of fluorphores: Internal conversion (IC) Intersystem crossing (ISC) Vibrational relaxation
Due to physical contact of an excited molecule with other particles with which energy, in the form of vibrations and rotations, can be transferred through collisions.
February 15, 2007
February 15, 2007
An Introduction to Fluorescence Spectroscopy So in relation to fluorescence and phosphorescence, where do the three factors appear?
An Introduction to Fluorescence Spectroscopy: Lanthanides
February 15, 2007
February 15, 2007

The nomenclature used describe each level is referred to as 2S+1LJ levels according to Russell- Saunders coupling schemes, where S is the spin multiplicity, L is the orbital angular momentum, and J is the total angular momentum. For f-element ions in solids, especially trivalent lanthanide ions, the electronic transitions only have a weak coupling to lattice vibrations and electric fields due to the 4f electrons being shielded by the 5s and 5p electrons. However, despite the weak ion lattice interaction, this perturbation is responsible for the spectral fine structure in which the optical spectra of f-f transitions have extremely sharp lines almost of atomic
February 15, 2007
February 15, 2007

Many luminescent lanthanide ions have desirable properties, such as luminescence ranging from the visible to the near-infrared, long-lived luminescent lifetimes, and resilience to photobleaching, yet use of these ions has often been limited due to their low molar absorption coefficients. Each line in the absorption spectrum corresponds to an individual energy level inside the 4f shell (only f-f transitions occur), while the luminescence spectrum corresponds to the transitions between two energy levels, but not necessarily involving the ground state
February 15, 2007
February 15, 2007

When a trivalent lanthanide ion is located at a crystal-lattice site with perfect symmetry, the transitions between the intra-4f levels in the ion are strictly parityforbidden by LaPorte selection rules, whereby no change in angular momentum (L) between the ground state 4f and the excited state 4f occurs: d-d transitions in an octahedral field are always gerade gerade, thus forbidden (Gerade orbitals have a center of inversion,Ungarade do not have a center of inversion) (Do we need a refresher on this? Next slide) But for an octahedral complex, the Laporte selection rule can be relaxed by either a static (crystal packing or ligand differences) or a dynamic (vibrations) departure from perfect octahedral symmetry.

The Selection Rules governing transitions between electronic energy levels of transition metal complexes are: !S = 0 The Spin Rule !l = +/- 1 The Orbital Rule (Laporte) The first rule says that allowed transitions must involve the promotion of electrons without a change in their spin. The second rule says that if the molecule has a centre of symmetry, transitions within a given set of p or d orbitals are forbidden (i.e. those which only involve a redistribution of electrons within a given subshell). Relaxation of the Rules can occur through: a) Spin-Orbit coupling - this gives rise to weak spin forbidden bands b) Vibronic coupling - an octahedral complex may have allowed vibrations where the molecule is asymmetric. Absorption of light at that moment is then possible. c) "-acceptor and "-donor ligands can mix with the d-orbitals so transitions are no longer purely d-d. Types of transition Charge transfer, either ligand to metal or metal to ligand. These are often extremely intense and are generally found in the UV but they may have a tail into the visible. The d-d transitions, these can occur in both the UV and visible region, but since they are forbidden transitions they typically have small intensities.
February 15, 2007
February 15, 2007

However, if the ion is in a lattice lacking inversion symmetry, the forbidden transitions are relaxed due to the mixing of opposite parity states into the 4fn configuration, due to an asymmetric crystal field. As a result, the observed transitions for lanthanide ions are a result of magnetic dipole (MD) transitions, induced electric dipole (ED) transitions, and electric quadrupole (EQ) transitions. Of the three, the MD and ED are studied the most due to the luminescent intensity of the transition and the structural information that they provide.
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February 15, 2007
February 15, 2007
February 15, 2007

In the simplest case of a single fluorescence decay process, the fluorescence intensity, f(t), will follow an exponential dependence on time:

Taking the above effects into account, the actual measured time dependent fluorescence intensity becomes a convolution of the instrumental response function P(t) and the theoretical sample decay.
where # is the characteristic fluorescence lifetime and f(0) is the fluorescence intensity at time zero. More complex fluorescence decays can be represented by a sum of up to four exponential terms, and by a constant background, (A):
In practice, instrumental processes affect the measured fluorescence decay. The theoretical fluorescence decay is superimposed by noise (Poisson noise), and the initial part of the decay can be broadened by the finite pulse width of the excitation source, the transit time spread of the detector, and other potential optical and electronic contributions.
The aim of the numerical analysis is to fit the function F(t) to the measured sample decay, thus extracting the theoretical fluorescence decay model f(t) by eliminating the effects of the instrumental response function and the effects of the noise.
February 15, 2007 Chem 312, Spring 2007
February 15, 2007
February 15, 2007
February 15, 2007
February 15, 2007
February 15, 2007
An Introduction to Fluorescence Spectroscopy: Lanthanides Sensitized emission

Many luminescent lanthanide ions have desirable properties, such as luminescence ranging from the visible to the nearinfrared, long-lived luminescent lifetimes, and resilience to photobleaching, yet use of these ions has often been limited due to their low molar absorption coefficients.
Up-conversion processes
February 15, 2007
February 15, 2007
Many luminescent lanthanide ions have desirable properties, such as luminescence ranging from the visible to the near-infrared, long-lived luminescent lifetimes, and resilience to photobleaching, yet use of these ions has often been limited due to their low molar absorption coefficients.
Sensitivity to quenching for NIR applications
February 15, 2007
February 15, 2007
An Introduction to Fluorescence Spectroscopy: Lanthanides Schematic diagram of the avidin-biotin pocket
Bio-applications: visible and NIR
February 15, 2007
February 15, 2007
An Introduction to Fluorescence Spectroscopy: Lanthanides Current bioapplications: DELFIA analysis
February 15, 2007
February 15, 2007

Chem 312 L11a Photoluminescence Spectros

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An Introduction to Fluorescence Spectroscopy Spectroscopy Definition of fluorescence Photoluminescence: An Introduction to Fluorescence Spectroscopy

Lanthanide chemistry Special topic: Lanthanide-based Fluorescence

February 15, 2007

Chem 312, Spring 2007

February 15, 2007

An Introduction to Fluorescence Spectroscopy

An Introduction to Fluorescence Spectroscopy

part of talk part of talk

February 15, 2007

Chem 312, Spring 2007

February 15, 2007

Chem 312, Spring 2007

An Introduction to Fluorescence Spectroscopy

An Introduction to Fluorescence Spectroscopy

February 15, 2007

Chem 312, Spring 2007

February 15, 2007

Chem 312, Spring 2007

An Introduction to Fluorescence Spectroscopy

An Introduction to Fluorescence Spectroscopy

February 15, 2007

Chem 312, Spring 2007

February 15, 2007

Chem 312, Spring 2007

An Introduction to Fluorescence Spectroscopy

An Introduction to Fluorescence Spectroscopy

February 15, 2007

Chem 312, Spring 2007

February 15, 2007

Chem 312, Spring 2007

An Introduction to Fluorescence Spectroscopy So what affects the quantum yields of fluorophores?

An Introduction to Fluorescence Spectroscopy So what affects the quantum yields of fluorophores?

February 15, 2007

Chem 312, Spring 2007

February 15, 2007

Chem 312, Spring 2007

An Introduction to Fluorescence Spectroscopy So what affects the quantum yields of fluorophores?

An Introduction to Fluorescence Spectroscopy So what affects the quantum yields of fluorophores?

February 15, 2007

Chem 312, Spring 2007

February 15, 2007

Chem 312, Spring 2007

An Introduction to Fluorescence Spectroscopy: Lanthanides

February 15, 2007

Chem 312, Spring 2007

February 15, 2007

Chem 312, Spring 2007

An Introduction to Fluorescence Spectroscopy: Lanthanides

An Introduction to Fluorescence Spectroscopy: Lanthanides

February 15, 2007

Chem 312, Spring 2007

February 15, 2007

Chem 312, Spring 2007

An Introduction to Fluorescence Spectroscopy: Lanthanides

An Introduction to Fluorescence Spectroscopy: Lanthanides

February 15, 2007

Chem 312, Spring 2007

February 15, 2007

Chem 312, Spring 2007

An Introduction to Fluorescence Spectroscopy: Lanthanides

An Introduction to Fluorescence Spectroscopy: Lanthanides

February 15, 2007