CYN-525

Advanced Molecular
Spectroscopy
Lecture 13

Dr. Pavan Kumar

Spin-spin decoupling

Simplifying the spectra – removing scalar spin-spin coupling

Double resonance

Second RF generator coil - Decoupler

HA & HX - they are coupled (JAX)

Rapid shuttling between the two spin states – average spin

Scalar product of µA⋅ µX

Enhancement – homonuclear/heteronuclear

Broadband decoupling
 Original Overhauser Effect
Nuclear spin with electron spin
Enhancement observed in nuclear spin

W – probability of relaxation transitions (maintenance of boltzman distribution

W1 & W1’ correspond to probability for longitudinal

Albert Overhauser relaxation of nuclear and electronic spins
W2 & W0 correspond to transition probabilities
where both spins flip simultaenously
Population Probability

At equilibrium

Boltzmann law

Population differences are defined by a

larger energy gap
 Nuclear Overhauser Effect
Solomon equation
Z-magnetization of nucleus X
Equilibrium magnetization

For a homonuclear case 𝛾𝐴 = 𝛾𝑋 signal enhancement of 50%

Negative NOE – negative gyromagnetic ratio – 15N or 29Si

NOE will be less if relaxation is occurring via other pathways

than dipolar mechanisms
Chemical Shift reagents

Paramagnetic species

Dipolar through-space interaction

between magnetic moments

Tris-(dipivalometha- Tris-(6,6,7,7,8,8,8-heptafluoro-
nato) europium 2,2-dimethyl-3,5-octanedionato)
europium

On the basis of the angle factor – shifts to both lower or higher

Frequency – LIS – Lanthanide induced shift

Poor man’s high field NMR

Simplifies 2nd order spectrum to first order

Acidic groups not compatible

Line broadening occurs but minimal with lanthanides
Chemical Shift reagents

First order spectrum (100 MHz) Second order spectrum (60 MHz)
13 C NMR
12C and 13C are naturally occurring isotopes

Natural abundance of 12C 98.9% (I=0, NMR Inactive)

Natural abundance of 13C 1.1% (I=1/2, NMR Active)

13C NMR can give information in these cases

Factors affecting chemical shifts of 1H also affect the 13C spectra

TMS is the reference – so no need to change reference when recording 1H and 13C

Resonating frequency is 4 times less than protons

Usually 13C spectra are recorded with broadband decoupling (but coupling with other NMR active nuclei will be active still)
13 C NMR
13C is about 6000 times less sensitive compared to 1H
Requires 6000 x 6000 scans for same S/N as 1H
Longer to acquire useful spectra
13 C NMR
13C is about 6000 times less sensitive compared to 1H
Requires 6000 x 6000 scans for same S/N as 1H
Longer to acquire useful spectra
13 C NMR

No C-C coupling are generally observed

Satellite peaks with intensity about 0.5% of the

main peak will be observed in 1H NMR or 13C
NMR JCH
1J 2 3
C-H - 120-150 Hz, JC-H , JC-H - 2-15 Hz
13 C NMR
19F

Large chemical shift range - Less overlapping of signals

CFCl3 – 19F NMR internal reference

Most NMR shifts are negative ~1%

Ring current effects or local magnetic anisotropies – no role
Most solvents don’t have Fluorine and hence compatible
Record parts of the spectrum – Pulse excitation not sufficient
31P

H3PO4 – 31P NMR internal reference

Satellite peaks
D2O Shake