You are on page 1of 55

1

l lM8 Soect·oscooy 
ClM 244 - C·gan|c C|em|st·y ll
M|se·|co·o|a bn|ve·s|ty
L·. l·an| ?eoez Casn||o 
So·|ng 2014
1
1yoes o¦ Soect·oscooy
2
L|¦e·ent ·eg|ons o¦ t|e e|ect·omagnenc soect·um a·e useo to
o·obe o|¦e·ent asoects o¦ mo|ecu|a· st·uctu·e
Magnenc o·ooe·nes o¦ luc|e|
1|e so|nn|ng c|a·ge |n t|e
nuc|eus c·eates a MAClL1lC
MCMLl1 (Magnenc ¦e|o)  
S
luc|ea· so|n 8 Lxte·na| Magnenc l|e|os
/
luc|ea· so|n 8 Lxte·na| Magnenc l|e|os
8
lnst·umentanon (Connnuous vave)
19
lnst·umentanon (l1 lM8)
20
lnst·umentanon (l1 lM8)
21
C|em|ca| S||¦s
24
! Leg·ee o¦ s||e|o|ng w||| oeoeno on t|e oens|ty o¦ t|e e|ect·on
c|ouo c|·cu|anng a·ouno a nuc|eus
! 1|e o|¦e·ence |n t|e abso·onon oos|non o¦ a oa·ncu|a· o·oton
¦·om t|e abso·onon oos|non o¦ a !"#"!"$%" o·oton |s ca||eo t|e
%&"'(%)* ,&(- o¦ t|e oa·ncu|a· o·oton 
C|em|ca| S||¦s
2S
Anyt||ng t|at a¦ects t|e oens|ty o¦ t|e e|ect·on
c|ouo a·ouno a oa·ncu|a· nuc|eus w||| a¦ect |ts
c|em|ca| s||¦: 
! L|ect·oneganv|ty e¦ects (|noucnon)
! lyb·|o|zanon e¦ects (|noucnon) 
! Ac|o|ty ano exc|angeab|e o·otons, l-bono|ng
! Magnenc An|sot·ooy
C|em|ca| S||¦s
! l·otons |n o|¦e·ent c|em|ca| env|·onments a·e s||e|oeo by
o|¦e·ent amounts
! 1|e |yo·oxy| o·oton |s not s||e|oeo as muc| as t|e met|y|
o·otons so t|e |yo·oxy| o·oton abso·bs at a |owe· ¦e|o t|an
t|e met|y| o·otons
! ve say t|at t|e o·oton |s oes||e|oeo somew|at by t|e
o·esence o¦ t|e e|ect·oneganve oxygen atom.
26
C|em|ca| S||¦s
2/
lM8 S|gna|s
! 1|e !"#$%& o¦ s|gna|s s|ows |ow many o|¦e·ent
||nos o¦ o·otons a·e o·esent 
! 1|e '()*+(! o¦ t|e s|gna|s s|ows |ow s||e|oeo o·
oes||e|oeo t|e o·oton |s 
! 1|e ,!-%!.,-/ o¦ t|e s|gna| s|ows t|e numbe· o¦
o·otons o¦ t|at tyoe 
! 1|e .0',1!2 s|ows t|e numbe· o¦ o·otons on
ao¦acent atoms
28
C|em|ca| S||¦s
29
1|e most gene·a||y use¦u| ·e¦e·ence
comoouno |s tet·amet|y|s||ane (1MS) 
1|e ze·o on t|e lM8 sca|e |s oe¦neo by
t|e oos|non o¦ t|e oea| ¦o· 1MS.
1|e c|em|ca| s||¦ |s a measu·e o¦ |ow ¦a· t|e s|gna| |s ¦·om
t|e ·e¦e·ence s|gna|
1|e common sca|e ¦o· c|em|ca| s||¦s |s |e ! (oe|ta) sca|e
!! # #$%&$'()*+,-.(' /0(12(,34 5/ .6( *,).027(,.
#8$%& 
C|em|ca| S||¦s
30
C|em|ca| S||¦s
31
C|em|ca||y equ|va|ent o·otons: o·otons |n t|e same c|em|ca|
env|·onment
Lac| set o¦ c|em|ca||y equ|va|ent o·otons |n a comoouno
g|ves ·|se to a s|gna| |n an 1l lM8 soect·um o¦ t|at
comoouno
32
1
l lM8 soect·um o¦ 1-b·omo-2,2-
o|met|y|o·ooane
33
lumbe· o¦ s|gna|s
 
Lqu|va|ent ls |ave t|e
same c|em|ca| s||¦ 
1
l lM8 soect·um o¦ 1-b·omo-2,2-
o|met|y|o·ooane
34
C|em|ca| S||¦s
3S
C|em|ca| S||¦s - Magnenc An|sot·ooy
40
C|em|ca| S||¦s - Magnenc An|sot·ooy
41
C|em|ca| S||¦s - Magnenc An|sot·ooy
42
lnteg·a|s ano lnteg·anon
ln t|e lM8 soect·um, t|e a·ea unoe· eac|
oea| |s o·ooo·nona| to t|e numbe· o¦
|yo·ogens gene·anng t|at oea|.
1|e |nteg·anon te||s us t|e ·e|anve numbe· o¦
o·otons t|at g|ve ·|se to eac| s|gna|, not t|e
abso|ute numbe·
 
 
4S
1
l lM8 soect·um o¦ 1-b·omo-2,2-
o|met|y|o·ooane
4/
low many |yo·ogens` 
48
lnteg·a|s ano lnteg·anon
49
So||mng o¦ t|e s|gna|s
! An
1
l lM8 s|gna| |s so||t |nto / - 1 oea|s, w|e·e /
|s t|e numbe· o¦ equ|va|ent o·otons bonoeo to
ao¦acent ca·bons
! Couo|eo o·otons so||t eac| ot|e·'s s|gna|
! 1|e numbe· o¦ oea|s |n a s|gna| |s ca||eo t|e
mu|no||c|ty o¦ t|e s|gna|
! 1|e so||mng o¦ s|gna|s, causeo by so|n-so|n
couo||ng, occu·s w|en o|¦e·ent ||nos o¦ o·otons
a·e c|ose to one anot|e·
S4
So||mng o¦ t|e s|gna|s
lt |s not t|e numbe· o¦ o·otons g|v|ng ·|se to a s|gna|
t|at oete·m|nes t|e mu|no||c|ty o¦ t|e s|gna|
lt |s t|e numbe· o¦ o·otons bonoeo to t|e
|mmeo|ate|y ao¦acent ca·bons t|at oete·m|nes t|e
mu|no||c|ty
 
S6
So||mng o¦ t|e s|gna|s
Lqu|va|ent o·otons oo not so||t eac| ot|e·'s s|gna| 
S/
S8
S9
60
So|n Couo||ng, Mu|no|ets
ano So|n Systems
So|n Couo||ng, Mu|no|ets ano So|n Systems
62
So||mng o¦ t|e s|gna|s
So||mng |s obse·veo |¦ t|e o·otons a·e seoa·ateo by no mo·e
t|an t|·ee " bonos 
63
Long-range
coupling occurs
over # systems,
such as benzene
64
So|n Couo||ng, Mu|no|ets ano So|n Systems
6S
So|n Couo||ng, Mu|no|ets ano So|n Systems
6/
68
69
/0
/1
Couo||ng Constants
1|e couo||ng constant (0) |s t|e o|stance between two
ao¦acent oea|s o¦ a so||t lM8 s|gna| (|n lz)
/2
Coupled
protons have
the same
coupling
constant
1yo|ca|
1
l-lM8 Abso·onons by tyoe o¦ comoounos
/4
1yo|ca|
1
l-lM8 Abso·onons by tyoe o¦ comoounos
/S
1yo|ca|
1
l-lM8 Abso·onons by tyoe o¦ comoounos
/6
1yo|ca|
1
l-lM8 Abso·onons by tyoe o¦ comoounos
//
1yo|ca|
1
l-lM8 Abso·onons by tyoe o¦ comoounos
/8
1yo|ca|
1
l-lM8 Abso·onons by tyoe o¦ comoounos
/9
1yo|ca|
1
l-lM8 Abso·onons by tyoe o¦ comoounos
80
1yo|ca|
1
l-lM8 Abso·onons by tyoe o¦ comoounos
81
1yo|ca|
1
l-lM8 Abso·onons by tyoe o¦ comoounos
82
1yo|ca|
1
l-lM8 Abso·onons by tyoe o¦ comoounos
83
1yo|ca|
1
l-lM8 Abso·onons by tyoe o¦ comoounos
84
Summa·y
! 1|e numbe· o¦ c|em|ca| s||¦s (!) soec|¦y t|e
numbe· o¦ o|snnct o·oton env|·onments |n t|e
comoouno
! 1|e c|em|ca| s||¦ (!) va|ues soec|¦y t|e natu·e o¦
t|e c|em|ca| env|·onment: a||y|, a||ene, etc.
! 1|e |nteg·anon va|ues soec|¦y t|e ·e|anve numbe·
o¦ o·otons ¦o· eac| s|gna|
! 1|e so||mng soec|¦es t|e numbe· o¦ ne|g|bo·|ng
o·otons
! 1|e couo||ng constants soec|¦y t|e o·|entanon o¦
t|e couo|eo o·otons
8S