victor furer
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Victor Furer. Molecular structure and IR spectra of phosphorus dendrimers by DFT calculations. Kazan State Architect and Civil Engineering University. Scheme of dendrimer synthesis. Divergent. Convergent. A. Juris , Annu. Rep. Prog. Chem., Sect. C , 2003 , 99, 177. 2. - PowerPoint PPT PresentationTRANSCRIPT
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Victor Furer
Molecular structure and IR spectra of phosphorus dendrimers by DFT calculations
Kazan State Architect and Civil Engineering University
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Scheme of dendrimer synthesis
Divergent
Convergent
A. Juris, Annu. Rep. Prog. Chem., Sect. C, 2003, 99, 177
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1
1
NNB
G
BCNBC
MNNNMNMMW G
BB
G
BRUCC 1
1
NNZ G
BCNumber of terminal groups
Number of repeated units
Molecular mass
Topology of dendrimers
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4N. Launay et al, Angew. Chem., Int. Ed. Engl. 1994, 33, 1589
Structural scheme of growing denrimer generations
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Core Number of repeated unit Number of terminal groups
Generation Molecular mass P
S
H-C-O
CH3
- =N-N-
P
S
P
S
H-C-O
O-
(-Сl)
G’0 (G 0) 426 (168) 1 - - - 3 G’1 (G1) 1423 (903) 1 3 - 3 6 G’2 (G2) 417 (2389) 1 9 3 6 12 G’3 (G3) 7405 5349) 1 21 9 12 24
G’4 15381 1 45 21 24 48 G’5 31332 1 93 45 48 96 G’6 63234 1 189 93 96 192 G’7 127038 1 381 189 192 384 G’8 254647 1 765 381 384 768 G’9 509866 1 1533 765 768 1536
G’10 1020301 1 3069 1533 1536 3072 G’11 2041175 1 6141 3069 3072 6144
Note: in parents presented data for the series with terminal chlorine atoms.
Composition and mass of molecules of 11 generations of phosphorus
dendrimers, series G’i (Gi)
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P
S
Core H-C-O
CH 3
- =N-N- P
S
Repeated unit H-C-O
O-Terminal group
IR spectra of series G’i phosphorus dendrimers
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IR spectra of series Gi phosphorus dendrimers
P
S
Core H-C-O
CH 3
- =N-N- P
S
Repeated unit Terminal group -Cl
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Raman spectra of series G’i phosphorus dendrimers
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1640 1620 1600 1580 1560 1540 1520 1500 1480
G'2
G 3
Пог
лощ
ение
, см-1
Comparison of IR spectra series Gi и G’i
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8а 19а
1600 см-1 1500 см-1
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1800 1600 1400 1200 1000 800 600 4000
1
2
3
4
,см-1
4
3
2
1
Пог
лощ
ение
1600 1400 1200 1000 800 600 4000
1
2
3
4
1
2
3
4
,см-1
Пог
лощ
ение
MeMeMe
OSP
O
MeMeMe- C=N
OCH3
PN
SO
HO
n
MeMeMe
HC
O
- Cl2
Calculated absorption curves for the chain with number of units n = 1 (1), n = 11 (3) and
experimental IR spectra of dendrimers G’1 (2) and G’11 (4).
Calculated absorption curves for the chain with number of units n = 2 (1), n = 3 (3) and
experimental IR spectra of dendrimers G2 (2) and G3 (4).
IR spectra, theoretical curves and model fragments(approximation of linear chains)
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L.A.Gribov, Theory of IR spectra of polymers, М.: Nauka, 1977.
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1800 1600 1400 1200 1000 800 600 400
0
1
2
,см-1
2
1
Пог
лощ
ение
1800 1600 1400 1200 1000 800 600 400
0,0
0,5
1,0
1,5
2,0
, см-1
2
1
Пог
лощ
ение
O HO
S
N P3CH
OMeMeMe
MeMeMeMeMeMe
NC=- O HO
S
N P3CH
OMeMeMe NC=-
Cl
Cl
fragment II fragment IIIfragment I
Sum of theoretical absorption curves for the fragments I and II (1) and
experimental IR spectra of generation G’5 (2).
Sum of theoretical absorption curves for the fragmentsI and III (1) and
experimental IR spectra of generation G3 (2).
IR spectra, theoretical curves and model fragments(fragment approximation)
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Experimental IR spectra, theoretical curves (DFT)
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PRIRODAFunctional PBE
Базис TZ2PD. Laikov, Chem. Phys. Lett., 1997, 281, 151
M.-L.Lartigue et al, Macromolecules, 1997, 30, 7335
1600 1400 1200 1000 800 600 400
G'0
exp. cryst.
exp. melt
calc
Wavenumber,cm-1
1600 1400 1200 1000 800 600 400
G1
exp.
calc.
Wavenumber, cm-1
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R
T T
C
RRRR
TTT
T R R T
T
R TT
R RR
RT
T
TT
R
RT T
RT
T R
R
RRT
TT T
RR
TT
R=c(rn-1)/(r-1) T=crn (G0) С=1, R=0, T=c
(G1) С=1, R=c, T=cr
(G2) С=1, R=c(r+1), T=cr2 G0= С+3Т and G1= С+3R+3Т
G1 - G0 =C+3R+6T–2(C+3T) =3R–C
G2-G1=С+9R+12T–2(C+3R+6T)=3R–C
G3-G2 =C+21R+24T-2(C+9R+12T)=3R-C
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Theory of spectral «additivity»
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Experimental IR spectra of generation G2 and the difference IR spectra (G3 – G2)
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1600 1400 1200 1000 800 600 400
G2
G3
G2
Wavenumber,cm-1
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Experimental IR spectra of generation G’2 and the difference IR spectra (G’3 – G’2)
and (G’11 – G’10)
1800 1600 1400 1200 1000 800 600
G'10
G'11
G'2
G'3
G'2
Wavenumber,cm-1
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The difference Raman spectra
1800 1600 1400 1200 1000 800 600 400
G'2
G'8
G'10
G'6
G'8
G'4
G'6
G'2
G'4
G'0
Wavenumber,cm-1
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Experimental IR spectra of generations G3, G’2 and the difference IR spectra (G’2 – G3)
1800 1600 1400 1200 1000 800 600 400
G3
G'2
G3
G'2
Wavenumber,cm-1
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Experimental IR spectra of generations G’2v and the difference IR spectra (G’3v – G’2v) and (G’2 – G’2v)
1800 1600 1400 1200 1000 800 600 400
G'2v
G'2v
G'2
G'3v
G'2v
Wavenumber,cm-1
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CONCLUSIONS
1. Based on analysis of vibrational spectra series of 12 generations phosphorus dendrimers the main features of their structure were derived. It was shown that practically the same spectral picture of dendrimers started from the 2-3 generation and higher is derived by relation of terminal groups and repeated units. The zero and first generation have different structure phase state.
2. Theoretical bases for the calculation of vibrational spectra of complex molecules of dendrimers in the frame of the fragment approximation are presented.
3. The analysis of the difference vibrational spectra of dendrimers leaned on the peculiarities of its structure. The obtained results expand the possibilities of vibrational spectroscopy in analysis of conformational state, electronic effects and so on.
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Publications.
1. Kovalenko V.I., Furer V.L., Vandyukov A.E., Shagidullin R.R., Majoral J.P., Caminade A.-M. The Vibrational spectra of the elementoorganic starburst dendrimers.
J. Mol. Struct., 2002, v.604, 45-56.2. Furer V.L., Kovalenko V.I., Vandyukov A.E., Majoral J.P., Caminade A.M.,
Calculation of IR spectra of the elementorganic dendrimers. Spectrochim. Acta А, 2002, v.58, 2905-2912. 3. Furer V.L., Kovalenko V.I., Vandyukov A.E., Majoral J.-P., Caminade A.M..The vibrational analysis of the starting "monomer" and first generation of the starburst elementorganic dendrimer. Vibr. Spectr., 2003, v.31, No1, 71-79.4. Furer V.L., Vandyukov A.E., Majoral J.P., Caminade A.M., Kovalenko V.I.
Fourier-Transform Infrared and Raman Difference Spectroscopy Studies of the Phosphorus-
containing dendrimers. Spectrochim. Acta А, 2004, v.60, 1649-1657.5. Furer V.L., Vandyukov A.E., Majoral J.-P., Caminade A.-M., Kovalenko V.I. DFT
calculation of molecular structure and vibrational spectra of the phosphorus-containing G’1 generation dendrimer with terminal aldehyde groups. Chem. Phys., 2006, v.326, 417-424
6. Furer V.L., Vandyukov A.E., Majoral J.P., Caminade A.M., Kovalenko V.I. DFT study and IR spectra of the phosphorus-containing G1 generation dendrimer.
J. Mol. Struct. 2006, v.785, 133-138.7. Furer V.L., Vandyukov A.E., Majoral J.-P., Caminade A.-M., Kovalenko V.I. DFT study and
vibrational spectra of the phosphorus-containing G’0 generation dendrimer Vibr. Spectrosc., 2006, 40, No2, pp. 155-160
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10. Furer V.L., Vandyukov A.E., Majoral J.-P., Caminade A.-M., Kovalenko V.I. DFT calculation of molecular structure and vibrational spectra of the phosphorus-containing G’1 generation dendrimer with terminal aldehyde groups. Chem. Phys., 2006, v.326, 417-424
11. Furer V.L., Vandyukov A.E., Majoral J.P., Caminade A.M., Kovalenko V.I. DFT study and IR spectra of the phosphorus-containing G1 generation dendrimer.
J. Mol. Struct. 2006, v.785, 133-138.12. Furer V.L., Vandyukov A.E., Majoral J.-P., Caminade A.-M., Kovalenko V.I. DFT study
and vibrational spectra of the phosphorus-containing G’0 generation dendrimer Vibr. Spectrosc., 2006, 40, No2, pp. 155-160
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Thanksgiving:Сaminade A.-M., Majoral J.-P.
Laboratorie de Chimie de Coordination, CNRS, Toulouse, France
Kovalenko V.I., Vandyukov A.E., Vandyukova I.I. A.E. Arbuzov Institute of Organic and Physical Chemistry, Russian Academy of Science, Kazan, Russia
RFFI №99-03-33477а,АST 07-7.4-133/2002(Ф)
DCMS RAS program №7 2003-2007for financial support
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Thank YouThank You