Molecular Structure and IR Spectra of Phosphorus Dendrimers: DFT Calculations

1. Victor Furer Molecular structure and IR spectra of phosphorus dendrimers by DFT calculations Kazan State Architect and Civil Engineering University

2. Scheme of dendrimer synthesis Divergent Convergent A. Juris, Annu. Rep. Prog. Chem., Sect. C, 2003, 99, 177 2

3. Topology of dendrimers Number of terminal groups Number of repeated units Molecular mass 3

4. Structural scheme of growing denrimer generations 4 N. Launayet al, Angew. Chem., Int. Ed. Engl. 1994, 33, 1589

5. Composition and mass of molecules of 11 generations of phosphorus dendrimers, series G’i (Gi) 5

6. Repeated unit Terminal group Core IR spectra of series G’iphosphorus dendrimers 6

7. Repeated unit Terminal group -Cl Core IR spectra of series Giphosphorus dendrimers 7

8. Raman spectra of series G’i phosphorus dendrimers 8

9. Comparison of IR spectra series Gi и G’i 8а 19а 1600 см-1 1500 см-1 9

10. - Cl2 IR spectra, theoretical curves and model fragments (approximation of linear chains) L.A.Gribov, Theory of IR spectra of polymers, М.: Nauka, 1977. 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) andG’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) andG3(4). 10

11. IR spectra, theoretical curves and model fragments (fragment approximation) fragmentI fragmentII fragmentIII Sum of theoretical absorption curves for the fragments IandII (1) and experimental IR spectra of generation G’5(2). Sum of theoretical absorption curves for the fragments IandIII (1) and experimental IRspectra of generation G3(2). 11

12. Experimental IR spectra, theoretical curves (DFT) PRIRODA FunctionalPBE Базис TZ2P D. Laikov,Chem. Phys. Lett., 1997, 281, 151 M.-L.Lartigue et al,Macromolecules, 1997, 30, 7335 12

13. Theory of spectral «additivity» 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+3ТandG1= 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 13

14. Experimental IR spectra of generationG2and the difference IR spectra (G3 – G2) 14

15. Experimental IR spectra of generationG’2and the difference IR spectra (G’3 – G’2)and (G’11– G’10)

16. The difference Raman spectra 16

17. Experimental IR spectra of generationsG3,G’2and the difference IR spectra (G’2 – G3) 17

18. Experimental IR spectra of generationsG’2vand the difference IR spectra (G’3v – G’2v) and (G’2 – G’2v) 18

22. 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. 18

23. 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 19

24. 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 20

25. 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, АST07-7.4-133/2002(Ф) DCMS RASprogram №72003-2007 for financial support 21

26. Thank You