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

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

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

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

Core Repeated unit Terminal group IR spectra of series G’ i phosphorus dendrimers 6

IR spectra of series G i phosphorus dendrimers Core Repeated unit Terminal group -Cl 7

Raman spectra of series G’ i phosphorus dendrimers 8

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

- Cl 2 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 G 2 (2) and G 3 (4). IR spectra, theoretical curves and model fragments (approximation of linear chains) 10 L.A.Gribov, Theory of IR spectra of polymers, М.: Nauka, 1977.

fragment IIfragment 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 fragments I and III (1) and experimental IR spectra of generation G 3 (2). IR spectra, theoretical curves and model fragments (fragment approximation) 11

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

R=c(r n-1 )/(r-1)T=cr n (G 0 ) С=1, R=0, T=c (G 1 ) С=1, R=c, T=cr (G 2 ) С=1, R=c(r+1), T=cr 2 G 0 = С+3Т and G 1 = С+3R+3Т G 1 - G 0 =C+3R+6T–2(C+3T) =3R–C G 2 -G 1 =С+9R+12T–2(C+3R+6T)=3R–C G 3 -G 2 =C+21R+24T-2(C+9R+12T)=3R-C 13 Theory of spectral «additivity»

Experimental IR spectra of generation G 2 and the difference IR spectra (G 3 – G 2 ) 14

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

16 The difference Raman spectra

17 Experimental IR spectra of generations G 3, G’ 2 and the difference IR spectra (G’ 2 – G 3 )

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

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

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, 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, 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, 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, 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, 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, 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

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, Furer V.L., Vandyukov A.E., Majoral J.P., Caminade A.M., Kovalenko V.I. DFT study and IR spectra of the phosphorus-containing G 1 generation dendrimer. J. Mol. Struct. 2006, v.785, 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

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 № а, АST /2002(Ф) DCMS RAS program № for financial support 21

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