1. Kirill P. Birin, Yulia G. Gorbunova, Aslan Yu. Tsivadze Lviv, 2010

2. Heteroleptic lanthanide (porphyrinato)(phthalocyaninates) as promising starting materials for development of molecular information storage devices. J. Org. Chem. 2000, 65, 7379-7390 J. Mater. Chem., 2002, 12, 808–828 Inorg. Chem. 2006, 45, 5479-5492, etc. 4 stable redox states! 6 stable redox states! Multi-step complicated synthesis…

3. K.P. Birin et al. J. Porphyrins Phthalocyanines, 2009, 13, № 2, 283-290.

4. Stage 1 Stage 2 K.P. Birin et al. J. Porphyrins Phthalocyanines, 2009, 13, № 2, 283-290.

5. Single isomer of triple-decker complex! Stage 3 K.P. Birin et al. J. Porphyrins Phthalocyanines, 2009, 13, № 2, 283-290.

6. (Pc) Y (An 4 P) 61% of HOMO is localized at Pc-ligand ((MeO) 8 Pc) Y (An 4 P) 6 6 % of HOMO is localized at Pc-ligand Extended Huckel calculation of HOMO of MM+ optimized molecule of double- decker complex for explanation of selectivity K.P. Birin et al. J. Porphyrins Phthalocyanines, 2009, 13, № 2, 283-290.

7. R=corresp. porphyrin HTPPH 2 OMeAn 4 PH 2 BrBr 4 TPPH 2 R’=corresp. phthalocyanine HPcH 2 OMe(MeO) 8 PcH 2 OBu(BuO) 8 PcH 2 fused 15-crown-5(15C5) 4 PcH 2 Ln(acac) 3 Ln=La-Eu

8. HOMeOBu(15C5) HNd BrNd La, Nd, Eu OMeNdLa-Eu Triple-decker complexes are obtained for the whole La-Eu series Synthesis is independent from porphyrin meso -substituents Only double-decker complexes are obtained. Crucial influence of electron-donating substituents in Pc-macroycle Porphyrin meso -substituents Phthalocyanine substituents

9. All synthesized complexes are characterized with: MALDI-TOF mass-spectrometry UV-Vis spectroscopy 1 H- and 13 C-NMR

10. NMR of [An 4 P] La [(15C5) 4 Pc] La [An 4 P] K.P. Birin et al. Magn. Reson. Chem., 2010, 48, 505-515.

11. NMR of [An 4 P] La [(15C5) 4 Pc] La [An 4 P] and [Br 4 TPP] La [(15C5) 4 Pc] La [Br 4 TPP] X = Br X = OMe

12. NMR of series of [An 4 P] Ln [(15C5) 4 Pc] Ln [An 4 P] complexes Lanthanide-induced paramagnetic shifts complicate the spectra K.P. Birin et al. Magn. Reson. Chem., 2010, 48, 505-515.

13. LIS results from magnetic interaction between f- electrons of lanthanide and observed nuclei LIS:  =  para –  dia In turn, two mechanisms are possible for interaction: through-bond, or contact (  con ) through-space, or dipolar (  dip ) LIS is a function of molecular structure Finally, LIS is considered as  =  con +  dip C. Piguet, C.F.G.C. Geraldes. Handbook on the physics of rare earths, vol. 33, ch. 215, 353-463.

14. Contact contribution is presumed to be negligible if lanthanide and observed nuclei is separated by 5 or more  -bonds Dipolar contribution is bound to geometry of the molecule and decreases as 1/R 3, where R – distance between lanthanide and nuclei Contact and dipolar terms for each lanthanide ion are tabulated values, designated as Ln and D Ln, respectively

15.  = F i Ln + A 2 0 G i D Ln If more than one lanthanide center is present, resulting LIS is a combination of contributions.

16. In order to explain the particular behavior of each peak in spectra upon LIS, MM+ calculation of structure of complex was performed. Averaged coordinates of protons are plotted with G i -diagram K.P. Birin et al. Magn. Reson. Chem., 2010, 48, 505-515.

17. Two opposite aims: Explanation of features of NMR spectra from structural parameters of molecules Determination of structural parameters of molecules in solution from features of NMR spectra Utilization of dipolar contribution of LIS as structural probe Separation of contact and dipolar contributions is unavoidable

18. Separation of contributions of LIS is possible through statistical analysis of series of NMR datasets for isostructural complexes Model compounds [An 4 P]Ln[(15C5) 4 Pc]Ln[An 4 P] Ln=La-Eu, 5 paramagnetic lanthanides and La complex as diamagnetic reference

19. First step is verification of isostructurality of the series of compounds. Datasets for all types of protons in the molecule are plotted in  H i / Ln vs  H j / Ln coordinates. Linearization equation is Fine linearization of datasets testifies the isostructurality of the whole series of compounds. K.P. Birin et al. Magn. Reson. Chem., 2010, 48, 505-515.

20. Next step is separation of contact and dipolar contributions Datasets are plotted as  H i / Ln and their linearization is performed according to equation Here the slope of gives the value of dipolar term and intercept corresponds to contact term. Finally, tables of contact and dipolar contributions of LIS for each proton of each complex are obtained. K.P. Birin et al. Magn. Reson. Chem., 2010, 48, 505-515.

21. Starting point for structure determination – coordinates of protons of (15C5) 4 Pc- ligand in symmetrical environment [Pc] Sm [(15C5) 4 Pc] Sm [Pc] A. G. Martynov et al. Eur. J. Inorg. Chem., 2007, 30, 4800. K.P. Birin et al. Magn. Reson. Chem., 2010, 48, 505-515.

22. Determination of lanthanides positions Ln Ln…Ln = 3.886A K.P. Birin et al. Magn. Reson. Chem., 2010, 48, 505-515.

23. Determination of positions of porphyrin decks Coordinates of protons of porphyrin deck are obtained from MM+ optimization of molecular geometry K.P. Birin et al. Magn. Reson. Chem., 2010, 48, 505-515.

24. Ln Pc...Por = 3.395 Å

25. Finally, protons of the molecule are located and may act as binding points for the whole structure The described procedure allows determination of structural parameters of complexes in solutions Ln...Ln = 3.886 Å Pc...Por = 3.395 Å Ln...N 4 (Pc) = 1.943 Å Ln...N 4 (Por) = 1.453 Å ms -An skew = 41 o

26. Further refinement of structure needs application of LIS data for carbon atoms of molecular skeleton. 13 C{H} spectra of triple-decker complexes [An 4 P]Ln[(15C5) 4 Pc]Ln[An 4 P] Ln = La Ln = Nd

27. Assignment of 13 C-NMR spectra is possible in several ways: INEPT and DEPT techniques to determine signals of C, CH, CH 2 and CH 3 fragments Heteronuclear 13 C- 1 H COSY to correlate directly bound 1 H and 13 C atoms Pulse-field gradient techniques: HMQC – to correlate directly bound 1 H and 13 C atoms HMBC – to correlate 1 H and quaternary 13 C atoms

28. HMQC 13 C- 1 H correlation of triple-decker complexes [An 4 P]Ln[(15C5) 4 Pc]Ln[An 4 P] Ln = Nd Ln = La Proton dimension Carbon dimension

29. Application of 13 C data for structure determination allows to operate with most atoms of molecular core, except quaternary carbons.

30. The developed methodology for structural analysis of heteroleptic porphyrinato-phthalocyaninates in current state:  Allows precise determination of relative positions of atoms of molecule  Involves all protons of the molecule and most carbon atoms of molecular core  Allows to determine structural parameters of molecule in solution

31. This work was supported by Russian Foundation for Basic Research (grant#08-03- 00835) and programs of Russian Academy of Sciences. Thank you for your attention!