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Avancées en chimie de coordination des phosphines nitroaromatiques : synthèse et chimie supramoléculaire de dérivés alkyl - aryl-carbo-benzènes

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(1)Avancées en chimie de coordination des phosphines nitroaromatiques : synthèse et chimie supramoléculaire de dérivés alkyl - aryl-carbo-benzènes Chongwei Zhu. To cite this version: Chongwei Zhu. Avancées en chimie de coordination des phosphines nitroaromatiques : synthèse et chimie supramoléculaire de dérivés alkyl - aryl-carbo-benzènes. Coordination chemistry. Université Paul Sabatier - Toulouse III, 2017. English. �NNT : 2017TOU30281�. �tel-01955747�. HAL Id: tel-01955747 https://tel.archives-ouvertes.fr/tel-01955747 Submitted on 14 Dec 2018. HAL is a multi-disciplinary open access archive for the deposit and dissemination of scientific research documents, whether they are published or not. The documents may come from teaching and research institutions in France or abroad, or from public or private research centers.. L’archive ouverte pluridisciplinaire HAL, est destinée au dépôt et à la diffusion de documents scientifiques de niveau recherche, publiés ou non, émanant des établissements d’enseignement et de recherche français ou étrangers, des laboratoires publics ou privés..

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(13) Acknowledgment. .

(14)

(15) Acknowledgment. Acknowledgment Time flies so quickly, after an intensive period of thirty-nine months, my PhD career has quietly come to an end. Over the past three years, I gained tremendous acknowledge in chemistry, my experimental skill and research ability were also significantly improved. Undoubtedly, it would not be possible to conduct my research and complete my dissertation without these people who have supported and helped so much during this period. Take this opportunity, I want here to thank all of you for your great help, and the good time we spent together.. Foremost, I would first like to express my sincerest gratitude to my supervisors Dr. Valérie MARAVAL and Prof. Remi CHAUVIN for your greatest support of my PhD study and research. The door of your office was always open for us whenever I ran into trouble or had any question not only in research, but sometimes also in life.. Without you, Valérie, this thesis would not have been completed or written. Your appearance always brought me energy and hope, especially in my most difficult time when working on carbomer chemistry in the beginning and writing this thesis. I really enjoyed the time working with you, your excited expression when we determined new final products or analyzed their structures of single crystals together, deeply impressed and greatly encouraged me. At that moment, I definitely realized that research brought us happiness, I am particularly grateful to you for everything that you have done for me.. Prof. Remi Chauvin, you are one of the greatest chemist in the world, your motivation for. .

(16) Acknowledgment. chemistry, enthusiasm for people, immense knowledge and meticulous working attitude have had a profound impact on me. I have learnt so much from and because of you, you always can enlighten me when I encountered difficulties. I sincerely thank you for your guidance and helping me grow as a research chemist. It has been my honor to be your PhD student.. Additionally, I would like to acknowledge my thesis committee members: Prof. Mogens Brøndsted NIELSEN (University of Copenhagen, Denmark), Dr. Irena STARA (Institute of Organic Chemistry and Biochemistry, Czech Republic), Dr. Philippe BLANCHARD (Universite d'Angers, France), Dr. Suzanne FERY-FORGUES (Université Paul Sabatier, France), Prof. Xiuling CUI (invited people, Huaqiao University and Zhengzhou University, China), and Dr. Emmanuel GRAS (invited people, LCC-CNRS, France) for their time, their encouragement, and insightful comments, which broaden my horizons in the future research.. I would like to thank the other past and present group members: Dr. Y. CANAC, many thanks to you for your help in my first year; Dr. C. LEPETIT, thank you for your concern in my first year; Prof. V. BERNARDES-GENISSON, you are a very kind lady, I always feel warm when seeing you; C. BARTHES, you always answered very patiently my questions whatever any question I asked, thank you so much for what you have done for me; K. COCQ, you are the King in carbomer chemistry, at least in my opinion. Thank you very much for sharing your experience with me and your pertinent suggestion for me; C. POIDEVIN, thank you for taking me to visit city center of Toulouse when I arrived here, and your French lesson to me despite some bad words sometimes; D. LISTUNOV, although you look serious sometimes, you are a good chemistry and warm-hearted. .

(17) Acknowledgment. person, many thanks to you for discussion with me; C. D. MBOYI and A. MANKOU, You are really nice people, and helped me a lot in my first year, many thanks to both of you; M. CHAMMAM, thank you for what you have done for me, especially in my defense recently; E. M. CARVALHO, thanks for your help, man.. My appreciation also goes to our collaborators: Dr. E. GRAS, who works at LCC in Toulouse, supervised me as a co-supervisor in my first year and gave me a great support, I whole-heartedly appreciate you. Also, I want to thank Prof. H. F. HSU for the measurements of DSC, POM and PXRD experiments in Taiwan, Prof. Chun-hsien Chen for conducting STM measurement in Taiwan in carbo-mesogen project, Dr. A. POATER for performing the calculation for carbo-OPEs in Spain, Prof. J. L. MALDONADO for exploring of OPV application in Mexico.. I am also indebted to the following crystallographers: Dr. C. DUHAYON, it is so nice of you, you got involved in all the measurements and analyses of single crystals in my PhD career, I very much appreciate you. Dr. B. KAUFFMANN, who is from Bordeaux, my paper would not have been possible to be published without the high-quality data of single crystals. My appreciation also goes to Dr. N. SAFFON for attempts at picking single crystals.. I am hugely appreciative to Dr. A. SAQUET for electrochemical measurements of all the molecules in carbo-mer research.. I would like to thank Dr. Y. COPPEL for launching solid NMR experiment and helping resolve NMR spectra, and Dr. C. BIJANI for NMR measurements by using 500 MHz and 600. .

(18) Acknowledgment. MHz spectrometer, and F. LACASSIN for carrying out. 103. Rh NMR experiments for the RhI. complexes in the first chapter of this manuscript.. Special mention goes to my M.sc supervisor Prof. X. L. CUI for coming to my defense from the distant China.. I am grateful for conversations with the following people: O. SADEK, S. AYALAMARISCAL, A. POCINHO, W. KHODJA, A. FERNANDEZ-ALVAREZ, C. ZHANG, X. D. LIN, L. CHEN, J. R. QIU, Y. P. WANG, who all work at LCC. Many thanks also go to my friends in Toulouse: L. Q. LANG, Q. LIAO, J. H. WANG, Z. H. ZHAO, you made my free time enjoyable by playing cards and eating together at weekends.. I also want to thank LCC (CNRS) for providing a safe and comfortable workplace, and UPS for offering us various interesting and useful courses and training.. My sincere thanks go to CSC (China Scholarship Council) for my PhD scholarship. The IDEX emergence program 2014 of Toulouse is acknowledged for financial support (carbo-device project).. Last but not the least, I would like to thank my family for their unconditional support and encouragement in these years, I haven’t been able to find more time to accompany you, in particular for my grandfather, I couldn’t go back to see you last time until you left us forever. But I want to say I really love all of you, thank you.. .

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Figure

Figure 1. a) top : alternative manners to tune the P-s-donating ability of benzimidazolophosphines towards a Lewis acid (LA): C-nitration vs
Table 1. Crystallographic data for the complexes 5 a–c, 5 f,g and 5 a ’ .
Figure 3. Lewis structure of the dinuclear side-products formed along with the target complexes 5 b,c, 5 e–g (Scheme 3; top), crystallographic molecular view of 6 f with thermal ellipsoids at the 50 % probability level (bottom left), and free van der Waals
Fig. 1 Aromatic region of the 1 H NMR spectra of 4 and 11 in highly diluted CDCl 3 solutions (400 MHz, 12 h acquisition time).
+7

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