Ph. D. THESIS 2009

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General Introduction The chemistry of the bicyclic compounds and their derivatives is a challenging domain. Particularly, bicyclo[3.3.1]nonane derivatives represent important intermediates in the synthetic routes to alkenes containing piramidalized carbon atoms, to derivatives of potential interest for the treatment of Alzheimer’s disease as well as to derivatives of dioximes type which can form self-assembled supramolecular structures through intermolecular hydrogen bonds. The fabrication of metallic structures based on two-photon absorption represents a new and promising domain due to the innovative technique and to the multiple applications in microelectronics, biosensing and spectral filtering devices. This work reflects my activity accomplished within the framework of two powerful research groups. Even if the subjects developed seem to be disconnected, at the first sight, they belong to the field of the chemical reactions assisted by the electromagnetic radiation. The aim of this thesis is to bring a contribution within these fields. The thesis is structured in two parts. The first part – Part A – refers to the contributions to the synthesis of some bicyclo[3.3.1]nonane derivatives and their structural analysis. The second part –Part B – presents innovative issues for the engineering of 3D metallic micro- and nanostructures by laser induced photochemistry. The second part presents also some aspects concerning optical and spectroscopic characteristics of such metallic structures. 5
Part A: Synthesis and Structural Analysis of Some Bicyclo[3.3.1]nonane Derivatives 1. Bicyclo[3.3.1]nonane-3,7-dione Due to its special characteristics, which involve a preorganisation of the molecular structure, bicyclo[3.3.1]nonane-3,7-dione 2 is of interest for the synthesis of some bicyclic derivatives and thus, for macrocycles as a supramolecular connector. Thus, a series of macrocyclic compounds containing bicyclic units have been already obtained [1]. The properties of synthesized macrocyclic compounds are significantly dependent on the spatial arrangement of the synthon at molecular level. In this respect we focused on the synthesis and structural aspects of compound 2, as well as on the structural analysis of its precursor, namely tetramethyl 3,7dihydroxybicyclo[3.3.1] nona-2,6-diene-2,4,6,8-tetracarboxylate 1. 1 .2 . Sy n th esis o f bicy clo [3 .3 .1 ]n o n an e -3 ,7 -d io n e Sy n t h esis o f b icy clo [3 .3 .1 ]n o n a n e -3 ,7 -d io n e st a r in g fr o m t etr a m eth y l 3 ,7 -d ih y d r o xy b icy clo [3 .3 .1 ] n o n a -2 ,6 -d ien e - 2 ,4 ,6 ,8 -t e t r a ca r b o xy la t e 1 r ep r esen t ed a ch a llen ge d u e t o t h e h a r d co n d it io n s o f r e a ct io n . Th e lit er a t u r e d a t a in d ica t e a t wo -st ep s h y d r o ly sis-d eca r b o xy la t io n r o u t e, in vo lv in g gen er a t io n o f b icy clic β -d ik etotetr a est er s a s in t er m ed ia r , a n d t h en it s co n v er sio n in t o b icy clic d ik eton e m a in ly u sin g a cid ic ca t a ly st s (e.g. h y d r o ch lo r ic a cid [2 ] o r a m ixt u r e o f h y d r o ch lo r ic a cid a n d a cet ic a cid [3 ]). In t h e ligh t o f t h e se a sp ect s we p r o p o se a st r a igh t fo r wa r d co n ver sio n o f co m p o u n d 1 in t o co m p o u n d 2 sim p ly h ea t in g a t h igh t em p er a t u r e a m ixt u r e o f t etr a est er 1 a n d a sm a ll a m o u n t o f wa t er , p la ce d in t o in a sea led b o r o silica t e t u b e. H 3COOC HO H 3COOC COOCH 3 (a) OH O (b) H2O, K-10 MW irrad. 1 COOCH3 2 6 H 2O O
Page 1 and 2: “BABES-BOLYAI” UNIVERSITY CLUJ-
Page 3 and 4: General Introduction OUTLINE Part A
Page 5: 3.6.1. Dots 188 3.6.2. 3D structure
Page 9 and 10: H 3C H 3C O O O C C O O 1a O O C C
Page 11 and 12: The two forms are in equilibrium an
Page 13 and 14: Figu re 4 . Th e 13 C-NMR APT (CDCl
Page 15 and 16: set used , the anarmonicities that
Page 17 and 18: Figure 9. ORTEP diagram for the bic
Page 19 and 20: 1.5.1. Tetramethyl 3,7-dihydroxybic
Page 21 and 22: Table 7. The selected molecular par
Page 23 and 24: a b Figure 14. 1 H NMR spectrum (CD
Page 25 and 26: Figure 16. 13 C NMR spectrum APT (C
Page 27 and 28: Absorbance (a. u.) Absorbance (a.u.
Page 29 and 30: icyclo[3.3.1]nonane-3,7-dione solut
Page 31 and 32: m u lt ip let a t a t δ ==1 .7 6 p
Page 33 and 34: Figure 22. 13 C NMR APT spectrum of
Page 35 and 36: Figure 24. NMR investigation of the
Page 37 and 38: (mol·l -1 ) syn 8.8 x10 -3 1.4373
Page 39 and 40: a b Figure 29. 3D FTIR spectra in s
Page 41 and 42: Figure 32. ORTEP diagram for the cy
Page 43 and 44: H2 … N3 = 1.839 Å H5 … N6 = 1.
Page 45 and 46: 2. Conclusions of the part A Differ
Page 47: 20. L. J. Bellamy, “Advanced in I
Page 50 and 51: 2. Experimental part: fabrication a
Page 52 and 53: 3 m 30 m a b Figure 4. Optical imag
Page 54 and 55: (NA 1.25) in phase-contrast (a) and
Page 56 and 57:
was chosen instead of an aqueous on
Page 58 and 59:
Our goal is to develope a lasser as
Page 60 and 61:
Figure 15. a Optical image of gold
Page 62 and 63:
the power as parameter exhibits a m
Page 64 and 65:
a b Figure 21 a) Optical image of g
Page 66:
4.5.3. 3D structures The 3D structu
Page 69 and 70:
Selected References 1. E. S. Wu, J.
Page 71:
VIII. J. Bosson-Ehoomann, A. Mihut,
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Ph. D. THESIS 2009

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