Acetylenic Porphyrins: Synthesis of Porphyrin Substituted Tetraethynylethenes and Polytriacetylenes Diplomarbeit carried out

Краткое описание

ACKNOWLEDGEMENTS
I wish to warmly thank Prof. Dr. François Diederich for the particular opportunity to
work in his research group, the proposition of the interesting and fascinating subject, and all
his support.
Furthermore, I want to express my gratitude to Dr. Rik Tykwinski for his very helpful
support in theory and in practice and for proofreading the manuscipt. His patience and
encouragement, as well as his remarkable ability to impart scientific knowledge was of
immense help and allowed me to rapidly deepen my understanding in the subject.
Special thanks go to Adrien Zingg, Rainer Martin, Martin Schreiber, Tilo Habicher, Dr.
Kevin Fitzpatrick, Dr. Jean-François Niergarten, Dr. Jennifer Wytko, and all of those who,
in one way or another, have contributed to aid me during my diploma thesis.
The exceptionally pleasant environment and working atmosphere in the ‘Diederich
Group’ helped to make my diploma thesis an unforgettable experience for me.
Zurich, 12th of June 1996 Volker Berl
Table of Contents
- I -
TABLE OF CONTENTS
1. ABSTRACT ...............................................................................1
2. INTRODUCTION ......................................................................2
3. GENERAL ASPECTS.................................................................5
3.1. Porphyrins..................................................................................... 5
3.1.1. General.......................................................................................................5
3.1.2. Nomenclature ...........................................................................................5
3.1.3. Some Selected Properties ........................................................................6
3.1.4. Natural Occurrence..................................................................................8
3.1.5. Synthetic Porphyrins ...............................................................................9
3.2. Tetraethynylethenes .................................................................... 11
3.2.1. Carbon Networks.....................................................................................11
3.2.2. Tetraethynylethene Nanoarchitecture and Generalities about
Conjugated Polymers ..............................................................................12
3.1.3. Tetraethynylethenes and Nonlinear Optics .........................................16
4. OBJECTIVES .............................................................................18
5. RESULTS AND DISCUSSION ....................................................24
5.1. Synthesis of the Iodinated Porphyrins...................................... 24
5.2. Synthesis of a Tetraethynylethene and a Hex-3-ene-1,5-
diyne Derivative........................................................................... 30
5.3. Synthesis of the Bis(porphinyl) Substituted TEE
Building Block............................................................................... 32
5.4. Synthesis of a Tetrakis(porphinyl) Substituted TEE............... 38
5.5. Synthesis of Porphinyl Substituted Polytriacetylene
Oligomers ...................................................................................... 39
5.6. Synthetic Approach towards an Interesting Fullerene-
Porphyrin Macrocycle ................................................................. 41
Table of Contents
- II -
5.7. Synthesis of a Linear Porphyrin-hex-3-en-1,5-diyne
Polymer.......................................................................................... 44
6. CONCLUSION AND OUTLOOK ...............................................46
7. EXPERIMENTAL SECTION .......................................................48
7.1. General Remarks .......................................................................... 48
7.2. Syntheses ....................................................................................... 50
8. REFERENCES AND NOTES.......................................................67
9. APPENDIX................................................................................71
9.1. Abbreviations................................................................................ 71
9.2. List of Products............................................................................. 73
Abstract
- 1 -
1. ABSTRACT
In this diploma thesis, the synthesis of laterally porphinyl substituted
polytriacetylene oligomers, linear porphinyl-hex-3-en-1,5-diyne oligomers, as well as
a tetrakis(porphinyl)tetraethynylethene is described. In addition, the synthesis of a
versatile building block, which could lead to the construction of a macrocyclic
fullerene-porphyrin structure, has been achieved.
Important steps towards the proposed target molecules were the synthesis of the
revised porphyrin system, its selective mono- and diiodination in meso-position with
[bis(trifuoroacetoxy)iodo]benzene and zincation of the latter to access the first two
important building blocks. In parallel, the synthesis of (E)-l,6-
bis[(triisopropylsilyl)ethynyl]hex-3-ene-l,5-diyne and (E)-3,4-bis[tert-butyldimethylsilyloxymethyl]
hex-3-ene-1,5-diyne from readily available starting materials has
been achieved. The modification and optimization of a procedure for acetylenic
palladium couplings using [Pd2(dba)3], AsPh3, and CuI led to the target molecules in
acceptable yields. Deprotection of the (E)-3,4-bis[(triisopropylsilyl)ethynyl)]-1,6-
bis[Zn(II)-5’,15’-bis(4’’-(ethyl-4’’’-butyryl)oxyphenyl)porphinyl]-hex-3-ene-l,5-diyne
and subsequent oxidative Glaser-Hay couplings successfully completed the route to
the desired oligomeric TEE derivatives. Although the quantities of the oligomers
necessary for complete characterization and study are still forthcoming, initial
investigations have established the ground work required for the realization of these
materials.
Introduction
- 2 -
2. INTRODUCTION
Tetrapyrrolic macrocycles such as porphyrins, chlorins, and bacteriochlorins are
vital to life on this planet. In fact, photosynthesis relies on the existence of the
chlorophyll and cytochrome porphyrins, by means of which photonic energy is
converted and stored as chemical energy. It is likely that cytochromes were
responsible for respiration long before oxygen was abundant in the Earth’s
atmosphere. With the advent of photosynthesis, the oxygen it produces is the
terminal electron acceptor for all aerobic respiration. It is this ability of
hemoproteins to then deal with the biochemistry of molecular oxygen that enables
cellular redox activity, not only by oxygen storage (monomeric myoglobin) and
transport (tetrameric hemoglobin) but also by electron transport (cytochromes) and
catalysis (oxygenases, peroxidases, etc).
This suggests the central role that porphyrins have played in chemical, biological
and physical research. Thus, massive contributions to our knowledge of the
structure and chemistry of porphyrins, metalloporphyrins, and related
compounds[1-3] were accumulated in the first half of this century. It was over 150
years ago that Verdeil converted chlorophyll to a red pigment prompting him to
suggest a structural relationship between chlorophyll, heme, and other porphyrins.
Shortly thereafter, Hoppe-Seyler strengthened this hypothesis by showing the spectral
resemblances between hematoporphyrin and an acid degradation product of
chlorophyll. The final steps in these structural elucidations were initiated by
Willstätter and culminated in the trailblazing work of Hans Fischer who
demonstrated the remarkable fact that but for the presence of two hydrogens, grass
would be coloured red and not green. Since then, the chemistry of porphyrins has
flourished into a vast and ever developing area of scientific endeavour. But natural
product chemists are no longer the only group interested in porphyrins. There is a
much larger constituency of chemists fascinated by the practical applications of
porphyrins to a wide diversity of fields.[3] In fact, the research carried out during
Introduction
- 3 -
this diploma thesis was not focused on the biological properties of porphyrins[4] but
on the synthesis of porphyrin systems with potential materials science and
technological applications.
To give the interested reader a brief, but by no means exhaustive insight into
current research being undertaken on sophisticated porphyrin systems, I would like
to mention the following topics: porphyrins designed to bind to electrodes and
surfaces,[5-7] porphyrin derived multi-electron reduction and oxidation catalysts,[8-18]
synthetic porphyrins as light harvesting antenna-systems,[19-21] porphyrinic materials
exhibiting nonlinear optical (NLO) properties,[19, 22-27] optical information storage
using porphyrins in matrices,[28-30] as well as possible porphyrin containing organic
electric conductors, semi- and superconductors,[28, 31] organic ferro-magnets,[32] and
liquid crystals.[33]
Compared to the relatively well investigated porphyrins, tetraethynylethene
(TEE) derivatives, the second important unit in my diploma thesis, are a class of
molecules only recently introduced. Though reported for the first time in 1969 by
Hori and co-workers[34] and synthetically advanced by Hauptmann in the mid-
1970’s,[35] tetraethynylethenes (TEEs) have only recently been developed.[36] Progress
in the early 1990’s by the works of Diederich et al.[37] then afforded TEEs with
virtually any desired substitution and protection patterns. TEEs are carbon rich,
rigid and very stable molecules, featuring undistorted full two-dimensional
conjugation and tolerating bulky pendant groups without loss of linear conjugation.
They are ideal precursors and building blocks for the design of new carbon
allotropes and networks, carbon-rich materials (e.g. polymers, molecular wires[38]),
as well as nanomaterials.[39, 40] Additionally, recent exciting studies on donoracceptor
substituted TEE compounds (so-called push-pull TEEs) have revealed their
interesting second and third order nonlinear optical properties and electrochemical
behaviour.[41]
In order to extend the present research[42, 43] towards the construction of
conjugated all-carbon backbone polymers by preparing polytriacetylenes (PTAs), it
was decided to link TEE compounds to porphyrins. The combination of the
chemistry and the chemical properties of these two types of compounds in one
Introduction
- 4 -
molecule was hoped to bring about new and interesting advanced materials for
electronic, photonic, and nonlinear optic applications.
In fact, the versatility of the TEE building block was fundamental to the planning
of the project carried out during my diploma thesis. The project was initiated by
Mark McLaughlin, an English undergraduate student, whose work targeted the
feasibility of synthesizing the proposed model systems. His success in achieving the
desired molecules encouraged the resumption of the investigations, pursuing them
to access the porphyrin substituted polytriacetylene oligomers.

Список литературы

8. REFERENCES AND NOTES
[1] K. D. Smith, Ed., Porphyrins and Metalloporphyrins, Elsevier, New York, 1975.
[2] D. Dolphin, Ed., The Porphyrins, Academic Press, New York, 1978, Vol. I - VII.
[3] R. H. Thomson, Ed., The Chemistry of Natural Products, 2nd Ed., Blackie A & P,
London, 1985.
[4] (a) P. J. Dandliker, F. Diederich, M. Gross, C. B. Knobler, A. Louati, E. M.
Sanford, Angew. Chem. 1994, 106, 1821-1824; (b) P. J. Dandliker, F. Diederich,
J.-P. Gisselbrecht, A. Louati, M. Gross, Angew. Chem. 1995, 107, 2906-2909;
[5] M. Yoneyama, A. Fujii, S. Maeda, T. Murayama, Chem. Lett. 1991, 929-932.
[6] F. Bedioui, S. G. Granados, J. Devynck, New J. Chem. 1991, 15, 939-941.
[7] D. K. Luttrull, J. Graham, J. A. DeRose, D. Gust, T. A. Moore, S. M. Lindsay,
Langmuir 1992, 8, 765-768.
[8] R. R. Durand, C. S. Bencosme, J. P. Collman, F. C. Anson, J. Am. Chem. Soc.
1983, 105, 2710-2718.
[9] J. P. Collman, J. E. Hutchinson, M. A. Lopez, R. Guilard, R. A. Reed, J. Am.
Chem. Soc. 1991, 113, 2794-2796.
[10] Y. L. Mest, M. L'Her, N. H. Hendricks, K. Kim, J. P. Collman, Inorg. Chem. 1992,
31, 835-847.
[11] C. K. Chang, I. Abdalmuhdi, Angew. Chem., Int. Ed. Eng. 1984, 23, 164-165;
Angew. Chem. 1984, 96, 154-155.
[12] P. S. Traylor, D. Dolphin, T. G. Traylor, J. Chem. Soc., Chem. Commun. 1984, 279-
280.
[13] T. G. Traylor, K. W. Hill, W. P. Fann, S. Tsuchiya, B. E. Dunlap, J. Am. Chem.
Soc. 1992, 114, 1308-1312.
[14] P. E. Ellis, J. E. Lyons, Coord. Chem. Rev. 1990, 105, 181-193.
[15] J. T. Groves, R. S. Myers, J. Am. Chem. Soc. 1983, 105, 5791-5791.
[16] D. Mansuy, P. Battioni, J. P. Renaud, R. Guerin, J. Chem. Soc., Chem. Commun.
1985, 155-156.
[17] Y. Naruta, F. Tani, N. Ishihara, K. Maruyama, J. Am. Chem. Soc. 1991, 113, 6865-
6872.
[18] K. Konishi, K. I. Oda, K. Nishida, T. Aida, S. Inoue, J. Am. Chem. Soc. 1992, 114,
1313-1317.
[19] J.-M. Lehn, Supramolecular Chemistry - Concepts And Perspectives, VCH,
Weinheim, 1995.
References
- 68 -
[20] M. Gouterman, P. M. Rentzepis, K. D. Straub, Porphyrins, ACS Symposium
Series 321, Washington, 1986.
[21] V. S.-Y. Lin, S. G. DiMagno, M. J. Therien, Science 1994, 264, 1105-1111.
[22] P. N. Prasad, D. J. Williams, Introduction to Nonlinear Optical Effects in Molecules
and Polymers, John Wiley & Sons, New York 1991, 243-245.
[23] G. H. Wagnière, Linear and Nonlinear Optical Properties of Molecules, VCH,
Weinheim, 1993.
[24] Ch. Bosshard, K. Sutter, Ph. Prêtre, J. Hulliger, M. Flörsheimer, P. Kaatz,
P. Günter, Advances in Nonlinear Optics - Organic Nonlinear Optical Materials,
Vol. 1, Gordon and Breach Publishers, Basel, 1995.
[25] H. S. Nalwa, Adv. Mater. 1993, 5, 341-358.
[26] D. V. G. L. N. Rao, F. J. Aranda, J. F. Roach, D. E. Remy, Appl. Phys. Lett. 1991,
58, 1241-1243.
[27] H. L. Anderson, S. J. Martin, D. D. C. Bradley, Angew. Chem. 1994, 106, 711-713,
Angew. Chem. Int. Ed. Engl. 1994, 33, 655-657.
[28] F. Vögtle, Supramoleculare Chemie, Teubner, Stuttgart, 1991.
[29] M. Pope, Mol. Cryst. Liq. Cryst. 1993, 228, 1-22.
[30] U. P. Wild, S. Bernet, B. Kohler, A. Renn, Pure Appl. Chem. 1992, 64, 1335-1342.
[31] J. Metz, M. Hanack, J. Am. Chem. Soc. 1983, 105, 828-830.
[32] J. S. Miller, J. C. Calabrese, R. S. McLean, A. J. Epstein, Adv. Mater. 1992, 4,
498-501.
[33] (a) B. A. Gregg, M. A. Fox, J. A. Bard, J. Chem Soc. Chem. Commun. 1987,
1134-1135; (b) B. A. Gregg, M. A. Fox, J. A. Bard, J. Am. Chem Soc. 1989, 111,
3024-3029.
[34] Y. Hori, N. Noda, S. Kobayashi, H. Tanigushi, Tetrahedron Lett. 1969, 3563-3566.
[35] (a) H. Hauptmann, Angew. Chem. 1975, 87, 490-491; (b) H. Hauptmann,
Tetrahedron Lett. 1975, 1931-1934; (c) H. Hauptmann, Tetrahedron 1976, 32, 1293-
1297.
[36] P. J. Stang, F. Diederich, Eds., Modern Acetylene Chemistry, VCH, Weinheim,
1995.
[37] Y. Rubin, C. B. Knobler, F. Diederich, Angew. Chem. Int. Ed. Eng. 1991, 30,
698-700; Angew. Chem. 1991, 103, 708-710.
[38] J.-M. Lehn, Angew. Chem. Int. Ed. Engl. 1988, 27, 89-112; Angew. Chem. 1988, 100,
91-116.
[39] F. Diederich, Nature (London) 1994, 369, 199-207.
[40] F. Diederich, Y. Rubin, Angew. Chem. 1992, 104, 1123-1146; Angew. Chem. 1992,
31, 1101-1124.
[41] (a) Ch. Bosshard, R. Spreiter, P. Günter, R. R. Tykwinski, M. Schreiber,
F. Diederich, Adv. Mater. 1996, 8, 231; (b) R. R. Tykwinski, M. Schreiber,
V. Gramlich, P. Seiler, F. Diederich, Adv. Mater. 1996, 8, 226-231.
References
- 69 -
[42] M. Schreiber, J. Anthony, F. Diederich, M. E. Spahr, R. Nesper, M. Hubrich,
R. Bommeli, L. Degiorgi, P. Wachter, P. Kaatz, Ch. Bosshard, P. Günter,
M. Colussi, U. W. Suter, C. Boudon, J.-P. Gisselbrecht, M. Gross, Adv. Mater.
1994, 6, 786-790.
[43] M. Schreiber, R. R. Tykwinski, R. Spreiter, Ch. Bosshard, P. Günther,
C. Boudon, J.-P. Gisselbrecht, M. Gross, U. Jonas, H. Ringsdorf, F. Diederich,
Adv. Mater. 1996, in preparation.
[44] W. Küster, Z. Physiol. Chem. 1912, 82, 463-483.
[45] H. Fischer, K. Seile, Ann. Chem. 1929, 468, 98-116.
[46] J. L. Soret, Compt. Rend. 1883, 97, 1267.
[47] A. Gamgee, Z. Biol. (Munich) 1897, 34, 505.
[48] A. Stern, G. Klebs, Ann. Chem. 1932, 500, 91-108; 1933, 504, 287-297; 1933, 505,
295-306.
[49] J. M. Osgerby and S. F. MacDonald, Can. J. Chem. 1962, 40, 1585-1589.
[50] P. S. Clezy, A. J. Liepa, A. W. Nichol, G. A. Smythe, Aust. J. Chem. 1970, 23,
589-602.
[51] A. D. Adler, F. R. Longo, J. D. Finarelli, J. Goldmacher, J. Assour, L. Korsakoff,
J. Org. Chem. 1967, 32, 476.
[52] G. M. Badger, R. L. N. Harris, R. A. Jones, J. M. Sasse, J. Chem. Soc. 1962,
4329-4337.
[53] G. H. Barnett, M. F. Hudson, K. M. Smith, Tetrahedron Lett. 1973, 2887-2892.
[54] H. Fischer, K. Platz, K. Morgenroth, Z. Physiol. Chem. 1929, 182, 265-288.
[55] P. Rothemund, J. Am. Chem. Soc. 1936, 58, 625-627.
[56] G. P. Arsenault, E. Bullock, S. F. MacDonald, J. Am. Chem. Soc. 1960, 82,
4384-4389.
[57] J. S. Lindsey, R. W. Wagner, J. Org. Chem. 1989, 54, 828-836.
[58] W. Krätschmer, L. D. Lamb, K. Fostiropoulos, D. R. Huffmann, Nature (London)
1990, 347, 354-362.
[59] A. M. Boldi, F. Diederich, Angew. Chem. Int. Edn. Engl. 1994, 33, 482;
Angew. Chem. 1994, 106, 482-485.
[60] W. R. Salaneck, I. Lundström, B. Rånby, Conjugated Polymers and Related
Materials, Oxford University Press, Oxford 1993.
[61] J. S. Miller, Adv. Mater. 1993, 5, 671-676.
[62] M. McLaughlin, Diplomarbeit 1995, ETH-Zürich.
[63] (a) M. Schreiber, Arbeitsbericht 1995; (b) S. G. DiMagno, V. S.-Y. Lin,
M. J. Therien, J. Am. Chem. Soc. 1993, 115, 2513-2515.
[64] B. Dietrich, P. Viout, J.-M. Lehn, Macrocyclic Chemistry - Aspects of Organic and
Inorganic Supramolecular Chemistry, VCH, Weinheim, 1993.
[65] W. A. Little, Sci. Am. 1965, 212 (2), 21-27.
[66] W. A. Little, J. Polym. Sci.: Part C 1967, 3-12.
[67] J. Bardeen, L. N. Cooper, J. R. Schreiffer, Phys.Rev. 1957, 108, 1175.
References
- 70 -
[68] J. M. Manriquez, G. T. Yee, R. S. McLean, A. J. Epstein, J. S. Miller, Science 1991,
252, 1415-1417.
[69] I. Z. Steinberg, E. Haas, E. Katchalski-Katzir in Time-Resolved Fluorescence
Spectroscopy in Biochemistry and Biology (R. B. Cundall, R. E. Dale, Eds.), Plenum
Press, New York 1983, 411-450.
[70] Th. Föster, Pure Appl. Chem. 1973, 34, 225-234.
[71] J. S. Manka, D. S. Lawrence, Tetrahedron Lett. 1989, 30, 7341-7344.
[72] R. Chong, P. S. Clezy, A. J. Liepa, A. W. Nichol, Aust. J. Chem. 1969, 22, 229-238.
[73] (a) R. W. Boyle, C. K. Johnson, D. Dolphin, J. Chem. Soc., Chem. Commun. 1995,
527-528. (b) Y. Ogato, K. Aoki, J. Am. Chem. Soc. 1968, 90,
6187-6191. (c) E. B. Merkushev, N. D. Simakhina, G. M. Koveshnikova,
Synthesis 1990, 486-487.
[74] E. Sanford, Dissertation, UCLA 1991.
[75] (a) J. Anthony, A. M. Boldi, Y. Rubin, M. Hobi, V. Gramlich, C. B. Knobler,
P. Seiler, F. Diederich, Helv. Chim. Acta 1995, 78, 13-45; (b) J. Anthony,
Dissertation, UCLA 1993.
[76] S. M. LeCours, H.-W- Guan, S. G. DiMagno, C. H. Wang, M. J. Therien, J. Am.
Chem. Soc. 1996, 118, 1497-1503.
[77] H. L. Anderson, C. J. Walter, A. Vidal-Ferran, R. A. Hay, P. A. Lowden, J. K. M.
Saunders, J. Chem. Soc., Perkin Trans. 1 1995, 2275-2279.
[78] R. W. Wagner, T. E. Johnson, F. Li, J. S. Lindsey, J. Org. Chem. 1995, 60,
5266-5273.
[79] C. Grant, P. Hambright, J. Am. Chem. Soc. 1969, 91, 4195-4198.
[80] X. Yan, D. Holten, J. Phys. Chem. 1988, 92, 5982-5986.
[81] 1H-NMR analysis supported this structure, although vigorous analysis was not
done.
[82] H. Imahori, Y. Sakata, Chem. Lett. 1996, 199-200.
[83] C. Bingel, Chem. Ber. 1993, 126, 1957-1959.