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9781574445121

Polyynes: Synthesis, Properties, and Applications

by ;
  • ISBN13:

    9781574445121

  • ISBN10:

    157444512X

  • Edition: 1st
  • Format: Hardcover
  • Copyright: 2005-08-29
  • Publisher: CRC Press

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Summary

Polyynes: Synthesis, Properties, and Applications compiles information found scattered throughout the literature in inorganic, organic, and polymer chemistry into one cohesive volume.In addition to being a precursor of fullerenes, polyynes are one of the key precursors in the formation of soot and carbon dust, or elemental carbon in the galaxy, and their properties can be linked to interstellar band phenomena and other astrophysical behavior. More than 1,000 organic molecules produced by plants, fungi, and other microorganisms are also classified as polyynes, playing a biological role in nature that may be used in the treatment of diseases as antibiotics, anticancer, or anti-infective agents. Polyynes: Synthesis, Properties, and Applications covers breakthrough discoveries, particularly the simplified synthesis of polyynes in solution stabilized by using appropriate end groups and carbon films achieved using chemical, electrochemical, and other sophisticated techniques. The book explains in great detail the conditions, apparatus, and experimental procedures to synthesize polyynes with consistent and reproducible results.By presenting new and unpublished results along with recent discoveries and theories, Polyynes: Synthesis, Properties, and Applications reflects the thriving research status of polyynes in various disciplines as well as new ideas and guidelines for future research, discoveries, and applications of these molecules.

Table of Contents

Preface iii
Editor vii
Contributors ix
Chapter 1 Carbon Chain Molecules in Cryogenic Matrices 1(14)
Tomonari Wakabayashi and Wolfgang Krätschmer
1.1 Introduction
1(2)
1.2 Matrix-Isolation Experiments of Carbon Vapor
3(7)
1.3 Flashing Carbon
10(1)
1.4 Conclusions
11(1)
References
12(3)
Chapter 2 Synthesis and Characterization of Carbynoid Structures in Cluster-Assembled Carbon Films 15(22)
L. Ravagnan, F. Siviero, E. Salis, P. Piseri, P. Milani, C. Lenardi, A. Li Bassi, C.S. Casari and C.E. Bottani
2.1 Introduction
15(2)
2.2 Experimental
17(4)
2.3 Experimental Results
21(8)
2.3.1 Film Morphology
21(1)
2.3.2 Raman Characterization of the As-Deposited Carbon Films
22(2)
2.3.3 Gas Exposure
24(4)
2.3.4 Thermal Stability
28(1)
2.4 Discussion
29(4)
2.5 Summary and Conclusions
33(1)
Acknowledgments
33(1)
References
33(4)
Chapter 3 Epitaxial Growth by D.C. Magnetron Sputtering of Carbyne (Chaoite) Microcrystals on CVD-Deposited Polycrystalline Diamond 37(16)
Robert B. Heimann, Igor Burlacov, Jacob I. Kleiman and Sergey Horodetsky
3.1 Introduction
37(2)
3.2 Proposed Epitaxy of Carbyne on Diamond
39(3)
3.3 Equipment
42(3)
3.3.1 Chemical Vapor Deposition (CVD) Reactor
42(1)
3.3.2 D.c. Magnetron
43(2)
3.4 Deposition and Characterization of Carbyne
45(4)
3.5 Conclusions
49(1)
Acknowledgments
50(1)
References
50(3)
Chapter 4 Electrochemical Synthesis of Carbyne-Like Materials and Other Nanocarbons 53(26)
Ladislav Kavan
4.1 Introduction
53(6)
4.1.1 Electrochemical vs. Chemical Carbonization: Fundamentals
54(3)
4.1.2 Electrochemical Carbonization: Refined Model
57(2)
4.2 Electrochemical Routes to Carbyne-Like Chains
59(9)
4.2.1 Carbyne-Like Materials Made by "Wet" Electrochemistry
62(4)
4.2.1.1 Low-Molecular Weight Precursors
62(2)
4.2.1.2 Polymeric Precursors
64(2)
4.2.2 Carbyne-Like Materials Made by "Dry" Electrochemistry
66(2)
4.3 Electrochemical Synthesis of Fullerenes and Carbon Onions
68(1)
4.4 Electrochemical Synthesis of Carbon Nanotubes
69(2)
4.4.1 Indirect Synthesis of Nanotubes from Polyyne
70(1)
Acknowledgment
71(1)
References
71(8)
Chapter 5 Synthesis of Carbynoid Structures by the Combustion Flame Method 79(20)
Jean-Baptiste Donnet, Hanae Oulanti, Raymond Wey, Thang Le Huu, Wang Chuang Cun and Loic Vidal
5.1 Introduction
79(3)
5.2 Experimental Details
82(2)
5.2.1 Deposition of Carbyne Films
82(1)
5.2.2 Characterization
83(1)
5.3 Results and Discussions
84(11)
5.3.1 Scanning Electron Microscopy and Energy Dispersive X-Ray Analysis
84(2)
5.3.1.1 Carbon Film Deposited at τ= 1.15
84(1)
5.3.1.2 Carbon Film Deposited at τ= 1.1
85(1)
5.3.1.3 Carbon Film Deposited at τ=1.05
86(1)
5.3.2 Raman Spectroscopy Analysis
86(4)
5.3.2.1 Carbon Film Deposited at τ = 1.15
86(1)
5.3.2.2 Carbon Film Deposited at τ= 1.1
87(3)
5.3.3 Transmission Electron Microscopy Analysis
90(2)
5.3.4 Atomic Force Microscopy Analysis
92(3)
5.4 Conclusions
95(1)
References
95(4)
Chapter 6 Cyclic Polyynes: Generation, Characterization, and Reactions 99(28)
Yoshito Tobe and Tomonari Wakabayashi
6.1 Introduction
99(2)
6.2 Monocyclic Carbon Rings
101(11)
6.2.1 Theory and Detection: An Historical Overview
101(1)
6.2.2 Generation from Structurally Well-Defined Organic Precursors
102(3)
6.2.3 Cumulenic vs Acetylenic Forms
105(3)
6.2.4 Photoelectron Spectroscopy
108(3)
6.2.5 Towards the IR Detection of Cyclic C10
111(1)
6.3 Multicyclic Polyynes
112(5)
6.3.1 Class of Hybrid sp—sp² Carbon Networks
112(1)
6.3.2 Bicyclic and Tricyclic Polyynes
113(4)
6.4 Three-Dimensional Polycyclic Polyynes
117(3)
6.4.1 Macrocyclic Polyynes to Size-Selective Fullerene Formation
117(3)
6.5 Conclusions
120(1)
Acknowledgment
120(1)
References
120(7)
Chapter 7 Formation of C2nH2 Polyynes by Laser Ablation of Graphite, Coal or C60 Particles Suspended in Selected Solvents 127(28)
Masaharu Tsuji, Shingo Kuboyama, Takeshi Tsuji and Taro Hamagami
7.1 Introduction
127(2)
7.2 Experimental
129(1)
7.3 Results and Discussion
130(16)
7.3.1 Polyynes from Graphite
130(9)
7.3.2 Polyynes from Coals
139(1)
7.3.3 Polyynes from C60
140(6)
7.4 Formation Mechanism of Polyynes from Three Carbon Sources in Solutions
146(5)
7.5 Conclusions
151(1)
Acknowledgments
152(1)
References
152(3)
Chapter 8 Polyynes: Synthesis with the Submerged Electric Arc 155(26)
Franco Cataldo
8.1 Introduction
156(1)
8.2 Experimental Aspects on the Synthesis and Analysis of Polyynes with the Electric Arc
157(4)
8.2.1 Synthesis of Polyynes in a Submerged Electric Arc
157(2)
8.2.2 HPLC Analysis of the Polyynes
159(1)
8.2.3 Study of the End-Capping of the Polyyne Chains
159(1)
8.2.4 The Electric Arc Between Graphite Electrodes in η-Hexane
159(1)
8.2.5 The Electric Arc Between Graphite Electrodes at Very High Current Density
160(1)
8.2.6 Electric Arc Between Titanium Electrodes in η-Hexane
160(1)
8.2.7 The Electric Arc Between Titanium Electrodes in Methanol: A Comparison with Carbon Arc
161(1)
7.3 Results and Discussion
161(16)
8.3.1 Some Kinetic Aspects on the Formation of Polyynes
161(3)
8.3.2 Detection and Identification of Polyynes by HPLC–DAD and Other Analytical Techniques
164(5)
8.3.3 PAHs as Byproducts Formed with the Polyynes During Arcing
169(5)
8.3.4 The Role Played by the Nature of the Electrodes in the Polyynes Formation
174(2)
8.3.5 Formation of Carbon Coke or Pyrocarbon: A Comparison with a Series of Halogenated Solvents
176(1)
8.4 Conclusions
177(1)
Acknowledgments
178(1)
References
178(3)
Chapter 9 Polyynes (C2nH2, n = 2-5) and Other Products from Laser-Ablated Graphite: A Time-of-Flight Mass Spectroscopic Study in Combination with One-Photon Ionization 181(16)
Tomonari Wakabayashi, Yoshiyasu Kato, Takamasa Momose and Tadamasa Shida
9.1 Introductory Remarks
182(1)
9.2 Outline of the Study
182(1)
9.3 Experimental
183(2)
9.4 Results
185(8)
9.4.1 Comparison of One-Photon and Multi-Photon Ionization in the He Buffer Gas
185(2)
9.4.2 One-Photon Ionization in the H2 Buffer Gas
187(4)
9.4.3 Effect of Ablation Laser Power on the Mass Spectral Pattern
191(2)
9.4.4 Structure and Formation Mechanism of the Ablated Products
193(1)
9.5 Concluding Remarks
193(1)
Acknowledgment
194(1)
References
194(3)
Chapter 10 Polyyne-Type Materials 197(22)
Masashi Kijima
10.1 Introduction
197(1)
10.2 End-Capped Polyynes
198(4)
10.3 Polyyne-Type Polymers
202(11)
10.3.1 Poly(ρ-phenylene-alt-oligoethynylene)s
203(3)
10.3.2 Poly(aryleneethynylene)s
206(3)
10.3.3 Poly(arylenebutadiynylene)s and Other Analogs
209(4)
10.4 Summary and Conclusions
213(1)
References
214(5)
Chapter 11 Carbon Material with a Highly Ordered Linear-Chain Structure 219(34)
V.G. Babaev, M.B. Guseva, N.D. Novikov, V.V. Khvostov and P. Flood
11.1 Introduction
219(5)
11.2 Experimental Set-Up
224(1)
11.3 Methods of Characterization
225(1)
11.4 Results and Discussion
225(22)
11.4.1 Electron Band Structure
225(4)
11.4.2 EELS Measurements
229(2)
11.4.3 Raman Spectroscopy
231(3)
11.4.4 Atomic Force Microscopy
234(1)
11.4.5 Scanning Tunneling Microscopy
235(1)
11.4.6 Electric Conductivity
236(2)
11.4.7 Optical Properties
238(1)
11.4.8 Field Effect Measurements
238(2)
11.4.9 Al/sp¹-C/p-Si Heteroj unction
240(1)
11.4.10 Cold Electron Emission
241(1)
11.4.11 Injection of Electrons in Dielectrics
242(1)
11.4.12 The Dependence of Atomic Structure of sp¹-Hybridized Carbon Films on their Thickness
243(3)
11.4.13 Carbon Electronics
246(1)
11.5 The New Carbon Material Tetracarbon™
247(3)
11.6 Conclusions
250(1)
Acknowledgments
250(1)
References
251(2)
Chapter 12 Synthesis of Carbynoid Materials by Chemical Dehydrohalogenation of Halogen-Containing Polymers 253(18)
Sergey E. Evsyukov
12.1 Introduction
253(1)
12.2 Original Polymers
254(3)
12.3 Dehydrohalogenating Agents
257(2)
12.4 Characterization of the Dehydrohalogenation Products
259(5)
12.4.1 Vibrational Spectroscopy
259(2)
12.4.1.1 Infrared Spectroscopy
259(1)
12.4.1.2 Raman Spectroscopy
259(2)
12.4.2 UV—VIS Absorption Spectroscopy
261(1)
12.4.3 Electron Spectroscopy
261(1)
12.4.4 ¹³C Nuclear Magnetic Resonance Spectroscopy
262(2)
12.5 Conclusions
264(3)
References
267(4)
Chapter 13 Ion Irradiation of Solid Carbons 271(14)
G. Strazzulla, G.A. Baratta, S. Battiato and G. Compagnini
13.1 Introduction
271(2)
13.2 Synthesis and Characterization of Carbynoid-Rich Thin Films
273(3)
13.3 Ion Irradiation of Carbyne-Rich Thin Films
276(1)
13.4 Ion Irradiation of Related Materials
277(5)
13.4.1 Asphaltite
278(2)
13.4.2 Frozen Benzene
280(2)
13.5 Conclusions
282(1)
Acknowledgments
282(1)
References
282(3)
Chapter 14 Cyanoalkynes and Cyanopolyynes: From Crossed Beam Experiments to Astrochemistry 285(38)
Nadia Balucani and Ralf I. Kaiser
14.1 Introduction
285(5)
14.2 The Crossed Molecular Beam Method
290(3)
14.3 Data Analysis
293(5)
14.4 Results on the Reaction of the CN Radicals with Simple Alkynes
298(15)
14.4.1 The Reaction CN + C2H2
298(5)
14.4.2 The Reaction CN + CH3CCH
303(6)
14.4.3 The Reaction CN + CH3CCCH3
309(4)
14.5 Conclusions and Outlook
313(1)
Acknowledgments
314(1)
References
315(8)
Chapter 15 Synthesis of Monocyanopolyynes and Dicyanopolyynes with the Submerged Electric Arc 323(16)
Franco Cataldo
15.1 Introduction
324(1)
15.2 Experimental
324(2)
15.2.1 Synthesis of Monocyanopolyynes by the Submerged Electric Carbon Arc in Acetonitrile
325(1)
15.2.2 Synthesis of Dicyanopolyynes by the Submerged Electric Carbon Arc in Liquid Nitrogen
325(1)
15.2.3 Electric Arc Between Graphite Electrodes Submerged in η-Octane
326(1)
15.2.4 The Electric Arc Between Graphite Electrodes Submerged in Water
326(1)
15.3 Results and Discussion
326(10)
15.3.1 Monocyanopolyynes Produced in Acetonitrile
326(4)
15.3.2 Formation of Polyynes from Electric Arc in Liquid Nitrogen Between Graphite Electrodes
330(6)
15.3.3 Polyynes from the Electric Arc from Graphite Electrodes in Water
336(1)
15.4 Conclusions
336(1)
Acknowledgments
337(1)
References
337(2)
Chapter 16 Natural Carbynes, Including Chaoite, on Earth, in Meteorites, Comets, Circumstellar and Interstellar Dust 339(32)
Frans J.M. Rietmeijer and Alessandra Rotundi
16.1 Introduction
339(1)
16.2 Metastable Carbynes: Are They Minerals?
340(2)
16.3 The Carbon Phase Diagram Revisited: Carbon "Melting"
342(4)
16.4 Terrestrial Chaoite: A Special Case
346(2)
16.5 Carbyne Identification
348(4)
16.6 Carbynes in Meteorites
352(2)
16.7 Comets
354(2)
16.8 Carbyne Crystals: What Link to Cumulene and Polyyne Gas Molecules?
356(1)
16.9 Laboratory Carbon Condensation Experiments
357(1)
16.10 A New Carbyne Structure
358(2)
16.11 Circumstellar Dust
360(2)
16.12 Interstellar Dust
362(1)
16.13 Conclusions
363(1)
Acknowledgments
364(1)
References
364(7)
Chapter 17 Structures and Other Properties of Polyynes and their Isomers: Theoretical and Experimental Results 371(54)
Dieter Heymann and Franco Cataldo
17.1 Introduction
372(2)
17.2 C2H2 Isomers
374(3)
17.2.1 Introduction
374(1)
17.2.2 Vibrational, UV, and Rotational Data
374(2)
17.2.3 Isomerization
376(1)
17.3 C3H2 Isomers
377(7)
17.3.1 Introduction
377(1)
17.3.2 Vibrational Data
378(1)
17.3.3 Structure of 3O1(t)
379(2)
17.3.4 Electronic Spectra
381(3)
17.3.5 Rotational Data and Isomerization
384(1)
17.4 C4H2 Isomers
384(5)
17.4.1 Introduction
384(1)
17.4.2 Energies and Dipole Moments of the Open Molecules
384(1)
17.4.3 Vibrational Data
385(2)
17.4.4 Electronic Spectra
387(1)
17.4.5 Rotational Data
388(1)
17.5 C5H2 Isomers
389(2)
17.5.1 Introduction
389(1)
17.5.2 Comments
390(1)
17.5.3 Electronic Spectra and Rotational Data
390(1)
17.6 C6H2 Isomers
391(5)
17.6.1 Introduction
391(4)
17.6.2 Comment
395(1)
17.6.3 Electronic Spectra and Rotational Data
395(1)
17.7 C7H2 Isomers
396(7)
17.7.1 Introduction
396(5)
17.7.2 Relative Energies, Zero Point Vibrational Energies and Dipole Moments of the C7H2 Molecules
401(1)
17.7.3 Vibrational Frequencies, Electronic Spectra, and Rotational Data
402(1)
17.8 Isomers of C8H2, C10H2, C12H2, C14H2, and C16H2
403(5)
17.8.1 Isomers of C8H2
403(2)
17.8.1.1 Vibrational Data
404(1)
17.8.1.2 Electronic Spectra and Rotational Data
405(1)
17.8.2 Isomers of C10H2
405(1)
17.8.2.1 Vibrational Data, Electronic Spectra, and Rotational Data
405(1)
17.8.3 Isomers of C12H2
406(2)
17.8.4 Isomers of C14H2 and C16H2
408(1)
17.9 Isomers of C9H2, C11H2, C13H2 and C15H2
408(2)
17.10 Summary
410(4)
References
414(8)
Appendix 17.1 Constructs of All Molecules Presented in this Chapter
422(1)
Appendix 17.2 Calculations Carried out for this Chapter Using the Spartan 02 and 04 Programs
423(2)
Chapter 18 Polyynes: Possible Bulk Synthesis and Chemical Properties 425(28)
Franco Cataldo
18.1 Introduction
425(1)
18.1.1 Some Notes on Polyynes in Nature and their Biological Activity
426(1)
18.2 Possible Scale-Up Synthesis of Polyynes with the Submerged Carbon Arc Technique
426(8)
18.2.1 Preparation of Concentrated Solutions of Polyynes by Distillation
426(2)
18.2.2 Polyynes: Isolation as Acetylides
428(6)
18.3 Hydrogenation of Polyynes to Ene-Ynes: An Easy Access to Biologically Active Molecules
434(9)
18.4 Oxidative Degradation and Photolysis of Polyynes
443(5)
18.4.1 Stability of Polyyne Solutions in Air
443(1)
18.4.2 Oxidation of Polyynes with Ozone
444(1)
18.4.3 Addition of Bromine to Polyynes
445(1)
18.4.4 Polyyne Photolysis in Air (Low Pressure Hg Lamp)
445(2)
18.4.5 Polyyne Photolysis in Nitrogen (High Pressure Hg Lamp)
447(1)
18.5 Conclusions
448(2)
References
450(3)
Chapter 19 From Natural to Rationally Designed Artificial Enediynes: Towards New Anticancer Antibiotics Activable at Will 453(40)
Giuseppe Guanti, Luca Banfi, Andrea Basso and Renata Riva
19.1 Introduction
454(6)
19.1.1 The Natural Enediynes
454(1)
19.1.2 The Natural Enediynes of Type I
455(2)
19.1.3 Mechanism of Action of Type I Enediynes
457(1)
19.1.4 Rational Design of Artificial Enediynes
458(2)
19.1.5 Preliminary Testing of Artificial Enediynes
460(1)
19.2 Synthetic Methodologies for the Construction of Cyclic 10-Membered Enediynes
460(4)
19.2.1 Cyclization after Enediyne Construction
461(1)
19.2.2 Double-Bond Formation During or After Cyclization
462(2)
19.3 Monocyclic or Ortho-Fused Artificial Enediynes
464(5)
19.3.1 Monocyclic Carba Enediynes
464(2)
19.3.2 Cyclic Enediynes Fused with Arenes Through the Double Bond
466(1)
19.3.3 Aza, Oxa, and Thia Enediynes, Monocyclic or Fused with Arenes Through the Double Bond
467(1)
19.3.4 Cyclic Enediynes Fused with Other Rings Through Carbons 7-10
468(1)
19.4 Bridged Polycyclic Enediynes
469(9)
19.4.1 Compounds with a Double Bond as a Safety Catch
470(2)
19.4.2 Compounds with an Epoxide as a Safety Catch
472(4)
19.4.3 Compounds Where the Enediyne Double Bond is Formed by a Suitable Reaction
476(1)
19.4.4 Miscellaneous
476(2)
19.5 Acyclic Enediynes
478(5)
19.5.1 Influence of Substituents
479(1)
19.5.2 Metal-Ion Coordination
480(1)
19.5.3 The Myers–Saito Cycloaromatization
481(1)
19.5.4 Photochemical Cycloaromatization Reaction
482(1)
References
483(10)
Chapter 20 Polyynes: Simple Synthesis in Solution Through the Glaser Reaction 493(6)
Franco Cataldo and Yeghis Keheyan
20.1 Introduction
493(1)
20.2 Experimental
494(1)
20.2.1 Typical Synthesis of Polyynes by Glaser Reaction
494(1)
20.2.2 Liquid Chromatographic Analysis
494(1)
20.2.3 Stability of Polyynes in Concentrated Solutions
495(1)
20.3 Results and Discussion
495(3)
References
498(1)
Abbreviations 499(4)
Index 503

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