LINZ LECTURES. Lecture 1. The Development of Organic Conductors: Metals, Superconductors and Semiconductors

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1 LINZ LECTURES Lecture 1. The Development of Organic Conductors: Metals, Superconductors and Semiconductors Lecture 2A. Introduction and Synthesis of Important Conjugated Polymers Lecture 2B. Solid State Polymerization Lecture 3. Fullerene Chemistry Lecture 3B. Molecular Engineering

2 Carbon Allotropes Falcao EHL, Carbonaceous materials with exotic morphologies. PhD Dissertation, University of California, Los Angeles, CA, Ch. 1 (2006)

3 Popular Science August 1991, p 53

4 The Arc-Discharge Preparation Method

5 The Continuous Process Preparation

6 The Fullerene Bench-Top Reactor

7 Soxhlet Chromatography Separation

8 Physical Properties of Buckminsterfullerene Hard crystals, red by transmission, black by reflection, yellow in film form Sublimes above 500 Torr H f = 545 kcal/mol, l ρ = 1.78 g/ml, = -260 cgs ppm Cubic closed packed structure, individual molecules rotate at RT, transition to static Below 250 K Bond alternation: 1.37 and 1.45 Å

9 Molecular Orbital Energy Diagram

10 Electrochemical Properties Xie, Q.; Pérez-Cordero, E.; Echegoyen, L. j. Am. Chem. Soc. 1992, 114, 3978

11 A Chemical Equivalent Electron acceptor, dienophile, Electron acceptor, dienophile, dipolarophile electrophile dipolarophile electrophile

12 Dipolarophile: the first Crystalline Derivative

13 Dienophile: Crystalline Diels Alder Adduct

14 Dipolarophile: the first C 61, 60-π Electron Derivative

15 Dipolarophile: the first C 61, 60-π Electron Derivative 60-π Electron 58-π Electron

16 Electrophile: Nucleophilic Additions

17 Cyanide Addition

18 Electrochemistry of the Dicyano Derivative

19 Multi-cyanation of C 60 H N N N a 72% C 60 H(CN) H N N N b c C 60 58% 51% C 60 H(CN) 3 N N b N C 60 (CN) 2 22% N C 60 (CN) 4 Jousselme, B.; Sonmez, G.; Wudl, F. J. Mater. Chem., 2006, 16,

20 Negative MALDI-TOF spectra of C 60 H(CN) 3 (a) and C 60 (CN) 4 (b).

21 HPLC profile of (a) C 60, (b) C 60 H(CN), (c) C 60 (CN) 2, (d) C 60 H(CN) 3, (e) C 60 (CN) 4

22 Non-Regiospecific Addition of CN (-) Aromatic part spectrum 1 H NMR of (a) C 60 H(CN) 3 and (b) C 60 H(CN), in CD 2 Cl 2.

23 Electrochemistry of (Cyano)C 60 Differential Pulse Voltammetry of (a) C 60, (b) C 60 H(CN), (c) C 60 (CN) 2, (d) C 60 H(CN) 3, (e) C 60 (CN) 4 in 0.1 M TBAP/ODCB

24 Reduction Potentials of Cyano-Fullerenes Reduction potentials (V vs Ag/Ag + ) Compound E 1 E 2 E 3 E 4 C C 60 H(CN) C 60 (CN) C 60 H(CN) C 60 (CN)

25 Electrochemical pka Determination M. Niyazymbetov, D. Evans, S. Lerke, P. Cahill, C. Henderson, J. Phys. Chem., 1994, 98, DPV f C H(CN) (bl k) ith i l t f di lt ( d) (T l ft di t t DPV of C 60 H(CN) (black) with one equivalent of sodium salt (red). (Top left, sodium acetate; top right, sodium chloroacetate. Bottom left, sodium dichloroacetate; bottom right, sodium trifluoroacetate).

26 Electrochemical pka Determination DPV of C 60 H(CN) 3 (black) with one equivalent of sodium salt (red). (Top left, sodium acetate; top right, sodium chloroacetate. Bottom left, sodium dichloroacetate; bottom right, sodium trifluoroacetate).

27 Isomer Interconversions, Including Reversion to C to C 60

28 An Important Example, PCBM C 60 + C 6 H 5 C N 2 MeO 2 C(CH 2 ) 3 C H C6 H 5 (CH 2 2) 3 CO 2 Me C 6 H 5 (CH 2 ) 3 CO 2 Me H PCBM Preparation and Characterization of Fulleroid and Methanofullerene Derivatives. Hummelen, J. C.; Knight, B. W.; LePeq, F.; Wudl, F.; Yao, J.; Wilkins, C. L. J. Org. Chem. 1995, 60,

29 Dipolarophile: The Most Efficient Derivatizations

30 Synthetic Reactions Applicable to Fullerene Materials R C C R' R R' N 2 B-H DBU R R' R R' i or ii or iii or iv C 60 [R 2 C] n? C 60 [R 2 C] n Materials P R' NH R n C + 60 RCHO + R'NHCH 2CO 2H (+) (-) i, ÞC; ii, hν; iii, H ; iv, e Prato, M. Fullerene Materials. Topics in Current Chemistry 1999, 199, zz

31 High Yield Regioselective Additions Murata, Y.; Shiro, M.; Komatsu, K. J. Am. Chem. Soc. 1997, 119, Sawamura, M.; Ilkura, H.; Nakamura, E. J. Am. Chem. Soc. 1996, 118, Nakamura, E. Pure and Appl. Chem. 2003, 75, Isobe, H.; Tanaka, T.; Nakanishi, W.; Lemiegre, L.; Nakamura, E. J. Org. Chem. 2005, Isobe, H.; Tanaka, T.; Nakanishi, W.; Lemiegre, L.; Nakamura, E. J. Org. Chem. 2005, 70, 4826

32 Applications?

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34 Fullerene-PPV Plastic Solar Cell Electron Transfer PCBM MDMO-PPV Courtesy of Prof. Sariciftci

35 Proposed Interaction between Polymer and Fullerene Derivativ Courtesy of Prof. Sariciftci

36 Dipolar Cycloaddition of Azide: Synthesis of a PCBM Nitrogen Analog O O C O O N O O N PCBM 5,6-Open 5,6 APCBM 6,6-Closed 6,6 APCBM Changduk Yang

37 Electrochemical Data Cu urrent Den nsity (μa) C 60 Electrode Potential (V vs Fc/Fc+) PCBM 5,6-Open 6,6-Closed compound E 1 E2 E 3 E 1 red E red E 3 red 5,6-Open ,6-Closed PCBM C

38 Optical Data Absorban ce [a.u.] C 60 PCBM 6,6-Closed 5,6-Open Absorban nce [a.u.] C 60 PCBM 6,6-Closed 5,6-Open Wavelength (nm) UV-Vis absorption in CHCl 3 solution. compound 5,6-Open Absorption (nm) 332, 435(sh), 547, 602(sh) Wavelength (nm) 6,6-Closed 326, 423, 495, 607(sh), 685 PCBM 328, 430, 490, 603(sh), 695 C , 405, 540, 600, 623(sh)

39 OFET Results I ds (A A) PCBM Close Open Ca S & D electrodes V gs (V) (A A 1/2 ) I ds 1/2 I ds (μa A) Open 60V 50V 40V 30V 20V V ds (V) I ds (μ μa) 40 PCBM 60V 30 50V 20 40V 10 30V 20V I ds (μ μa) 25 Colse 60V 20 50V V 5 30V 0 20V V ds (V) V ds (V) PCBM: μ = 3.4 X ,6-Closed: μ = 2.8 X ,6-Open : μ = 4.1 X 10-2

40 Bulk Heterojunction Solar Cell Device ITO/PEDOT:PSS/Polymer/Al sity (ma A/cm 2 ) Curre ent Den P 3 HT : Close P 3 HT : Open P 3 HT : PCBM OPEN Voc : 0.58 V Isc:810mA/cm Fill Factor: 0.60 Max Efficiency: 2.8 % CLOSE Voc : 0.58 V Isc : 7.14 ma/cm 2 Fill Factor: 0.56 Max Efficiency: 2.3 % PCBM Voc : V Isc:811mA/cm Fill Factor: 0.66 Max Efficiency: 3.4 % Voltage (V)

41 White Light LED Hutchison, K.; Gao, J.; Schick, G.; Rubin, Y.; Wudl, F. Journal of the American Chemical Society 1999, 121, 23,

42 Hutchison, K.; Gao, J.; Schick, G.; Rubin, Y.; Wudl, F. Journal of the American Chemical Society 1999, 121, 23,

43 Electroluminescens Spectra Bucky Light Bulbs: White Light Electroluminescence from a Fluorescent C 60 Adduct-Single Layer Organic LED. Hutchison, K.; Gao, J.; Schick, G.; Rubin, Y.; Wudl, F. Journal of the American Chemical Society 1999, 121, 23, 5611-

44 C 60 POLYMERS pearl necklace polymer charm bracelet polymer star-like polymer Prato, M. Fullerene Materials in Topics in Current Chemistry 1999, 199,

45 C POLYMERS + Ar [Mo] = RO N Mo Bu t [Mo] RO m n Wudl, F.; Prato, M. et al. Chem. Mater. 1995, 7,

46 S S S S N 2 C 60 electrochemistry conjugated polymer Benincori, T.; Brenna, E.; Sannicolò, F.; Trimarco, L.; Zotti, G. et al. The First "Charm Bracelet" Conjugated Polymer: An Electroconducting polythiophene with covalently bound fullerene moieties. Angew. Chem., Int. Ed. Engl. 1996, 35,

47 Summary Though Buckminsterfullerene C 60 is easily derivatized through cycloaddition/nucleophilic addition, there are still major applications waiting to be invented/discovered Though Buckminsterfullerene C 60 is easily derivatized, most derivatization reactions occur in moderate-to-low yield

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