WO2015154190A1 - Conjugated polymers, and synthesis and use thereof - Google Patents

Abstract

Donor-acceptor conjugated polymers, their precursors, synthesis and use. Electron-accepting (A) and electron-donating (D) repeat units having a conjugated polymer backbone are able to operate under both positive and negative bias, making a device with a relatively high operating voltage possible. The specific energy and specific power exceeds what is attainable with conventional conjugated polymers.

Description

CONJUGATED POLYMERS, AND SYNTHESIS AND USE THEREOF

Field

The present invention relates to conjugated polymers. More particularly, polymers of the invention are donor-acceptor polymers useful as supercapacitor electrode materials.

Background

Conjugated polymers store charge differently than high surface area carbon (HSAC), which is receiving a lot of attention as an energy storage material for supercapacitors,^1"3 and particularly with the recent advancements made in carbon nanotube^4,5 and graphene based devices,^6"9 and the availability of commercial products.^10,11 HSAC supercapacitors store energy electrostatically through double- layer capacitance. This charge storage mechanism is physical rather than chemical and is non-Faradaic (no formal oxidation or reduction takes place). Due to this physical charge storage mechanism these devices can be charged and discharged very rapidly, which is important for a variety of applications.

Conjugated polymers also store charge electrostatically,¹² however they also exhibit a Faradaic charge storage mechanism, which is an important distinction from HSACs. This combination of non-Faradaic charge separation and Faradaic (formal chemical oxidation and reduction) allows conjugated polymers to store significantly more energy than HSAC.^{1 ,2} Oxidation or reduction occurs in a similar manner as a battery, however, the reaction quotient, or the extent of the reaction, depends on the applied potential; thus the materials are considered pseudocapacitative (Equations 1 and 2).

Ox + ze Red (1 ) Q = m = Ke (2)

^ [Ox] ¹

Some of the better known pseudocapacitive conjugated polymers include poly(3,4- ethylenedioxythiophene) (pEDOT), polypyrrole, and polyaniline. Recent work has focused on blending these polymers with carbon nanotubes^{5 13} or graphene¹⁴ to enhance energy density, however, all of the aforementioned polymers have early oxidation potentials and are only capable of positive (p-type), as opposed to negative (n-type) or ambipolar charging, limiting the operating voltage of the device.

The operating voltage of the device is limited to the positive charging voltage range of the polymer (typically 0.8-1 .4 V wide). This is important, because the energy stored in a capacitor is proportional to the square of the operating voltage and can be increased significantly by increasing the operating voltage window (Equation 3).

E = CV² (3)

Donor-acceptor polymers are typical in organic photovoltaic applications but atypical in supercapacitor research. When fabricated into a Type I I I supercapacitor, they can significantly increase the operating voltage of polymer-based supercapacitors because they can carry both a positive and negative charge depending on the applied potential.¹⁵ This ambipolar characteristic of the polymer gives these capacitors a wide operating voltage window, which increases voltage, energy, and power. Only a handful of donor-acceptor type polymers have been used in supercapacitors^15"21 and to the best of our knowledge, there is only one other example of an alternating donor-acceptor copolymer used in a Type I I I device configuration.²²

Summary

Here, a number of donor-acceptor polymers were synthesized and their electrochemical properties characterized. Polymers were fabricated into into electroactive films, used to fabricate Type I I I supercapacitors. The results shed light on the question of charge derealization within donor-acceptor polymers. While the positive charge derealization of donor-acceptor polymers is well established, the negative charge derealization on these materials somewhat ambiguous.²³ Estrada, et al. observed localization of the LUMO on the acceptor moiety and charge-pinning upon reduction of the polymer.²² Here, the use of several pEDOT-acceptor polymers for Type I I I supercapacitors was explored and it was demonstrated that two adjacent electron-accepting units can increase negative charge derealization and improve the performance of a Type I I I device. Donor-acceptor conjugated polymers can thus be used in high energy and high power supercapacitors. By coupling electron-accepting (A) and electron- donating (D) repeat units into a conjugated polymer backbone, the material is able to operate under both positive and negative bias, resulting in a device with a high operating voltage. The specific energy and specific power exceeds what is attainable with conventional conjugated polymers and sheds light on the design criteria of conjugated polymers for energy storage applications.

An aspect of the invention is an electropolymerizable monomer of formula (A):

wherein:

(A) X is S, O, Se, Te, NH, N(Ci_-30-alkyl) or -CR^5'CR^6'- and the fused rings

together form a bicyclic aromatic system;

(B) Z is S, O, Se, Te, NH, N(Ci_-30-alkyl);

(C) (i) each of R¹, R², R³, R⁴, R⁵, R^5', R⁶ and R^6' is, independently of the other, selected from the group consisting of:

hydrogen,

optionally substituted Ci-3o-alkyl,

optionally substituted C₂-3o-alkenyl,

optionally substituted C₂-3o-alkynyl,

optionally substituted C_3-2o-cycloalkyl,

(CH₂CH₂0)a-(CH₂)_b-CH₃ for a = 1 -100 and b = 0-100,

optionally substituted aryl, wherein each said optional substitution is made independently and up to six times for each R¹ , R², R³, R⁴, R⁵ and R⁶, and substituents are selected from:

halogen, -CN, -N0₂, -OH, C_1-10-alkoxy, -O-CH₂CH₂O-C_{1 -10}- alkyl, -O-COX¹ , -S-Ci_i₀-alkyl, -NH₂, -NHX¹ , -NX¹X², -NHC(0)X¹ , -C(0)OH, -C(0)OR⁷S, -C(0)NH₂,

-C(0)NHX¹ , -C(0)NX¹X², -C(0)H, C(0)X¹ , Ci-io-alkyl, C₂-io-alkenyl, C_2-io-alkynyl, C3-i₄-cycloalkyl, including bicycloalkyl, 3-14 membered cycloheteroalkyl, C_6--i₄- aryl, and 5-14 membered heteroaryl,

wherein each X¹ and X² is independently of the other C-i-io-alkyl, C_2-i₀-alkenyl, C_2-i₀-alkynyl, C_3-io-cycloalkyl, C5-io-cycloalkenyl, 3-14 membered cycloheteroalkyl, Ce- 14-aryl or 5-14 membered heteroaryl;

(ii) R¹ and R² are as defined in (i) and R³ and R⁴ together, are -CH₂CH₂-, or -CH₂CH₂CH₂-, or -CH₂C(R⁸)₂CH₂- where R⁸ is a group defined in (i); or

(iii) R¹ and R² together, and R³ and R⁴ together, are -CH₂CH₂-, or

-CH₂CH₂CH₂-, or -CH₂C(R⁸)₂CH₂- where R⁸ is a group defined in (i); and

(D) n = 1 or 2, or 3, or 4, or 5; and

including salts of the foregoing.

In another aspect, the invention is a conjugated polymer containing units having structural formula (B):

(B) wherein R¹ , R², R³, R⁴, R⁵, R^5', R⁶ and R^6', X, Z and n are each defined as in claim 1 , and m is an integer from 2 to 1000. Values of m can be between 10 and 900, 10 and 800, 20 and 800, 20 and 700, 20 and 600, 20 and 500, 20 and 400, 20 and 300 or 20 and 200, or is up to about 1000, 900, 800, 700, 600, 500, 400, 300, 200, 150, 100, 90, 80, 70, 60 or 50, or is at least 2, 5, 1 0, 15, 20, 25, 30, 35 or 40.

In a preferred aspects, X and Z are S, or X is -CHCH- and Z is S.

In an aspect, the invention is a polymer having a fully conjugated backbone, the polymer being the electropolymerization product of a monomer of formula (A).

A particular aspect of the invention is an electrically conductive polymer containing conjugated polybenzothiadiazole and polythiophene segments.

Where X = S, the fused bicyclic shown in the structural formula is a benzothiadiazole, and where two or more such units are directly covalently linked to each other, they are referred to as a polybenzothiadiazole segment of the polymer. In embodiments, the mole ratio of thiophene:benzothiadiazole units can be from 2: 1 to 1 : 1 . In a specific embodiment, there are benzothiadiazole units that are

unsubstituted i.e. R⁵ and R⁶ are both hydrogen atoms.

In particular polymers of the invention, the thiophene units are 3,4- dimethoxythiophene or 3,4-ethylenedioxythiophene.

An electrically conductive polymer of the invention can also be made up of conjugated polybenzotriazole and polythiophene segments; conjugated

polybenzoxadiazole and polythiophene segments; conjugated

polybenzoselenadiazole and polythiophene segments; or conjugated

polybenzotelluradiazole and polythiophene segments.

In the case of the benzothiadiazoles, benzoxadiazoles, benzoselenadiazoles and telluradiazoles, the locations of the heteroatoms are as indicated for the above structural formula of compound (A). Likewise, the locations of the bonds joining the benzene- (of e.g., quinoxaline) and the thiophene-rings to their neighbors to form a conjugated polymer backbone are as indicated in the structural formula of compound (A) regardless of whether explicit reference is made to the structural formula in describing a polymer of the invention.

The invention includes methods of polymerization. In one aspect, the method includes electropolymerizing a monomer (D-A-D) comprising a quinoxaline acceptor unit (A) covalently linked to two alkoxythiophene donor units (D), wherein the polymer formed has the structure poly(D-A-D) in which the acceptor and donor units are conjugated with each other. (For the sake of clarity, it should be mentioned here that formula (A) shown above is a designation of the structure, and is not intended to mean "acceptor unit".)

The invention includes a method of polymerization that includes

electropolymerizing a monomer (D-A-A-D) comprising a pair of benzothiadiazole acceptor units (A-A), each covalently linked to an alkoxythiophene donor unit (D), wherein the polymer formed has the structure poly(D-A-A-D) in which the acceptor and donor units are conjugated with each other.

The monomer can be contained in a non-aqueous solution and the polymer can be electropolymerized directly onto an electrically conductive substrate. Such substrate can be e.g., a metal electrode or carbon. The product of the method can be for use e.g., as a component of an electrical device, e.g., a supercapacitor, including a Type III supercapacitor as described in greater detail below.

The polymer can be formed to a thickness of at least 0.001 μιη. Polymer thickness can be between 0.001 and 10,000 μιη, or between 0.1 and 5,000, 0.1 and 1 ,000, 0.01 and 5,000, 0.01 and 1 ,000, 0.1 and 500 μπι.

Another aspect of the invention is a method of preparing a monomer from precursors having formulas (A1 ) and (D1 ),

(A1 )

wherein the method comprises: in an anaerobic environment, combining a palladium catalyst having an organic ligand, and precursors A1 and D1 , and obtaining a conjugated monomer containing quinoxaline and thiophene units with the formula D1 -A1 -D1 :

(D1 -A1 -D1 )

wherein each of X and Z and R¹, R², R⁵, R⁵ , R⁶ and R⁶ are, independently of each other, defined as above for monomer of formula (A); and

each Y is a halogen atom, tosylate, or mesylate and can be the same or different from each other.

The catalyst can be palladium acetate, and the combined mixture can further include an organic acid that can be pivalic acid. The mixture is typically heated to above 25°C, preferably to at least 50°C, or at least 60°C, or at least 70°C, or at least 80°C, or at least 90°C or at least 100°C. The combined mixture can further include a base, which can be e.g., potassium carbonate.

An electrode of the invention can thus be a polymer formed by

electropolymerization onto a supporting metal or carbon fiber or other conductive substrate, wherein the specific power of the polymer is at least 0.1 kW/kg, when measured in a Type III supercapacitor. An electrode of the invention can include a polymer that is the electropolymerization product of a monomer of formula (A), wherein the specific power of the polymer is at least 0.1 kW/kg, when measured in a Type I II supercapacitor.

Specific energy of the polymer of an electrode can be at least 0.76 Wh/kg, when measured in a Type III supercapacitor.

Power density of the polymer can be at least 0.01 kW/L, when measured in a Type I II supercapacitor. Energy density of the polymer can be at least 0.1 Wh/L, when measured in a Type I II supercapacitor.

An electrode having an average capacitance calculated from the discharge measurement of a galvanostatic charge-discharge experiment at 0.5 A/g of at least 17 F/g is achievable through application of the invention.

The term "alkyl" indicates the radical obtained when one hydrogen atom is removed from a hydrocarbon. An alkyl group can contain 1 to 30 carbon atoms (d- 3o), and unless specified as linear, can be linear or branched. An alkyl group can also contain 1 to 20, 1 to 18, 1 to 16, 1 to 14, 1 to 12, 1 to 10, 1 to 8, 1 to 6, 1 to 4, 1 to 3 or 1 or 2 carbon atoms. Examples are methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, t-butyl, pentyl, isopentyl, hexyl and isohexyl.

The term "cycloalkyi" indicates a saturated cycloalkyi radical having 3 to 20 carbon, 3 to 10, 3 to 8, or 3 to 6 carbon atoms, and includes fused bicyclic rings. Examples are cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and cycloheptyl.

The term "alkenyl" means a mono-, di-, tri-, tetra- or pentaunsaturated hydrocarbon radical having 2 to 30 carbon atoms, which can be branched or unbranched. An alkenyl radical can also contain 2 to 20, 2 to 1 8, 2 to 16, 2 to 14, 2 to 12, 2 to 10, 2 to 8, 2 to 6, 2 to 5, 2 to 4, or 2 to 3 carbon atoms. Examples include ethenyl, propenyl, butenyl, pentenyl or hexenyl. A cycloalkenyl radical is a cycloalkyi radical containing 1 , 2, 3, 4 or 5 carbon-carbon double bonds (C=C).

The term "alkynyl" indicates an hydrocarbon radical comprising 1 to 5 triple carbon-carbon triple bonds (C≡C) and 2 to 30 carbon atoms, and the radical can be branched or unbranched (linear). An alkynyl group can also contain 2 to 20, 2 to 18, 2 to 16, 2 to 14, 2 to 12, 2 to 10, 2 to 8, 2 to 6, 2 to 5, 2 to 4, or 2 to 3 carbon atoms. Examples include ethynyl, propynyl, butynyl, pentynyl or hexynyl.

The term "aryl" means a radical of aromatic carbocyclic rings having 6 to 20 carbon atoms, or 6 to 14, 6 to 12, 6 to 10 carbon atoms. Included are fused carbocyclic rings with at least one aromatic ring, such as phenyl, naphthyl, indenyl and indanyl.

The term "heteroaryl" indicates radicals of heterocyclic aromatic rings containing 1 to 6 heteroatoms (O, S and/or N) and 1 to 20 carbon atoms. There may be 1 to 12, 1 to 10, 1 to 8, 1 to 6 or 1 to 5 carbon atoms, and 1 to 5, or 1 to 4, or 1 to 3 heteroatoms. Fused bicyclic rings with 1 to 4 heteroatoms, and having at least one ring that is aromatic are included. Examples are pyridyl, quinolyl, isoquinolyl, indolyl, tetrazolyl, thiazolyl, imidazolyl, pyrazolyl, oxazolyl, isoxazolyl, thienyl, pyrazinyl, isothiazolyl, benzimidazolyl and benzofuranyl.

An "alkoxy" group is a radical of the formula -OR in which R is C-MO alkyl.

Examples are methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, isobutoxy, tert-butoxy, n-pentoxy, neopentoxy, isopentoxy, hexoxy, n-heptoxy, n- octoxy, n-nonoxy and n-decoxy.

A "cycloheteroalkyl" group is a cycloalkyl radical in which one to 5 carbon atoms, and any associated hydrogen atoms as necessary, are independently replaced with the same or different heteroatom. A cycle contains 3 to 14 atoms. Examples are epoxides and radicals formed by the removal of a hydrogen atom from imidazolidine, morpholine, piperazine, piperidine, pyrazolidine, pyrrolidine and quinuclidine.

"Halogen" means fluorine, chlorine, bromine, iodine or astatine.

Unless clearly indicated otherwise, the term "alkoxythiophene" is used herein to generally describe 3,4-disubstituted thiophenes, whether the substitutions be two methoxy groups as in 3,4-dimethoxythiophene, or a bridging dioxyethylene group, as in 3,4-(ethylenedioxy)thiophene, etc., and whether or not such thiophene is incorporated into a polymer or a separate molecule. Similarly, shorthand is used in connection with other molecules/polymer units, such as quinoxaline, and it is clear to the skilled person from the context the structure of the molecule or unit being described.

Brief Description of the Drawings

Figure 1 shows structures of the monomers studied. The first six monomers shown are composed of both donor and acceptor units. The aromatic cycles of donor units are those containing nitrogen atoms (bicyclics for all molecules except for

DPODA), and acceptor units are appended thereto;

Figure 2 shows synthetic outline of DEQ by direct heteroarylation and Suzuki- type synthesis of DDDBT. DEDQ and DDDQ were synthesized in a similar fashion to

DDDBT; Figure 3 shows electrochemical polymerization and deposition of polymers by cyclic voltammetry, the corresponding monomer for each being shown in the inset for each. Cyclic voltammograms of pEDOT, pDEQ and pDDDBT films (solid lines) and the respective monomers (dotted lines) are shown to the right;

Figure 4 shows scanning electron microscopy images of a cross-section of pDEQ (upper image) and pDDDBT (lower image) films. The platinum current collector appears light, at the bottom of each image, and the polymer appears darker, towards the middle of each image;

Figure 5 shows electrochemical characterization of Type I pEDOT (left column), Type I I I pDEQ (middle column), and Type I I I pDDDBT devices (polymer structure inset in corresponding column). Top row: cyclic voltammetry at 50, 100, 200, 500, 750, 1 000 mV s^~1. The electrodes are represented with a circle (o). The state of charge on the electrode for the discharged and charged device is indicated by "+" and "-"s. The middle plots show peak capacitance vs. scan rate. The bottom row shows charge-discharge at 1 A g^"1 current density;

Figure 6 is a photograph of the platinum button electrodes, the separator, and the Teflon casing (top) used to prepare the devices. An illustration of the assembled capacitor device is shown at the bottom , the Teflon casing being cut away for clarity. ;

Figure 7 shows changes in bond length along the acetylene backbone from neutral to + 1 (upper panels) and neutral to -1 (lower panels) singlet states for a) DEQ, b) DDDBT, c) EDOT-J -BT. The corresponding orbital diagram is above the plot;

Figure 8 shows optimized structures of DDDBT (left) and DDDQ (right) monomers;

Figure 9 shows bond length change for pEDOT model neutral minus +1 for all bonds excluding those to hydrogen;

Figure 10 shows bond length change for DEQ model neutral minus +1 for all bonds excluding those to hydrogen;

Figure 11 shows bond length change for DEQ model neutral minus -1 for all bonds excluding those to hydrogen;

Figure 12 shows bond length change for pDDDBT model neutral minus + 1 for all bonds excluding those to hydrogen; Figure 13 shows bond length change for pDDDBT model neutral minus -1 for all bonds excluding those to hydrogen;

Figure 14 shows bond length change for p(EDOT-J -BT) model neutral minus +1 for all bonds excluding those to hydrogen; and

Figure 15 shows bond length change for p(EDOT-BT) model neutral minus -1 for all bonds excluding those to hydrogen.

Detailed Description

Various embodiments of the present invention are described, by way of example only, with reference to the drawings.

Five donor-acceptor monomers were synthesized:

DEQ: 5,8-bis(2,3-dihydrothieno[3,4-J ][1 ,4]dioxin-5-yl)quinoxaline; DEDQ: 8,8'-bis(2,3-dihydrothieno[3,4-J ][1 ,4]dioxin-5-yl)-5,5'- biquinoxaline;

DDDQ: 8,8'-bis(3,4-dimethoxythiophen-2-yl)-5,5'-biquinoxaline; DDDBT: 7,7'-bis(3,4-dimethoxythiophen-2-yl)-4,4'- bibenzo[c][1 ,2,5]thiadiazole; and

DPODA: 2,5-diphenyl-1 ,3,4-oxadiazole.

The known monomer, 3,4-ethylenedioxythiophene (EDOT), was also synthesized. The structural formulas of these monomers are shown in Figure 1 .

The monomers permitted study the effect of increasing the acceptor to donor ratio in the polymers. See Table One. Synthesis as well as three molecular design factors are considered: solubility, film formation, and electrochemical potential range.

Donor-acceptor trimeric monomers with EDOT end groups, such as DEQ of the invention, are important compounds for both electrochromic^24"29 and, more recently, supercapacitor applications.²² Most syntheses involve at least three steps, require an alkyllithium reagent, and include the preparation of an alkyl-tin reagent. The highly toxic alkyl-tin compounds are used in excess (up to 2.5 times the stoichiometric requirement).²⁴ Here, apparently for the first time, direct

heteroarylation was used for the synthesis of a donor-acceptor trimeric monomers eliminating use of alkyllithium and alkyl-tin reagents, the need for cryogens, while achieving yields comparable to Stille coupling with higher atom economy. The direct heteroarylation described further below is a one-step, one-pot reaction conducted at moderate temperature. See Figure 2.

TABLE ONE

Physical data of monomers

The donor-acceptor tetrameric monomers, DEDQ, DDDQ, and DDDBT were synthesized using Suzuki-Miyamura coupling. First EDOT or 3,4- dimethoxythiophene is treated with an alkyllithium reagent followed by

isopropoxyboronic acid pinacol ester to yield the corresponding boronic ester. The boronic ester is then treated with the dibrominated acceptor molecule (5,8- dibromoquinoxaline or 4,7-dibromobenzo[c]-1 ,2,5-thiadiazole) in a one to one ratio. The mono-brominated product is then subjected to a one-pot in situ boronic esterification followed by coupling using half an equivalent of

bis(pinacolato)diboron.³⁰ Solubility is an important parameter for solution-based approaches to polymerization. Side-chains can increase the solubility of the monomer, however alkyl side-chains act as insulators and are not electrochemically active, thus it is typically desirable for the side-chain size to be minimized. For electropolymerized materials it is sufficient for the monomer to be soluble while this not a requirement of the corresponding oligomers/polymers formed, as deposition of insoluble

oligomers/polymers is usually desired. No solubilizing groups are required for the D- A-D trimeric monomers prepared, however it was found that the D-A-A-D tetrameric monomer DEDQ was only sparingly soluble and not suitable for polymerization. Substituting dimethoxythiophene for EDOT in the DDDQ and DDDBT tetrameric monomers increased the solubility significantly and allowed for the preparation of appropriately concentrated solutions (5 mM).

Electrochemical polymerization affords several advantages for polymer film formation: polymers are formed directly on the electrode surface and several micrometers thick films can be readily deposited. However, certain electronic factors will make electrochemical polymerization impossible and thus judicious selection of monomers is important. For example, although DPODA has a reversible reduction wave^{31 ,32}and appears to be a good candidate for an n-type polymer, it was not found possible here to be polymerized electrochemically because the oxidation potential of the monomer is too high. On the other hand, DEQ and DDDBT are readily polymerized by cyclic voltammetry in an analogous manner to EDOT (Figure 3), and several micrometer thick films of oligomers/polymers are formed.

The cross-sections of the pDEQ and pDDDBT films indicate that the morphologies of the two films are quite different, as shown in Figure 4. The pDEQ film is composed of small clusters of material with very small grain sizes. The pDDDBT film is composed of much larger domains of oligomer/polymer. This could be due to faster grain nucleation for DEQ compared with DDDBT.

Notably, although structurally similar to DDDBT, it was not found possible to electrochemically polymerize DDDQ. Oxidation was observed but the peak fails to increase with subsequent oxidation. A very thin film was observed on the electrode surface. Because the monomer is oxidized but only produces a very thin film, it is possible that the film formed is not suitably conductive for subsequent growth. This could be the result of steric hindrance that leads to a large dihedral angle between adjacent quinoxaline groups and disrupts the conjugation along the molecule (Figure 8). The predicted dihedral angle between the two quinoxalines of DDDQ is 49.0° (DFT calculation) compared to only 31 .2° between the benzothiadiazoles in DDDBT.

The electrochemical response of pEDOT, pDEQ, and pDDDBT was investigated using cyclic vol tarn metry in a standard three-electrode electrochemical cell (Figure 3, Table Two). Charge carrier derealization and pseudocapacitance are important criteria for conjugated polymer supercapacitors. A shift of the oxidation onset (or reduction onset) to lower (higher) potentials as the monomer is converted to the oligomer/polymer is indicative of derealization, which is due to the formation of low energy states, and results in a broad, rectangular cyclic voltammogram.

TABLE TWO

Electrochemical data of the polymer films

Oxidation Oxidation Reduction Reduction Onset Window Onset Window

Polymer Polymer Structure [V vs Ag/Ag⁺] [V] [V vs Ag/Ag⁺] [V] pEDOT -0.89 1.9 n/a n/a

-(¾ pDEQ -0.28 0.98 -1.32 0.88

pDDDBT 0.16 0.84 -1.08 1 .12

pEDOT has a wide, rectangular cyclic voltammogram, indicative of charge derealization. Similarly, the cyclic voltammogram of pDEQ exhibits a broad flat current response at oxidative potentials, which indicates gradual positive charging over a relatively broad potential range. However, at reductive potentials a much narrower peak is observed. Comparing the magnitude of the oxidative wave to the reductive wave of pDEQ, it is apparent that the material can store more positive charge than negative charge. In contrast to a large stabilization of the HOMO energy level (ca. 750 mV), the reduction onset increases only slightly (ca. 20 mV) and thus there is very little LUMO stabilization upon polymerization. These observations indicate that there is good delocalization in the positively charged film, but poor delocalization in the negatively charged film, and although pDEQ is reducible, it more closely resembles a redox couple than an ambipolar pseudocapacitative material. pDDDBT was designed with two electron acceptor heterocycles per monomeric unit to increase electron delocalization along the polymer backbone and to better match the amount of positive and negative capacitance of the material. The cyclic voltammogram of pDDDBT reveals several interesting results. First, the reduction onset of the DDDBT monomer is increased relative to DEQ. However, in contrast to a large stabilization (ca. 600 mV) of the HOMO energy level upon polymerization, there is almost no LUMO level stabilization. On the other hand, the dual acceptor units result in multiple reduction processes over a wide potential range.

Taken together it is clear that the width of the positive charging range decreases with increasing acceptor concentration. For pEDOT, pDEQ, and pDDDBT the positive charging range is 1400 mV, 980 mV, and 840 mV, respectively. This reduces the capacitive contribution of the positive electroactive range to the device. However, introducing two acceptor moieties in pDDDBT causes this capacitance in the negative electroactive range to more closely match the positive range. Finally, the voltage from the edge of the positive charging range to the edge of the negative charging range is 2.9 V and 3.2 V for pDEQ and pDDDBT, respectively. This will equate to a device that has a higher operating voltage than pEDOT.

Supercapacitors composed of conjugated polymers are fabricated in four configurations, termed Types l-IV.^15,33 Here, Type I and Type I II supercapacitors were examined. Types I and III are referred to as symmetric devices because both electrodes are composed of the same material. In a Type I device, both electrodes operate in one voltage range, either the positive or negative electrochemically active voltage range of the material, but not both. As p-type conjugated polymers are the most common, Type I conjugated polymer devices are most commonly operated in the positive charging potential range. In this configuration, the negative electrode operates in the lower half of the potential range while the positive electrode operates in the higher half of the potential range. When the device is discharged, the chemical potential across the device is zero and both electrodes retain the same partial positive charge. When the device is charged the positive electrode becomes fully positively charged and the negative electrode is neutral. The cell voltage of a Type I pEDOT device is limited to 1 .4 V, the difference between the fully charged and fully discharged potential.

In a Type III device, the positive electrode is operated in the positive charging range, while the negative electrode is operated in the negative charging range. When the device is discharged, both electrodes are neutral and the cell voltage is zero. Charging the device causes the positive electrode to become positively charged and the negative electrode to be negatively charged. A cell voltage that is higher than what can be achieved in a Type I device is thus possible. These two different operating mechanisms are illustrated on the device cyclic voltammograms by the symbols of Figure 5.

Type I II supercapacitors were fabricated using pDEQ and pDDDBT as the charge storage material and Type I devices were made using pEDOT to illustrate the differences in electrode materials and device performance. Briefly, each device was fabricated by polymerizing monomers using cyclic voltammetry on two platinum button electrodes. The cyclic voltammogram of the polymer in a three-electrode cell is used as a guide for conditioning the electrodes prior to device fabrication. First, the operating voltage of the device is determined (2.5 V) and then the electrodes are charged to the midpoint of the operating voltage range (-0.80 V, -0.51 V, and 0.30 V vs. Ag/AgN0₃ for the pDEQ, pDDDBT, and pEDOT devices respectively). This allows for the best overlap of the positive and negative electroactive regimes. The electrodes were rinsed in monomer free electrolyte solution and then coated with a polymethylmethacrylate/TBA⁺PF₆7acetonitrile electrolyte. One electrode was placed into one end of a custom made Teflon casing (Figure 6), a porous paper disk separator was placed on top of the gel coated electrode, and the second electrode coated with polymer electrolyte was inserted to create a sandwich-type device.

The performance of the Type III pDEQ and pDDDBT devices were measured over 2.5 V and the Type I pEDOT device was measured over 1 .4 V (Figure 5). Devices were cycled at various scan rates (50 mV s^"1 to 5 V s^"1). From the cyclic voltammogram it is apparent that the Type III devices only exhibit pseudocapacitance at potentials above 1 .5 V. However, due to the energy-voltage relationship (Equation 3) 75% of the energy in a capacitor is stored in the highest 50% of the operating voltage. This is advantageous because the vast majority of the charge on the devices is extracted at potentials above 1 .5 V. The current of the pDEQ device begins to diminish after 2.0 V, whereas the pDDDBT has a broader current profile up to 2.5 V. This is due to better capacitance matching of the negative and positive electrode. Peak capacitance measured from the discharge scan is plotted as a function of scan rate (Figure 5). The device electrodes exhibit excellent capacitance even at scan rates as high as 5 V s^"1 with a maximum value of 201 F g^"1 and 91 F g^"1 (obtained at 100 and 50 mV s^"1) for the pDEQ and pDDDBT devices respectively.

Charge-discharge measurements were performed on the devices at current densities of 0.2-50 A g^"1 (the 1 A g^"1 measurements are presented). The typical triangular charge-discharge curve is observed for the Type I pEDOT device.

However, for both Type I II devices, the shape is different due to the initial, fast, non- Faradaic charging at potentials too low for pseudocapacitance. This causes the potential of the Type-Ill device to increase sharply, followed by a more gradual increase in potential as the pseudocapacitative charging of the electrodes takes place. The pEDOT and pDDDBT devices are nearly symmetric upon

charging/discharging, however the pDEQ device is not. The cycling efficiency, as measured by the difference in area of the charging and discharging curve (measured

I A g^"1), is 98% for pEDOT, 38% for pDEQ and 60% for pDDDBT, again

demonstrating that adjacent electron acceptors improves device performance.

The specific energy and power for the devices are extracted from the charge/discharge plots and both exceed the specific energy of pEDOT (Figure 7, Table Three). The specific energy and specific power of the pDEQ device are

I I Wh kg^"1 (at 0.5 A g^"1) and 20 kW kg^"1 (at 50 A g^"1 with a specific energy of 3.6 Wh kg^"1) respectively. For the pDDDBT device the values are 4.8 Wh kg^"1 (at 0.5 A g^"1) and 55 kW kg^"1 (at 50 A g^"1 with a specific energy of 0.76 Wh kg^"1) respectively. The mass of the active layers was estimated by the charge passed during

electrochemical deposition. It was assumed that the deposition is 100 % efficient, however, the coulombic efficiency of electrochemical polymerization can be as low as 16 %, ' which means that these values are likely an underestimation of the true values. The volumetric performance is reported for the pDEQ and pDDDBT devices as their respective polymerization efficiencies are likely different. The energy and power density of the pDEQ device are 0.84 Wh L^"1 (at 0.5 A g^"1) and 1 .5 kW L^"1 (at 50 A g^"1 with an energy density of 0.28 Wh L^"1) respectively. For the pDDDBT device the values are 1 .0 Wh L^"1 (at 0.5 A g^"1) and 12 kW L^"1 (at 50 A g^"1 with an energy density of 0.16 Wh L^"1) respectively. Thus, on a volumetric scale, pDDDBT was found to perform slightly better than pDEQ.

TABLE THREE

Performance metrics of the supercapacitor devices

Peak Specific Specific Energy Power Capacitance Energy Power Density Density

Material [F g^"1]^a) [Wh kg^' [kW kg^"1]^c) [Wh L^"1]^d) [kW L^"1]^d) pEDOT 49 2.8 31

pDEQ 201 1 1 20 0.84 1 .5 pDDDBT 91 4.8 55 1 .0 12 ^a> Peak capacitance of an individual electrode;

b⁾ Specific energy calculated by integrating the area under the discharge curve multiplying by the current density (at 0.5 A g^"1);

c⁾ Specific power was calculated by dividing the specific energy by discharge time (at 50 A g-¹);

d⁾ Energy and power density values were calculated by measuring the thickness of the polymer layer from electron microscopy images and the area of the electrode

Theoretical Modeling

Capacitance matching of the positive and negative charging ranges is important for materials for Type III supercapacitors. It is also important that there be charge derealization in both the oxidized and reduced state of the polymer. The extent of charge derealization across the polymers was examined using

computational chemistry. Geometry optimizations (density functional theory) of model oligomers with twelve aromatic moieties were performed on pEDOT, pDEQ, and pDDDBT, as well as a hypothetical block copolymer version of pDDDBT (EDOT- J -BT; six monomers per block). Of interest is how the bond lengths along backbone of the polymer change in the +1 and -1 oxidation and reduction states, relative to the neutral ground states. Smaller bond length changes (in the +1 or -1 state compared to the ground state) that are spread over several repeat units indicate that the charge (positive or negative) is also spread over multiple repeat units and are thus indicative of the derealization of the oxidized or reduced form. Larger bond length changes that are isolated are indicative of greater localization. For clarity, only the bond length changes to the acetylene backbone are shown (Figure 7). The calculated HOMO and LUMO orbital distributions for the neutral polymer are presented with the + 1 and -1 bond length change plots respectively.

The block copolymer, EDOT-J -BT, can be generally represented by the formula (C):

in which R¹ and R² together form -CH₂CH₂-, R³ and R⁴ together form -CH₂CH₂-, R⁵ and R⁶ are each hydrogen, X is -CHCH-, Z is a sulfur atom (S), n=6, and p=3.

For pEDOT, the bond length change in the +1 singlet state is spread over many repeat units (Figure 9), which can be interpreted as a great deal of charge derealization across the model. The models for pDEQ and pDDDBT show more significant localization of the charges in both the +1 and -1 states. It is apparent that the positive charge resides mostly on the electron rich heterocycles where the negative charge resides on the electron deficient heterocycles. This reinforces the hypothesis that derealization of charge carriers in donor-acceptor copolymers is not as great as in the homopolymer pEDOT. Further, based on the model compounds, there is greater localization of both positive and negative charge when the number of acceptors is increased, as predicted for the in pDDDBT model where the negative charges are spread over two adjacent acceptor units. Considering all bond lengths (Figures 9 - 15) shows identical trends.

Experimental Section

Reagents were purchased from Sigma-Aldrich and used as received unless otherwise noted. THF, DMF, dichloromethane, and acetonitrile were purified and dried using an Innovative Technology Pure Solv system. All electrochemical experiments were performed in an Innovative Technology Pure Lab nitrogen filled glove box using a BioLogic SP-200 potentiostat. Acetonitrile and dichloromethane used for electrochemistry were stored over molecular sieves in the glove box. 2- (tributylstannyl)-3,4-(ethylenedioxy)thiophene was prepared according to a literature procedure. ³⁶

Synthesis

5, 8-bis(2, 3-dihydrothieno[3, 4-b][1 ,4]dioxin-5-yl)quinoxaline (DEQ) :

Stille-type coupling procedure (adapted from Durmus et al.²⁴)

5,8-Dibromoquinoxaline (0.513 g, 1 .78 mmol) was added to a dry 3-neck flask fitted with a condenser, a rubber septum, and a glass plug, under a nitrogen atmosphere. Anhydrous THF (100 ml_) and 2-(tributylstannyl)-3,4- (ethylenedioxy)thiophene (2.3 g, 5.3 mmol) were added to the flask. The solution was deoxygenated with bubbling nitrogen for 30 min. PdCl₂(PPh₃)₂ (0.1 18 g, 0.176 mmol) was suspended in a small amount of THF and added to the reaction mixture by a syringe. The mixture was heated to reflux for 36 hours where it turned from light yellow to dark orange/red as the reaction proceeded. The mixture was allowed to cool and the solvent was removed under vacuum to yield a red solid. Column chromatography on silica gel (3: 1 dichloromethane:hexanes) afforded the desired product, a bright orange solid (0.240 g, 33%).

Direct heteroarylation method

A 10 ml_ Shlenk flask was flame dried under vacuum and backfilled with nitrogen three times. 5,8-Dibromoquinoxaline (0.432 g, 1 .50 mmol), palladium (II) acetate (0.034 g, 0.15 mmol), pivalic acid (0.046 g, 0.45 mmol), and potassium carbonate (0.621 g, 4.5 mmol) were added to the flask under a nitrogen atmosphere. DMA (3 mL) and 3,4-(ethylenedioxy)thiophene (0.80 mL, 7.5 mmol) were added to the flask by syringe. The mixture darkened quickly and an orange solid appeared. The mixture was allowed to stir at 100 °C for 70 minutes and then left to cool to room temperature. The mixture was diluted with dichloromethane, washed with water (3X), brine, and the organic phase was separated, dried over MgS0₄, and filtered. The solvent was evaporated to yield the crude product, which was subsequently purified by column chromatography on silica gel (dichloromethane) to yield a bright orange solid (0.268 g, 44%).

¹H NMR (400 MHz, CDCI₃, δ): 8.94 (s, 2H), 8.57 (s, 2H), 6.56 (s, 2H), 4.39-4.29 (m, 8H); HRMS (DART) m/z: [M + H]⁺ calcd for C₂oHi5N₂0₄S2, 41 1 .04732; found, 41 1 .04746.

2-(2, 3-dihydrothieno[3,4-b][ 1 , 4 ]dioxin-5-yl)-4, 4, 5, 5-tetramethyl-1 , 3, 2-dioxaborolane (1):

Synthesized as previously reported.^{37 1}H NMR (400 MHz, CDCI₃, δ): 6.62 (s, 1 H), 4.35-4.13 (m, 4H), 1 .34 (s, 12H).

5-bromo-8-(2,3-dihydrothieno[3,4-b][1 ,4]dioxin-5-yl)quinoxaline (2):

5,8-Dibromoquinoxaline (1 .00 g, 3.47 mmol) and 1 (1 .33 g, 3.47 mmol) were added to a flame-dried, 250 mL 3-neck flask equipped with a condenser under an argon atmosphere. Toluene (140 mL) and water (8 mL) were added and the solution was degassed by three freeze-pump-thaw cycles. Potassium carbonate (1 .08 g, 7.81 mmol), tetrakis(triphenylphosphine)palladium(0) (0.200 g, 0.173 mmol), and Aliquat 336 (0.4 mL) were added to the flask and the reaction mixture was allowed to stir at 84 °C for 64 hours. The solution was diluted with dichloromethane and washed with water three times. The aqueous phase was extracted with dichloromethane. The combined organic phases were washed with brine, dried over magnesium sulfate, filtered, and concentrated. The crude product was purified by column

chromatography on silica gel (dichloromethane) to yield the title compound (0.105 g, 9% yield). ¹ H NMR (400 MHz, CDCI₃, δ): 8.99 (d, J = 1 .8 Hz, 1 H), 8.94 (d, J = 1 .7 Hz, 1 H), 8.44 (d, J = 8.3 Hz, 1 H), 8.10 (d, J = 8.3 Hz, 1 H), 6.59 (s, 1 H), 4.40-4.28 (m, 4H); HRMS (DART) m/z: [M + H]⁺ calcd for Ci₄H₁₀ Br₁ N₂0₂Si, 348.96464; found, 348.96579.

8,8'-bis(2,3-dihydrothieno[3,4-b][1,4]dioxin-5-yl)-5,5'-biquinoxaline (DEDQ) Potassium carbonate (0.081 g, 0.59 mmol) and 2 (0.068 g, 0.20 mmol) were added to a flame dried 10 mL Shienk flask under an nitrogen atmosphere. The flask was transferred into a nitrogen filled glove box and 1 , 1 '- bis(diphenylphosphino)ferrocene-palladium(ll)dichloride (0.0044 g, 0.006 mmol) and bis(pinacolato)diboron (0.027 g, 0.1 1 mmol) was added to the flask. The flask was removed from the glove box and dry DMF (1 .2 mL) was added. The mixture was stirred at 90 °C for 26 h, cooled to room temperature, diluted with methanol, and the solids were collected on a glass frit. The solids were washed with methanol, followed by water, allowed to dry on the frit, collected, suspended in dichloromethane, and washed by three centrifugation/resuspension cycles to yield the title compound

(0.027 g, 52 %). ¹H NMR (500 MHz, CD₂CI₂, δ): 8.87 (d, J = 1 .6 Hz, 2H), 8.69 (d, J = 1 .6 Hz, 2H), 8.66 (d, J = 1.1 Hz, 2H), 7.91 (d, J = 1.1 Hz, 2H), 6.59 (s, 2H), 4.43- 4.30 (m, 8H); HRMS (DART) m/z: [M + H]⁺ calcd for C₂₈H₁₉N₄0₄S₂, 539.08477; found, 539.08347.

2-(3, 4-dimethoxythiophen-2-yl)-4, 4, 5, 5-tetramethyl-1 ,3, 2-dioxaborolane (3) :

Prepared in an analogous manner as 1 using 3,4-dimethoxythiophene (4.975 g, 34.50 mmol) to give a mixture of 3,4-dimethoxythiophene and the title compound

(10 g, 89% crude yield), which was used in the next step without further purification.

¹H NMR (400 MHz, CDCI₃, δ): 6.46 (s, 1 H), 4.00 (s, 3 H), 3.82 (s, 3 H), 1 .31 (s, 12 H); ¹³C NMR (100 MHz, CDCI₃, δ): 154.62, 150.58, 147.82, 103.27, 96.29, 83.97,

61 .34, 57.72, 24.66; HRMS (DART) m/z: [M + H]⁺ calcd for Ci₂H₂₀BiO₄Si ,

217.1 1753; found, 271 .1 1666.

5-bromo-8-(3,4-dimethoxythiophen-2-yl)quinoxaline (4):

Prepared in an analogous manner as 2 using 3 (0.619 g, 2.29 mmol) and excess 5,8-dibromoquinoxaline (1 .980 g, 6.876 mmol). Column chromatography on silica gel (dichloromethane) allowed for recovery of the excess 5,8- dibromoquinoxaline and isolation of the title compound (0.416 g, 52%). ¹H NMR (400 MHz, CDC , δ): 8.99 (d, J = 1 .7 Hz, 1 H), 8.95 (d, J = 1 .8 Hz, 1 H), 8.19 (d, J = 8.1 Hz, 1 H), 8.14 (d, 1 H), 6.42 (s, 1 H), 3.91 (s, 3H), 3.79 (s, 3H); ¹³C NMR (101 MHz, CDCI₃, δ): 150.65, 145.69, 145.28, 144.41 , 141 .70, 140.85, 133.66, 132.36, 130.90,

123.06, 1 19.30, 98.80, 60.36, 57.43; HRMS (DART) m/z: [M + H]⁺ calcd for

, 350.98029; found, 350.97989. 8,8'-bis(3,4-dimethoxythiophen-2-yl)-5,5'-biquinoxaline (DDDQ): Prepared in an analogous manner to DEDQ using 4. The compound was purified by Soxhilet extraction (hexanes, dichloromethane) through a glass frit. The title compound was isolated by concentrating the dichloromethane extracts (0.340 g, 53%). ¹ H NMR (400 MHz, CDC , δ): 8.91 (d, J = 1 .7 Hz, 2H), 8.73 (d, J = 1 .7 Hz, 2H), 8.41 (d, J = 7.6 Hz, 2H), 7.94 (d, J = 7.6 Hz, 2H), 6.44 (s, 2H), 3.94 (s, 6H), 3.88 (s, 6H); ¹³C NMR (101 MHz, CDCb, δ): 150.67, 145.52, 144.36, 143.75, 142.34, 140.85, 137.55, 132.52, 132.20, 130.28, 120.37, 98.40, 60.52, 57.42; HRMS (DART) m/z: [M + H]⁺ calcd for C₂8H23N₄0₄S₂, 543.1 1607; found, 543.1 1697.

4-bromo-7-(3,4-dimethoxythiophen-2-yl)benzo[c][1,2,5]thiadiazole (5):

Prepared in an analogous manner as 2 using 4,7- dibromobenzo[c][1 ,2,5]thiadiazole (0.979 g, 3.33 mmol) and 3 (1 .00 g, 3.33 mmol). Column chromatography on silica gel (dichloromethane:hexanes 8:2) followed by trituration with methanol afforded the title compound (0.262 g, 22%).

1H NMR (600 MHz, CDCI₃, δ): 8.17 (d, J = 7.8 Hz, 1 H), 7.88 (d, J = 7.8 Hz, 1 H), 6.44 (s, 1 H), 3.91 (s, 3 H), 3.89 (s, 3 H). ¹³C NMR (126 MHz, CDCb, δ): 153.50, 152.34, 150.89, 132.50, 127.79, 125.76, 1 19.74, 1 12.14, 98.56, 60.12, 57.34; HRMS (DART) m/z: [M + H]⁺ calcd for Ci₂H₁oBr₁N₂0₂S₂, 356.93717; found, 356.93735.

7, 7'-bis(3, 4-dimethoxythiophen-2-yl)-4, 4 '-bibenzo[c][1 ,2, 5]thiadiazole (DDDBT)

Prepared in an analogous manner as DEDQ using 5. The product was purified by Soxhlet extraction (hexanes, dichloromethane) through a glass frit. The title compound was isolated by concentrating the dichloromethane extracts (0.219 g, 56%). ¹H NMR (500 MHz, CDCb, δ): 8.50 (d, J = 7.7 Hz, 2H), 8.45 (d, J = 7.6 Hz, 2H), 6.46 (s, 2H), 3.96 (s, 6H), 3.94 (s, 6H); ¹³C NMR (126 MHz, CDCI₃, δ): 154.00, 153.39, 151 .10, 145.91 , 131 .58, 128.22, 127.67, 126.22, 120.72, 98.62, 60.43, 57.50; HRMS (DART) m/z: [M + H]⁺ calcd for C₂₄H₁₉N₄0₄S₄, 555.02891 ; found, 555.02843.

2,5-diphenyl-oxadiazole (DPODA):

Synthesized as previously reported.^{38 1} H NMR (400 MHz, CDCI₃, δ): 8.18- 8.13 (m, 4H), 7.61 -7.48 (m, 6H); ¹³C NMR (101 MHz, CDCI₃, δ): 164.74, 131 .86, 129.23, 127.09, 124.12; HRMS (DART) m/z: [M + H]⁺ calcd for Ci₄Hn N₂0i ,

223.08714; found, 223.08756. Electrochemical Polymerization and Measurement

Electrochemical polymerization was performed in a standard 3-electrode electrochemical cell with a platinum disk working electrode (2 mm diameter), a platinum wire counter electrode, and a Ag/AgN0₃ reference electrode containing 0.1 M tetrabutyl ammonium hexafluorophosphate (TBAPF₆) and 0.01 M AgNC>3 in acetonitrile. The polymerization solution contained 5 mM of the appropriate monomer and 0.1 M TBAPF₆ in dichloromethane. Deposition was stopped when the charge required to deposit 3.5-4 μg of material had passed, ca. 30 cycles for the donor- acceptor monomers and 50 cycles for EDOT. Electrochemical measurements on polymer films were performed in a 3-electrode cell in acetonitrile with 0.1 M TBAPF₆.

Polymer Electrolyte Preparation

The polymer electrolyte was prepared in a nitrogen filled glove box by first making a solution of 1 M TBAPF₆ in acetonitrile. Polymethyl methacrylate (10% by weight; relative to the acetonitrile solvent) was added in small portions with stirring, waiting for each portion to fully dissolve before further addition. As the viscosity increased the solution was heated slightly to facilitate polymer dissolution.

Device Fabrication

After electrochemical polymerization, polymer coated electrodes were rinsed twice in dichloromethane/0.1 M TBAPF₆ and twice in acetonitrile/0.1 M TBAPF₆. The electrodes were then held at the midpoint of the operating voltage of the polymers vs. Ag/AgNOs (0.30 V for pEDOT, -0.80 V for DEQ, and -0.51 V for pDDDBT) until the current decayed to zero (2 minutes). One electrode was inserted into a Teflon casing and coated with the gel electrolyte. An oven dried paper circle cut from a Kimwipe was wetted with 0.1 M TBAPF₆ in acetonitrile and placed on top of the polymer electrolyte-coated electrode. A second electrode was coated with the polymer electrolyte and pressed against the first within the Teflon casing with the paper separator held in between each electrode. The polymer electrolyte is highly viscous and will not leak from the device. Device Characterization

The mass of the polymer films was determined by the amount of charge passed during film formation. The total mass of both polymer electrodes was used to calculate specific energy and specific power. Energy was calculated by integrating the area under the charge cycle of the charge-discharge curve and multiplying by the current density. Power was calculated by dividing the energy by the charging time. Specific capacitance of the electrodes was determined by multiplying the current peak of the discharge CV scan of the device by the scan rate (a correction factor 4 was used to account for the series connection and the mass difference between the device and a single electrode). Electron microscopy was performed using a Quanta FEG 250 ESEM.

Computational Methods

The geometries of the oligomers 12 rings long of pEDOT, pDEQ, and

pDDDBT, as well as a block copolymer version of pDDDBT (EDOT-J -BT) were optimized with the nonlocal hybrid Becke three-parameter Lee-Yang-Parr³⁹ with Handy and coworkers' long range corrected version using the Coulomb-attenuating method (CAM-B3LYP)⁴⁰ functional and the 6-31 1 g(d) basis set on the Gaussian 09 suit of programs.^{41 ,42} The geometry of oxidized and reduced versions of each oligomer was optimized with the same basis set and level of theory (+ 1 doublet, +2 singlet, -1 doublet, and -2 singlet). Cartesian coordinates for optimized geometries for model compounds using CAM-B3LYP 6-31 1 g(d) are listed Tables Four to

Sixteen. The frontier orbitals are visualized with an isocontour value of 0.03. Bond length change plots were made by taking difference of the optimized bond lengths of the neutral geometry and the oxidized or reduced geometries. The plots show the bond length change down the conjugated back bone, and are indicative of the changes seen if all bonds are considered. TABLE FOUR TABLE FOUR (con't)

DDDQ monomer DDDQ monomer

X Y Z X Y Z

c -5.8401620 -1 .6714410 1.0547420 c -6.2354580 5.9669310 -2.2594500 c -7.1561 160 -1 .5034620 0.7467440 c -5.5835760 6.2414960 -3.4480130 c -7.4153840 -0.2383560 0.1298230 c -6.9441970 7.0500950 -1 .6501620 c -6.2919210 0.5587160 -0.0268920 c -5.6262860 7.4990760 -4.0700050 s -4.8825280 -0.3129340 0.5783750 H -5.0142660 5.4561720 -3.9280060

H -5.3819760 -2.5398980 1.5046360 C -6.9816710 8.3402120 -2.2794690

0 -8.6874830 0.1227760 -0.2380140 N -7.5583040 6.8595850 -0.4514870

0 -8.1256890 -2.4506720 0.9532920 H -5.0943840 7.6298530 -5.0005890

C -9.1948620 -0.5803960 -1 .3835380 C -6.3290420 8.5741780 -3.5364460

H -9.2072990 -1 .6567870 -1 .2034120 N -7.6296830 9.3669720 -1 .6784280

H -10.2110700 -0.2183020 -1 .5356120 C -8.1751750 7.8808440 0.0945980

H -8.5894850 -0.3585130 -2.2673300 C -8.2124300 9.1502970 -0.5234810

C -9.0463220 -2.1380770 2.0060200 H -8.6582470 7.7164170 1.0555250

H -9.7488690 -2.9696540 2.0517850 H -8.7251940 9.9873660 -0.0550860

H -8.5206910 -2.0511290 2.9624770 C -6.3797520 9.8663600 -4.2289320

H -9.5848710 -1 .2102550 1.7986650 C -6.0213400 10.1344170 -5.5409010

C -6.2342560 1.9255060 -0.5563310 S -6.8730470 1 1 .3709840 -3.4512500

C -7.3877500 2.6872310 -0.7103210 C -6.1 110150 1 1 .5160930 -5.9033190

C -5.0037990 2.5604210 -0.9353690 O -5.5912770 9.1923810 -6.4419500

C -7.3696230 3.9861350 -1 .2418690 C -6.5406680 12.2967720 -4.8733500

H -8.3371250 2.2666050 -0.4144530 O -5.8379500 1 1 .9801210 -7.1642650

C -4.9894300 3.8849940 -1 .4894760 C -6.5372650 8.8934400 -7.4809360

N -3.8395710 1.8931210 -0.7490690 H -6.7121940 13.3629690 -4.8913200

H -8.3110860 4.5128040 -1 .3285010 C -4.4455990 1 1 .9917550 -7.5029180

C -6.2092800 4.6132270 -1 .6580380 H -6.7862070 9.7919320 -8.0484340

N -3.8082190 4.4681420 -1 .8282940 H -6.0529620 8.1663530 -8.1318980

C -2.7176320 2.4833460 -1 .0856570 H -7.4465350 8.4583970 -7.0557860

C -2.7048620 3.7854150 -1 .6327000 H -4.3836010 12.3759200 -8.5206430

H -1.7931960 1.9331780 -0.9253180 H -3.8917750 12.6532400 -6.8288140

H -1.7666350 4.2651490 -1 .9035020 H -4.0198930 10.9863950 -7.4605210

TABLE FIVE TABLE FIVE (cont'd)

DDDBT monomer DDDBT monomer

X Y Z X Y Z

C -5.8015690 -1 .7041560 1 .0381700 C -5.5357170 6.2727330 -3.4449830

C -7.1398180 -1 .5321990 0.8359210 C -7.1676700 6.9604220 -1 .8570720

C -7.4448850 -0.2822100 0.2079290 C -5.5649710 7.5494100 -4.0574520

C -6.3310350 0.4997990 -0.0522720 H -4.8550630 5.5424070 -3.8595870

S -4.8838560 -0.3591550 0.4633920 C -7.1920920 8.2776170 -2.4821210

H -5.3096340 -2.5611910 1 .4738520 N -7.9778880 6.8773450 -0.7985000

0 -8.7321 110 0.0921030 -0.0736780 H -4.9144400 7.7157700 -4.9044730

0 -8.0921970 -2.4670780 1 .1471030 C -6.3796150 8.5835780 -3.6290830

C -9.3431450 -0.6276330 -1 .1578820 N -8.0168180 9.1308540 -1 .8754040

H -9.3464200 -1 .7011550 -0.9598680 C -6.3999240 9.8861980 -4.2871690

H -10.3660320 -0.2597310 -1 .2270070 C -5.9617650 10.2031450 -5.5627340

H -8.8143170 -0.4224350 -2.0932570 S -6.9667680 11 .3474470 -3.4867120

C -8.8770420 -2.1566790 2.3063970 C -6.0530150 11 .5973730 -5.8756410

H -9.5974450 -2.9669890 2.41 18390 O -5.4581590 9.2919080 -6.4530130

H -8.2424910 -2.1122100 3.1971330 C -6.5709330 12.3318260 -4.8490790

H -9.4039210 -1 .2071090 2.1829100 O -5.7043220 12.1 174600 -7.0944790

C -6.2905790 1.8456570 -0.6156260 C -6.3182470 9.0054780 -7.5689510

C -7.3954960 2.6798290 -0.6251210 H -6.7597470 13.3950390 -4.8343040

C -5.1006070 2.4124580 -1 .1922120 C -4.2916990 12.2196600 -7.3186450

C -7.3854510 3.9843300 -1 .1767350 H -6.5492230 9.9152920 -8.1263100

H -8.3198770 2.3241380 -0.1922250 H -5.7700140 8.3104650 -8.2036610

C -5.0931830 3.7523270 -1 .7673640 H -7.2433910 8.5357360 -7.2223120

N -3.9139930 1.8089000 -1 .2534080 H -4.1717410 12.6224710 -8.3236500

H -8.3052120 4.5497120 -1 .1225550 H -3.8379650 12.9025860 -6.5935220

C -6.2798490 4.5678940 -1 .7671720 H -3.8105830 11 .2405970 -7.2525940

N -3.8937200 4.1044480 -2.2377800 S -8.7011250 8.3363180 -0.6168310

C -6.3137940 5.9154510 -2.3594450 S -2.8737830 2.8495800 -1 .9735630

TABLE SIX TABLE SIX (cont'd)

pEDOT neutral pEDOT neutral

X Y Z X Y Z

c -3.8907050 -3.7681740 1 .3384470 c 1.9669360 10.8959050 -4.0174970 s -2.2129280 -3.4352410 1 .1057920 c 7.0460160 1 1.5044030 -4.3314070 c -4.6552800 -2.6874610 1 .0542210 c 2.7587500 12.1538820 -3.7320640 c -2.5367050 -1.7903500 0.6102360 c 8.3906160 1 1.2609790 -4.3861600 c -3.8844990 -1.5624410 0.6397500 s 6.7250880 13.1592950 -4.7997480

0 -6.0128890 -2.6376500 1 .1589100 c 9.1613240 12.3763070 -4.7942060 c -1.4916540 -0.8637030 0.2454130 0 8.9559730 10.0557770 -4.0922780

0 -4.4591750 -0.3761400 0.2932040 c 8.4219440 13.4949730 -5.0624180 c -6.5714810 -1.5297490 0.4617730 0 10.5200010 12.3241 190 -4.8919740 c -0.1461290 -1.0982460 0.2177000 c 10.3566200 10.1504520 -3.8589670 s -1.8164780 0.7873420 -0.2292210 c 8.9008050 14.7794360 -5.5060220 c -5.7986880 -0.2633810 0.7617760 c 1 1.0148980 10.9904790 -4.9322770 c 0.6250940 0.0225290 -0.1766720 s 10.5955270 15.1078780 -5.7910170

0 0.4207490 -2.2992380 0.5242640 c 8.1614390 15.8975880 -5.7764400 c -0.1 175270 1 .1349270 -0.4597740 c 10.2735920 16.7585180 -6.2732940

0 1.9855510 -0.0213880 -0.2486210 c 8.9301930 17.0056780 -6.2073720 c 1.8178900 -2.1973590 0.7793700 0 6.8070510 15.9633740 -5.6360600 c 0.3598780 2.4226960 -0.8969520 c 1 1.3176580 17.6728000 -6.6606580 c 2.4883360 -1.3524340 -0.2823860 0 8.3617090 18.2004890 -6.5356510 c -0.3824650 3.5354890 -1 .1798220 c 6.2392540 17.0753030 -6.3190230 s 2.0564450 2.7612730 -1 .1569830 c 12.6613760 17.4266700 -6.7243450 c 0.3856530 4.6479460 -1 .6010740 s 10.9975650 19.3302300 -7.1202970

0 -1.7390290 3.5926190 -1 .0598080 c 7.0356020 18.3309910 -6.0361620 c 1.7312990 4.4089040 -1 .6467510 c 13.4321390 18.5421 170 -7.1320460

0 -0.1856460 5.8385350 -1 .9398000 0 13.2258910 16.2190610 -6.4386480 c -2.3041020 4.7010250 -1 .7511980 c 12.6936290 19.6635170 -7.3910400 c 2.7755980 5.3280880 -2.0220030 0 14.7901010 18.4875960 -7.2376360 c -1.5190870 5.9615590 -1 .4584400 c 14.6278280 16.3102390 -6.2120500 c 4.1213530 5.0890430 -2.0652350 c 13.1726220 20.9493250 -7.8306380 s 2.4531 140 6.9816510 -2.4939860 c 15.2822170 17.1531 120 -7.2855090 c 4.8917680 6.2065810 -2.4677760 c 12.4337890 22.0700260 -8.0918160

0 4.6880390 3.8859720 -1 .7657830 s 14.8665880 21.2766440 -8.1210510 c 4.1509200 7.3225580 -2.7430390 c 13.2024690 23.1793290 -8.5197450

0 6.2513360 6.1585850 -2.5545720 0 1 1.0801180 22.1372220 -7.9454050 c 6.0867470 3.9848070 -1 .5220990 c 14.5451490 22.9304850 -8.5925680 c 4.6292580 8.6078350 -3.1849070 0 12.6346860 24.3768340 -8.8387870 c 6.7505610 4.8264500 -2.5907010 c 10.51 13400 23.2533960 -8.6205700 c 3.8887940 9.7237030 -3.4616280 c 15.5888830 23.8459980 -8.9782390 s 6.3248690 8.9400170 -3.4601220 c 1 1.3103550 24.5065430 -8.3340640 c 4.6574080 10.8329420 -3.8899200 c 16.9318130 23.5983300 -9.0504870

0 2.5334470 9.7862690 -3.3296380 s 15.2689570 25.5075730 -9.4223080 c 6.0017700 10.5888960 -3.9474410 c 17.7022610 24.7162640 -9.4524570

0 4.0878900 12.0257220 -4.2239030 0 17.4961180 22.3876850 -8.7774990 TABLE SIX (cont'd) TABLE SIX (cont'd)

pEDOT neutral pEDOT neutral

X Y Z X Y Z

c 16.9640810 25.8406080 -9.6980780 H 6.4713330 2.9656420 -1 .5284930

0 19.0594910 24.6609090 -9.5650660 H 6.5667140 4.3921660 -3.5792070 c 18.8989820 22.4757410 -8.5555010 H 7.8248250 4.8973900 -2.4246410 c 17.4428710 27.1300480 -10.1287490 H 1.9570670 10.6943430 -5.0939770 c 19.5501140 23.3261590 -9.6249600 H 0.9417770 10.9865320 -3.6604220 c 16.7046660 28.2541590 -10.3747710 H 2.7831070 12.3459500 -2.6540840 s 19.1357540 27.4562950 -10.4259640 H 2.3259960 13.0150000 -4.2398590 c 17.4742680 29.3659670 -10.7967600 H 10.5355560 10.5927610 -2.8731090

0 15.3521210 28.3241240 -10.2205140 H 10.7382400 9.1301890 -3.8685300 c 18.8143020 29.1137950 -10.8797280 H 10.8221920 10.5570940 -5.9194860

0 16.9087960 30.5682500 -1 1.1008060 H 12.0906150 1 1.0581320 -4.7743920 c 14.7834500 29.4466310 -10.8855710 H 6.2227930 16.8754190 -7.3957450 c 19.8580590 30.0338910 -1 1.2643270 H 5.2163470 17.1677990 -5.9560200 c 15.5852270 30.6962400 -10.5917610 H 7.0664900 18.5213640 -4.9580570 c 21 .2000530 29.7877740 -1 1.3529990 H 6.6020620 19.1939050 -6.5402280 s 19.5420860 31 .7005170 -1 1.6870420 H 14.8126080 16.7484630 -5.2254390 c 21 .9726530 30.9165030 -1 1.7537470 H 15.0075210 15.2893290 -6.2274440

0 21 .7652300 28.5738200 -1 1.0989370 H 15.0835570 16.7239080 -8.2733520 c 21 .2152440 32.0179800 -1 1.9690220 H 16.3588630 17.2181310 -7.1329380

0 23.3282560 30.8602040 -1 1.8785960 H 10.4906760 23.0590820 -9.6982370 c 23.1704620 28.6612380 -10.8881820 H 9.4898940 23.3454090 -8.2533830 c 23.81 17510 29.5237780 -1 1.9538750 H 1 1.3452960 24.6913860 -7.2551410

H -4.2251820 -4.7378430 1 .6706870 H 10.8763190 25.3726110 -8.8322370

H -6.5597900 -1.7276080 -0.6158080 H 19.0879530 22.9061380 -7.5662430

H -7.6047780 -1.4465040 0.79731 10 H 19.2776350 21.4546430 -8.5802540

H -5.7947940 -0.0715730 1 .8401340 H 19.3471700 22.9048570 -10.6152940

H -6.2315900 0.5934750 0.2470750 H 20.6273910 23.3890360 -9.4760820

H 1.9785770 -1.7554200 1 .7684240 H 14.7590620 29.2604720 -1 1.9645780

H 2.2048020 -3.2155940 0.7746630 H 13.7633570 29.5379090 -10.5146130

H 2.3142350 -1.7856340 -1 .2731100 H 15.6235340 30.8729220 -9.51 16650

H 3.5608850 -1.2792050 -0.1068480 H 15.1515820 31.5667940 -1 1.0822870

H -2.3046950 4.5002850 -2.8278460 H 21.5525330 32.9944950 -12.2775170

H -3.3323540 4.7875790 -1 .4021360 H 23.3668180 29.0810390 -9.8957500

H -1.5040170 6.1528920 -0.3801570 H 23.5494720 27.6407570 -10.9267720

H -1.9509220 6.8214820 -1 .9690120 H 23.6001620 29.1100270 -12.9460840

H 6.2569470 4.4278850 -0.5350620 H 24.8909070 29.5804360 -1 1.8144570 TABLE SEVEN TABLE SEVEN (cont'd) pEDOT +1 pEDOT +1

X Y Z X Y Z

c -3.8107970 -3.7098780 1 .3368920 6.7417660 7.00441 10 -3.0444300 s -4.1 156920 -2.0652860 0.9183730 c 6.2503710 10.4782440 -3.9276370 c -2.4918330 -4.0092680 1 .2630550 0 8.3191470 9.2476210 -3.8629930 c -2.4196440 -1.7550150 0.6313840 c 8.1477480 7.0710260 -2.8197260 c -1.6996780 -2.8955680 0.8606450 c 6.7527220 11 .7246260 -4.3444120

0 -1.9478430 -5.2297850 1 .5205430 c 8.8119810 7.9039910 -3.8948450 c -1.9190470 -0.4703510 0.2076770 c 6.0214100 12.8880010 -4.5782850

0 -0.3476960 -2.9729640 0.7328580 s 8.4523600 12.0146950 -4.6636940 c -0.5420750 -5.1628540 1 .7340600 c 6.78911 10 13.9663610 -4.9950650 c -2.6427690 0.6680240 -0.0188270 0 4.6779060 12.9588620 -4.4178750 s -0.2265850 -0.1766600 -0.1037730 c 8.1527230 13.6886570 -5.1065720 c 0.1207220 -4.3188250 0.6670920 0 6.2650320 15.1822330 -5.2671 100 c -1.8607820 1 .7690640 -0.4389330 c 4.1 124200 14.0993580 -5.0646720

0 -3.9912770 0.7562040 0.1490310 c 9.1645100 14.5776770 -5.4934900 c -0.5232850 1 .4922140 -0.5411 100 c 4.9342170 15.3349550 -4.7654360

0 -2.4051360 2.9816470 -0.7221700 s 8.8672750 16.2563160 -5.9201380 c -4.5495220 1 .8880070 -0.5105840 c 10.5300050 14.3038370 -5.5906800 c 0.5258020 2.3940750 -0.9300290 c 10.5693190 16.551 1260 -6.2216510 c -3.7311780 3.1258710 -0.2142870 c 11 .3000020 15.3866940 -5.9911380 c 1 .8662580 2.1 198670 -1.0287640 0 11 .0542810 13.0887490 -5.3156130 s 0.2233630 4.0634640 -1.3438240 c 11 .0712300 17.7953810 -6.6452870 c 2.6472680 3.2247800 -1.4264530 0 12.6437230 15.3161790 -6.1497650

0 2.411 1400 0.8974520 -0.7771880 c 12.4746160 13.1245760 -5.1493860 c 1 .9224930 4.3715250 -1.6423950 c 10.3404070 18.9524760 -6.8882540

0 3.9942830 3.1518440 -1.5695470 s 12.77271 10 18.0955440 -6.9684650 c 3.8144490 0.9672620 -0.5492260 c 13.11 12880 13.9695150 -6.2321440 c 2.4228640 5.6441160 -2.0614980 c 11 .1109100 20.0358270 -7.3108570 c 4.4785250 1 .8085080 -1.6175470 0 9.0010070 19.0227300 -6.7264330 c 1 .6973960 6.7933010 -2.2848960 c 12.4648500 19.7590130 -7.4122950 s 4.1 163310 5.9310800 -2.3785570 0 10.5736660 21 .2516050 -7.5918290 c 2.4746840 7.8844280 -2.7046570 c 8.4249600 20.1884290 -7.3252360

0 0.3498850 6.8797150 -2.1 166990 c 13.4952350 20.6540630 -7.8014640 c 3.8222660 7.6050670 -2.8169030 c 9.2723290 21 .4076960 -7.0316600

0 1 .9427690 9.0980630 -2.9799800 c 14.8456210 20.3800640 -7.8908350 c -0.2063090 8.0029600 -2.7924280 s 13.2036200 22.3306220 -8.2316400 c 4.8518360 8.5005260 -3.2072250 c 15.6259100 21 .4750960 -8.2944850 c 0.6042160 9.2464290 -2.4974250 0 15.3756490 19.1641090 -7.6222090 c 6.2058890 8.2243830 -3.3093210 c 14.9001270 22.6221610 -8.5274980 s 4.5463490 10.171 1760 -3.6251400 0 16.9767800 21 .3948860 -8.4367230 c 6.9788970 9.3151610 -3.7073710 c 16.7982030 19.1926490 -7.4728150

5 TABLE SEVEN (cont'd) TABLE SEVEN (cont'd)

pEDOT +1 pEDOT +1

X Y Z X Y Z

c 15.4001830 23.8908900 -8.9585250 H 4.2784130 1 .3890310 -2.6081220 c 17.4269550 20.0487630 -8.5507520 H 5.5546230 1 .8677690 -1.4621040 c 14.6735410 25.0315570 -9.1990030 H -0.2262770 7.8086930 -3.8696860 s 17.0972270 24.1916130 -9.2760480 H -1.2269310 8.1069790 -2.4280390 c 15.4520930 26.1272600 -9.6260130 H 0.6320300 9.4347770 -1.4203450

0 13.3294920 25.1124680 -9.0337820 H 0.1935460 10.1171550 -3.0057140 c 16.7925520 25.8522120 -9.7221440 H 8.3377120 7.5020660 -1.8317940

0 14.9034560 27.3390200 -9.9177510 H 8.5114580 6.0452900 -2.8399930 c 12.7599950 26.2696030 -9.6486440 H 8.6162260 7.4775600 -4.8825820 c 17.8422790 26.7519410 -10.1142770 H 9.8867600 7.9714310 -3.7366990 c 13.6031320 27.4924900 -9.3594860 H 4.0736880 13.9185920 -6.1429470 c 19.1810120 26.4768900 -10.2045400 H 3.0993870 14.1990390 -4.6795320 s 17.5488140 28.4239890 -10.5416610 H 4.9785710 15.5119380 -3.6871700 c 19.9662230 27.5813460 -10.6093330 H 4.5216150 16.2128020 -5.2589590

0 19.7209690 25.2571660 -9.9444710 H 12.7069730 13.5317460 -4.1613670 c 19.2436920 28.7202510 -10.8369630 H 12.8137040 12.0918610 -5.2035310

0 21 .3188320 27.5007690 -10.7447470 H 12.8726840 13.5662270 -7.2206890 c 21 .1363860 25.3042620 -9.7665260 H 14.1921030 14.0125000 -6.1 117740 c 19.7450940 30.0023850 -11 .2673270 H 8.3452800 20.0305270 -8.4043690 c 21 .7771820 26.1559790 -10.8406620 H 7.4279600 20.2866310 -6.8997090 c 19.0265350 31 .1434560 -11 .4984720 H 9.3578860 21 .5613090 -5.9514090 s 21 .4374600 30.3010500 -11 .5866980 H 8.8456660 22.2988550 -7.4884290 c 19.8172040 32.2489970 -11 .9256090 H 17.0451050 19.5867350 -6.4828180

0 17.6800990 31 .2349210 -11 .3282340 H 17.1311720 18.1585580 -7.5432120 c 21 .1333080 31 .9423800 -12.0182210 H 17.1714010 19.6605180 -9.5419710

0 19.2709530 33.4613290 -12.2149580 H 18.5101360 20.0763430 -8.4448160 c 17.1232230 32.3831040 -11 .9659220 H 12.6890760 26.1054850 -10.7281390 c 17.9619210 33.6088280 -11 .6756710 H 11 .7586340 26.3724290 -9.2334570

H -4.6159850 -4.3703930 1 .6164640 H 13.6842170 27.6503620 -8.2789810

H -0.3391910 -4.7422110 2.7250130 H 13.1737870 28.3808690 -9.8200200

H -0.1783340 -6.1891 170 1 .7018210 H 21 .3636750 25.711 1450 -8.7762140

H -0.0919120 -4.7293250 -0.3253020 H 21 .4845120 24.2738410 -9.8204970

H 1 .1989490 -4.2735570 0.8134770 H 21 .5383890 25.7574710 -11 .8321850

H -4.5811 160 1 .7045520 -1.5896370 H 22.8588090 26.191 1810 -10.7196100

H -5.5663920 1 .9912330 -0.1349070 H 21 .9371150 32.5965940 -12.3159950

H -3.6886510 3.3010800 0.8652530 H 17.0697730 32.2089840 -13.0454760

H -4.1513230 4.0027910 -0.7045640 H 16.1147430 32.4924730 -11 .5696080

H 4.0043320 1 .3933170 0.4414540 H 18.0248550 33.7729360 -10.5943910

H 4.1813570 -0.0576120 -0.5746760 H 17.5351560 34.4940050 -12.1456770 TABLE EIGHT TABLE EIGHT (cont'd)

pDEQ neutral pDEQ neutral

X Y Z X Y Z

c -3.2197470 19.3073750 8.8725830 N 1 .2210200 6.0901910 0.6565130 s -3.8551910 17.8706600 8.1712960 C -0.5852220 3.2376200 -0.8851670 c -1.9056920 19.4650560 8.5939770 N 1 .7399770 3.8020520 -0.8054630 c -2.3029760 17.4243950 7.4918870 C 2.4368680 5.7638740 0.3153920 c -1.3827230 18.3975190 7.8067590 C -0.3447750 2.0086470 -1.6395410

0 -1.1495090 20.5283840 8.9922410 C 2.7010120 4.5994930 -0.4290860 c -2.0558790 16.1900340 6.7427920 C -1.2646460 1 .0257160 -1.9244950

0 -0.0699270 18.3803040 7.4306470 S 1 .1898550 1 .5915410 -2.3753440 c 0.2441900 20.2753560 8.8890120 C -0.7615220 -0.0227620 -2.7330100 c -0.7780450 15.7867880 6.4094560 0 -2.5627610 1 .0242800 -1.4986720 c -3.1084020 15.3221310 6.3184350 C 0.5514380 0.1290060 -3.0819230 c 0.5643590 19.6500860 7.5506990 0 -1.5198640 -1.0920610 -3.1088490 c -0.5100430 14.6226360 5.6765980 C -3.1878790 -0.2508180 -1.6011940 c -2.8373270 14.1400580 5.5738360 C 1 .3481960 -0.7595970 -3.8931230

N -4.3816590 15.6324500 6.6449170 C -2.9131 110 -0.8633660 -2.9550760 c -1.5005060 13.7732780 5.2214610 C 2.6530170 -0.5935720 -4.2652780

N -3.8549270 13.3371830 5.1970500 S 0.7333170 -2.2625620 -4.5326580

C -5.3410920 14.8354260 6.2639750 C 3.1576990 -1.6444210 -5.0695830

C -1.1889830 12.5773860 4.4398990 0 3.4126500 0.4731320 -3.8849160

C -5.0729350 13.6672250 5.5264270 C 2.2452910 -2.6399720 -5.3340390 c 0.0361590 12.2335420 3.9160740 0 4.4436770 -1.6216930 -5.5299880 s -2.3487590 11 .3179810 4.0652230 c 4.5865070 0.6248630 -4.6700320 c 0.0526270 10.9835360 3.2502570 c 2.4567400 -3.8176240 -6.1741010

0 1 .1675300 12.9924840 4.0138960 c 5.2787200 -0.7096400 -4.8244380 c -1.1557080 10.3443050 3.2443310 c 3.5790460 -3.9499490 -6.9699850

0 1 .17191 10 10.4804770 2.6551450 c 1 .5255120 -4.9005840 -6.2372740 c 2.1826920 12.6140620 3.0899060 c 3.8240250 -5.0755200 -7.7664720 c -1.4686440 9.0717510 2.6400020 c 1 .7754660 -6.0456120 -7.0454430 c 2.3645730 11 .1138800 3.0947410 N 0.3843960 -4.8219840 -5.5202370 s -0.2788980 8.1006750 1 .8107250 C 2.9659640 -6.1576740 -7.8296180 c -2.6765720 8.4318590 2.6381170 N 0.8709360 -7.0467300 -7.0868420 c -1.4400200 6.8417720 1 .4382020 C -0.4678040 -5.8073820 -5.5828170 c -2.6626160 7.1834290 1 .9694260 C 3.2627160 -7.3286770 -8.6536900

0 -3.7931670 8.9334210 3.2390820 C -0.2197540 -6.9402530 -6.3795470 c -1.1319990 5.6485650 0.651 1560 C 4.4350760 -7.5850180 -9.3276030

0 -3.7943220 6.4240780 1 .8759140 S 2.1272360 -8.6283970 -8.9608830 c -4.9879660 8.2986320 2.8067240 C 4.4188340 -8.7800660 -10.0875230 c -2.1247930 4.7977970 0.2021620 0 5.5397570 -6.7816410 -9.3062800 c 0.2019090 5.2863480 0.2853170 c 3.2409550 -9.4692180 -10.0092580 c -4.8034920 6.7988060 2.8076230 0 5.4917400 -9.2062400 -10.8133480 c -1.8616020 3.6377350 -0.5369770 c 6.7208730 -7.4322880 -9.7629690 c 0.4693610 4.1076940 -0.4668670 c 2.9171700 -10.7203160 -10.6515040 TABLE EIGHT (cont'd) TABLE EIGHT (cont'd)

pDEQ neutral pDEQ neutral

X Y Z X Y Z

c 6.4453770 -8.1800310 -11 .0468670 H 2.6177850 10.7679000 4.1028380 c 1 .7403240 -11 .41 14130 -10.5734510 H 3.1489990 10.8080300 2.4034500 s 4.0323720 -11 .5591120 -11 .6994210 H -5.7679630 8.6021510 3.5040220 c 1 .7271950 -12.6076960 -11 .3316510 H -5.2486110 8.6459490 1 .8010200

0 0.6657830 -10.9866550 -9.8488590 H -3.1553870 5.0275760 0.4213530 c 2.9004580 -12.8622070 -12.0045530 H -5.7123680 6.2864070 2.4941190

0 0.6250900 -13.4142580 -11 .3521270 H -4.5233990 6.4549550 3.8087890 c -0.2832670 -12.0161430 -9.6121410 H -2.7042230 3.0391850 -0.8452450 c 3.2024690 -14.0360090 -12.8226850 H 3.2410520 6.4259190 0.6248360 c -0.5578600 -12.7672720 -10.8943420 H 3.71561 10 4.3336900 -0.7131560 c 2.3538700 -15.1255070 -12.8742780 H -2.8129950 -0.9069250 -0.8087030 c 4.3905060 -14.1427150 -13.6121700 H -4.2533180 -0.0801510 -1.4507340 c 2.6070260 -16.2559250 -13.6631300 H -3.2690250 -0.1981070 -3.7492920 c 4.6471900 -15.2914660 -14.4120360 H -3.3980110 -1.8335500 -3.0568450

N 5.2855410 -13.1328720 -13.5833430 H 4.3243710 1 .0297820 -5.6535770 c 3.7272980 -16.3834610 -14.4602460 H 5.2181930 1 .3405750 -4.1451890

N 5.7856520 -15.3650560 -15.1348540 H 5.5223200 -1.1229100 -3.8400980

C 6.3737240 -13.2344350 -14.2950610 H 6.1925150 -0.6180010 -5.4105340

C 3.9518150 -17.5699270 -15.2896280 H 4.3082120 -3.1555250 -6.9897090

C 6.6287210 -14.3712980 -15.0843570 H 4.7276310 -5.0838040 -8.3548260 c 3.0654340 -18.59681 10 -15.5196700 H -1.3794720 -5.7218540 -4.9977530 s 5.4493550 -17.9142730 -16.1318020 H -0.9334520 -7.7581440 -6.4289760 c 3.5830460 -19.6455160 -16.3351520 H 7.4623000 -6.6478360 -9.9108220

0 1 .7948160 -18.6564160 -15.0226180 H 7.0780290 -8.1250110 -8.9938300 c 4.8565960 -19.4153090 -16.7279140 H 7.3431370 -8.6722220 -11 .4190270

0 2.8485280 -20.7404740 -16.6851270 H 6.0688960 -7.4914020 -11 .81 11040 c 0.9723430 -19.6032640 -15.6978340 H 0.0969140 -12.7020050 -8.8472000 c 1 .7041090 -20.9155610 -15.8622990 H -1.1825470 -11 .5270060 -9.2396120

H -3.8479500 19.9777520 9.4380510 H -0.9188110 -12.0773160 -11 .6641560

H 0.7420670 21 .2379570 9.0026360 H -1.2959870 -13.5543760 -10.7440550

H 0.5631850 19.6096840 9.6990830 H 1 .4520310 -15.1204700 -12.2830940

H 0.0626330 16.3854500 6.7229280 H 1 .8853900 -17.0570210 -13.6352800

H 1 .6328540 19.4670330 7.4428440 H 7.0799450 -12.4096600 -14.2556560

H 0.2278010 20.3044890 6.7397260 H 7.5385970 -14.4525960 -15.6727460

H 0.5219740 14.3900540 5.4672350 H 5.4661980 -20.0468590 -17.3550830

H -6.3575400 15.1038060 6.5387410 H 0.0789780 -19.7206100 -15.0855160

H -5.8759080 13.0057220 5.2130360 H 0.6873550 -19.2061290 -16.6777560

H 1 .9100450 12.9565480 2.0862540 H 1 .0772510 -21 .6558890 -16.3586360

H 3.0901670 13.1256150 3.4088250 H 2.0055410 -21 .3015530 -14.8818500 TABLE NINE TABLE NINE (cont'd)

pDEQ +1 pDEQ +1

X Y Z X Y Z

c -3.1267010 19.1198990 9.0358970 N 1 .1235510 6.2676170 0.2486060 s -3.7760810 17.7060130 8.3063260 C -0.6397170 3.2700900 -1.0367350 c -1.8098390 19.2718590 8.7649930 N 1 .6278440 4.0074410 -1.2475080 c -2.2266570 17.2591340 7.6191920 C 2.3146850 6.0285480 -0.2339030 c -1.2954610 18.2169930 7.9566310 C -0.3995370 2.0771080 -1.7980370

0 -1.0450620 20.3159530 9.1903040 C 2.5704620 4.8783430 -0.9968670 c -1.9900920 16.0450990 6.8399370 C -1.3179590 1 .0510650 -2.0615560

0 0.0144540 18.1952430 7.5816540 S 1 .1378060 1 .6964990 -2.5529160 c 0.3465970 20.0462370 9.0954270 C -0.8136840 0.0236740 -2.8511450 c -0.7167670 15.6533670 6.4728460 0 -2.5935160 1 .0247260 -1.5957840 c -3.0499370 15.1814000 6.4164250 C 0.5210100 0.1951050 -3.2227530 c 0.671 1720 19.4518540 7.7445940 0 -1.5375020 -1.0490590 -3.2311860 c -0.4617350 14.5061890 5.7103150 C -3.1887700 -0.2714110 -1.6627770 c -2.7900560 14.01591 10 5.6452170 C 1 .2864040 -0.6730950 -4.0142070

N -4.3169270 15.4822650 6.7700840 C -2.9416540 -0.8896120 -3.0187850 c -1.4601 150 13.6637700 5.2602080 C 2.6143460 -0.4904980 -4.4043480

N -3.8110590 13.2144990 5.2734750 S 0.6740120 -2.1813860 -4.6725940

C -5.2820760 14.6903500 6.3930210 C 3.1 178230 -1.5164540 -5.1961680

C -1.1623380 12.4826020 4.4504670 0 3.3333400 0.5897770 -4.0369870

C -5.0238440 13.5350590 5.6315490 C 2.1962540 -2.5372090 -5.4688630 c 0.0564300 12.1514430 3.8972760 0 4.4008860 -1.5021220 -5.6412650 s -2.3338770 11 .2412030 4.0731580 c 4.5443360 0.7447000 -4.7799780 c 0.0599560 10.9191910 3.2069940 c 2.4227480 -3.7071040 -6.2691870

0 1 .1874680 12.9095310 3.9872500 c 5.2338540 -0.5919090 -4.9227830 c -1.1557970 10.2815190 3.2065510 c 3.6204070 -3.9143450 -6.9593480

0 1 .1616630 10.4218020 2.5900960 c 1 .4364840 -4.7379230 -6.4226680 c 2.1688250 12.5654300 3.0146710 c 3.8705360 -5.0387640 -7.7284410 c -1.4706370 9.0286760 2.5883960 c 1 .6921340 -5.8932980 -7.2051280 c 2.3699650 11 .0684620 2.9831340 N 0.2470220 -4.5930220 -5.8090630 s -0.3022690 8.1010880 1 .6869310 C 2.9496220 -6.0791210 -7.8847230 c -2.6852350 8.3802230 2.6055420 N 0.7460940 -6.8405580 -7.3262950 c -1.4687730 6.8348300 1 .3207080 C -0.6533150 -5.5312080 -5.9469400 c -2.6882350 7.1605030 1 .9110420 C 3.2394550 -7.2431530 -8.6732870

0 -3.7824960 8.8728470 3.2412350 C -0.3994070 -6.6763030 -6.7182430 c -1.1797480 5.6681020 0.5358060 C 4.4417350 -7.5367430 -9.3134950

0 -3.8036770 6.3931530 1 .8412680 S 2.0956860 -8.5442700 -8.9842290 c -4.9897180 8.2663830 2.7992280 C 4.4320200 -8.7408680 -10.0346660 c -2.1591720 4.7205780 0.2228450 0 5.5462150 -6.7517510 -9.2692380 c 0.1324820 5.3921600 0.0071200 c 3.2363970 -9.4208310 -9.9685830 c -4.8250170 6.7652270 2.7712890 0 5.5086900 -9.1949300 -10.7313170 c -1.9011620 3.5813060 -0.5214590 c 6.7376820 -7.3973070 -9.7275250 c 0.3924070 4.2277600 -0.7603360 c 2.9220970 -10.6704000 -10.5935700 TABLE NINE (cont'd) TABLE NINE (cont'd)

pDEQ +1 pDEQ +1

X Y Z X Y Z

c 6.4617150 -8.1734480 -10.9935580 H 2.6721740 10.7049970 3.9702360 c 1 .7328660 -11 .3524590 -10.5232690 H 3.1220710 10.7835650 2.2489600 s 4.0543810 -11 .5456910 -11 .5994530 H -5.7626770 8.5644740 3.5055960 c 1 .7244260 -12.5594650 -11 .2568000 H -5.2471760 8.641 1320 1 .8031700

0 0.6584240 -10.9050620 -9.8252540 H -3.1670150 4.8751520 0.5705960 c 2.9136140 -12.8368580 -11 .8977150 H -5.7335690 6.2686100 2.4347100

0 0.6141650 -13.3521680 -11 .2913030 H -4.5556590 6.3943260 3.7642610 c -0.3382690 -11 .9036050 -9.6210090 H -2.7248400 2.9121440 -0.7098900 c 3.2208460 -14.0268390 -12.6911450 H 3.0974330 6.7512280 -0.0246610 c -0.5729200 -12.6689190 -10.9022260 H 3.5588480 4.6801820 -1.4007340 c 2.3530800 -15.1000430 -12.7595580 H -2.7689560 -0.9013260 -0.8730760 c 4.43451 10 -14.1627290 -13.4328100 H -4.2522040 -0.1275640 -1.4812030 c 2.6138680 -16.2460200 -13.5219900 H -3.3528720 -0.2572620 -3.8104630 c 4.6994780 -15.3248590 -14.2073960 H -3.3760310 -1.8849490 -3.0889500

N 5.3451480 -13.1674550 -13.3819220 H 4.3090800 1 .1627630 -5.7626140 c 3.7618290 -16.4040430 -14.2748320 H 5.1558030 1 .4520230 -4.2231 150

N 5.8601430 -15.4262640 -14.8881060 H 5.461 1450 -1.0122080 -3.9387150

C 6.4564290 -13.2969420 -14.0528590 H 6.1539750 -0.5030310 -5.4972770

C 3.9972150 -17.6034950 -15.0766890 H 4.3949460 -3.1669480 -6.9029600

C 6.7190770 -14.4472560 -14.8202280 H 4.8231490 -5.1037670 -8.2273230 c 3.1057730 -18.6279550 -15.3097610 H -1.6054650 -5.3924970 -5.4434950 s 5.5094590 -17.9717080 -15.8830630 H -1.1466250 -7.4556950 -6.8321090 c 3.6319530 -19.6912320 -16.0992190 H 7.4643820 -6.6038520 -9.8941 170

0 1 .8272310 -18.6692300 -14.8401600 H 7.1048330 -8.0664890 -8.9442520 c 4.9151900 -19.4739120 -16.4689350 H 7.3599100 -8.6728290 -11 .3529190

0 2.8992590 -20.7861720 -16.4455630 H 6.0822330 -7.5070930 -11 .7751020 c 1 .0103610 -19.6319090 -15.5056550 H -0.0146320 -12.5833560 -8.8266570 c 1 .7429990 -20.9471210 -15.6356600 H -1.2368150 -11 .3780910 -9.3011630

H -3.7484280 19.7823050 9.6178510 H -0.8807530 -11 .9862080 -11 .7007980

H 0.8561540 20.9984390 9.2381770 H -1.3365620 -13.4341790 -10.7712450

H 0.6471710 19.3566210 9.8921090 H 1 .4298310 -15.0711220 -12.2031820

H 0.1278590 16.2481720 6.7818530 H 1 .8775760 -17.0336640 -13.5109540

H 1 .7368980 19.2512290 7.6433590 H 7.1760710 -12.4850020 -13.9974680

H 0.3548880 20.1317290 6.9471890 H 7.6468760 -14.5512430 -15.3754910

H 0.5666230 14.2821710 5.4751140 H 5.5336260 -20.1209840 -17.0712940

H -6.2937700 14.9518670 6.6897240 H 0.1 109910 -19.7354250 -14.9001250

H -5.8309030 12.8765100 5.3230280 H 0.7370650 -19.2525000 -16.4953460

H 1 .8515880 12.9265080 2.0310160 H 1 .1226230 -21 .6949590 -16.1281850

H 3.0825590 13.0804890 3.3074260 H 2.0309470 -21 .3171350 -14.6452980 TABLE TEN TABLE TEN (cont'd)

pDEQ -1 pDEQ -1

X Y Z X Y Z

c -3.1077110 19.0404760 9.3010480 C -4.7268070 6.6767210 2.9570090 s -3.7530590 17.6182580 8.5761430 C -1.9047900 3.6300610 -0.5796830 c -1.8132080 19.2329710 8.9610120 C 0.3806900 4.2901360 -0.8064820 c -2.2312910 17.2295080 7.7987610 N 1 .0997540 6.3370190 0.2256770 c -1.3140630 18.2073830 8.1052180 C -0.6442900 3.3242450 -1.0986910

0 -1.0548910 20.2957150 9.3615930 N 1 .6172890 4.0891690 -1.2927720 c -2.0050100 16.0300620 6.9872940 C 2.2903720 6.1056240 -0.2654120

0 -0.0202270 18.2305900 7.6624410 C -0.3958650 2.1352140 -1.8712590 c 0.3349350 20.0763590 9.1710010 C 2.5555660 4.9663860 -1.0351350 c -0.7415580 15.6690070 6.5605090 C -1.2922320 1 .1076990 -2.1441270 c -3.0619320 15.1552850 6.5943790 S 1 .1399890 1 .7531960 -2.6506150 c 0.5915230 19.5080950 7.7938470 C -0.7818450 0.0806340 -2.9484980 c -0.4930890 14.5409160 5.7692930 0 -2.5812830 1 .0730650 -1.6854860 c -2.8124240 14.0074310 5.7887400 C 0.5329890 0.2566080 -3.3334910

N -4.3195880 15.4235200 7.0089960 0 -1.5209660 -1.0125210 -3.3158120 c -1.4911330 13.6829930 5.3406450 C -3.1945920 -0.2038330 -1.8089690

N -3.8346350 13.1981680 5.4427160 C 1 .3183960 -0.6026950 -4.1471750

C -5.2836080 14.6191360 6.6547100 C -2.9104670 -0.7966600 -3.1709240

C -1.2033820 12.5286340 4.4983650 C 2.6272770 -0.4135060 -4.5465510

C -5.0374940 13.4871390 5.8569240 S 0.7251030 -2.1214480 -4.8111020 c -0.0051710 12.2343370 3.8846620 C 3.1419970 -1.4345390 -5.3507940 s -2.3513410 11 .2467540 4.1484340 0 3.3584120 0.6779910 -4.1673370 c 0.0014950 11 .0112580 3.1749060 C 2.2482060 -2.4698700 -5.6242740

0 1 .1097510 13.0219830 3.9406300 0 4.4358690 -1.3851310 -5.8180170 c -1.1876280 10.3340690 3.221 1140 C 4.5422960 0.8440650 -4.9280600

0 1 .0959430 10.5623000 2.4909980 C 2.4761570 -3.6371910 -6.4257570 c 2.0876700 12.6934920 2.9586990 c 5.2462950 -0.4859280 -5.0847100 c -1.5026600 9.0743160 2.5992560 c 3.6851430 -3.8495950 -7.1235860 c 2.2946450 11 .1973440 2.9003490 c 1 .4871910 -4.6645010 -6.5753210 s -0.3476960 8.1640630 1 .6490380 c 3.9287390 -4.9721010 -7.8796520 c -2.6882560 8.3942250 2.6584320 c 1 .7465020 -5.8379280 -7.3642100 c -1.4915870 6.8732420 1 .3300850 N 0.301 1850 -4.5198330 -5.9674210 c -2.6834120 7.1660000 1 .9578100 C 2.9969080 -6.0194680 -8.0309870

0 -3.7745310 8.8467050 3.3499920 N 0.7983060 -6.7822740 -7.4836460 c -1.1889750 5.7052580 0.5097590 C -0.6084350 -5.4714400 -6.1080750

0 -3.8016790 6.3715430 1 .9256820 C 3.2859220 -7.1958160 -8.8142550 c -4.9747710 8.1669040 3.0130770 C -0.3580100 -6.6036670 -6.8668140 c -2.1596900 4.7624660 0.1847090 C 4.4689270 -7.5109780 -9.4702580 c 0.1 100960 5.4522120 -0.0194280 S 2.1276270 -8.4898860 -9.0924480

10 TABLE TEN (cont'd) TABLE TEN (cont'd)

pDEQ -1 pDEQ -1

X Y Z X Y Z

c 4.4429850 -8.7265490 -10.1732000 H -5.8438240 12.8197330 5.5652340

0 5.5979470 -6.7221250 -9.4650170 H 1 .7623770 13.0644170 1 .981 1490 c 3.2517700 -9.4082850 -10.0846440 H 2.9997510 13.2118330 3.2536430

0 5.5161810 -9.2048040 -10.8714260 H 2.6000180 10.8210550 3.8834350 c 6.7632950 -7.4379550 -9.8275150 H 3.0530880 10.9316170 2.1646440 c 2.9304900 -10.6710900 -10.6718280 H -5.6999810 8.4214160 3.7858130 c 6.5182950 -8.2266040 -11 .0948480 H -5.3414680 8.5217470 2.0435360 c 1 .7398650 -11 .3550700 -10.5918510 H -3.1691320 4.9087390 0.5355780 s 4.0615550 -11 .5824660 -11 .6468400 H -5.6409670 6.1322800 2.7206890 c 1 .7307350 -12.5820690 -11 .2818660 H -4.3386000 6.3262830 3.9200990

0 0.6497280 -10.8806920 -9.9123390 H -2.7274370 2.9628170 -0.7787260 c 2.9192970 -12.8958160 -11 .9175240 H 3.0688510 6.8345870 -0.0538070

0 0.6191790 -13.3782670 -11 .2904970 H 3.5450650 4.7766820 -1.4421770 c -0.2847420 -11 .8989270 -9.6137790 H -2.8132920 -0.8704410 -1.0279000 c 3.2158670 -14.1007990 -12.6659350 H -4.2622170 -0.0448980 -1.6554570 c -0.5629140 -12.7153320 -10.8555800 H -3.2694550 -0.1 197740 -3.9553930 c 2.3261100 -15.1659730 -12.7370160 H -3.3915240 -1.7675640 -3.2887800 c 4.4474120 -14.2905360 -13.3798130 H 4.2953410 1 .2513080 -5.9152160 c 2.5826740 -16.3294380 -13.4654290 H 5.1595650 1 .5625680 -4.3880780 c 4.7046320 -15.4831250 -14.1196800 H 5.4696030 -0.9048660 -4.0962400

N 5.3781120 -13.3182540 -13.3385150 H 6.1753080 -0.3781390 -5.6455880 c 3.7469940 -16.5363580 -14.1855670 H 4.4563560 -3.0980510 -7.0692960

N 5.8824880 -15.6293240 -14.7660800 H 4.8800850 -5.0458810 -8.3821360 c 6.5048280 -13.4887630 -13.9774190 H -1.5599950 -5.3260960 -5.6031400 c 3.9721650 -17.7637440 -14.9535170 H -1.1061270 -7.3842810 -6.9815380 c 6.7604050 -14.6649470 -14.7008950 H 7.5506760 -6.6969810 -9.9696060 c 3.0699680 -18.7740850 -15.1914410 H 7.0525170 -8.1 187150 -9.0178250 s 5.5006750 -18.18681 10 -15.7012470 H 7.4118580 -8.7660980 -11 .4100520 c 3.5957180 -19.8695530 -15.9375080 H 6.2036810 -7.5501170 -11 .8975870

0 1 .7705420 -18.7801350 -14.7570380 H 0.1051010 -12.5463620 -8.8192690 c 4.8936990 -19.6951270 -16.2732580 H -1.1862860 -11 .4004960 -9.2581520

0 2.8436170 -20.9565710 -16.2860770 H -0.9308790 -12.0629120 -11 .6545330 c 0.9581860 -19.7147460 -15.4530040 H -1.2970880 -13.4983140 -10.6649520 c 1 .6475760 -21 .05841 10 -15.52861 10 H 1 .3904850 -15.1034320 -12.2054220

H -3.7172460 19.6766720 9.9235090 H 1 .8275340 -17.0999420 -13.4555990

H 0.8202420 21 .0444380 9.2943560 H 7.2377510 -12.6881510 -13.9265670

H 0.7121460 19.3870100 9.9351740 H 7.7009370 -14.8061890 -15.2275050

H 0.1040430 16.2751260 6.8455360 H 5.5133060 -20.3671920 -16.8460320

H 1 .6561470 19.3551410 7.6195090 H 0.0228330 -19.7798250 -14.8974660

H 0.1957420 20.1851530 7.0290760 H 0.7506810 -19.3437760 -16.4630140

H 0.5287920 14.3406890 5.4891860 H 1 .0227320 -21 .7943120 -16.0350620

H -6.2868940 14.8535100 7.0006740 H 1 .8746360 -21 .4168580 -14.5177700 TABLE ELEVEN TABLE ELEVEN (cont'd)

pDDDBT neutral pDDDBT neutral

X Y Z X Y Z

c -5.5058920 -1.6231 150 0.7901600 c -7.5846890 15.9715260 -4.1341550 c -6.8469750 -1.4292990 0.7622810 0 -7.7333830 14.0637590 -2.6099680 s -4.6488360 -0.2980060 0.1 128850 c -7.2315890 17.6174170 -6.0365370 c -7.2021960 -0.1691650 0.1910210 0 -7.9948010 16.8690840 -3.1911350

0 -7.7681070 -2.3391 150 1 .1917120 c -6.8165350 14.4107610 -1.5715520 c -6.1227950 0.5826160 -0.2061030 c -7.2501630 18.7708850 -5.2937160

0 -8.5036050 0.2285760 0.0838680 c -7.1685170 17.8149720 -7.4581870 c -8.4526180 -1.9599150 2.3823380 c -9.3680210 16.741 1550 -2.8190260 c -6.1375520 1 .9303420 -0.7735620 c -7.2222800 20.0693170 -5.8654330 c -9.2602200 -0.5001510 -0.8836290 c -7.1471220 19.1395020 -8.0410110 c -7.2309850 2.7532920 -0.6964700 N -7.1 117490 16.8514460 -8.3647170 c -5.0005060 2.4944960 -1.4450100 c -7.1760730 20.3137840 -7.2120210 c -7.2658770 4.0606070 -1.2498950 N -7.0741280 19.1099230 -9.3656660 c -5.0375890 3.8245840 -2.0130380 S -7.0365430 17.5541890 -9.8247600

N -3.8291 180 1 .8973780 -1.6047380 C -7.1575550 21 .6742700 -7.7754670 c -6.2191450 4.6382000 -1.9165260 C -7.7061850 21 .9819050 -8.9918520

N -3.8861080 4.1684710 -2.5758550 C -6.5586920 22.7825560 -7.0825520

S -2.8585120 2.9256190 -2.3996400 C -7.7136770 23.2849210 -9.5538770

C -6.2926500 5.9884390 -2.5004960 C -6.5596510 24.1101550 -7.6584950

C -5.6015640 6.3472890 -3.6267120 N -5.9392010 22.7385130 -5.9098690 c -7.1054730 7.0279440 -1.9302230 C -7.1660820 24.3792100 -8.9329460 c -5.6688600 7.6323970 -4.2247380 N -5.9447230 25.0028010 -6.8979960 c -7.1689090 8.3409670 -2.5354750 S -5.4104090 24.2349460 -5.5728080

N -7.8398630 6.9407150 -0.8284050 C -7.1829340 25.7130390 -9.5268440

C -6.4379550 8.6560990 -3.7316500 C -7.9477120 26.1457310 -10.5832100

N -7.9441530 9.1804580 -1.8664450 S -6.1395810 27.0048100 -8.9814290

S -8.5402170 8.3840070 -0.5851730 C -7.6789240 27.4847210 -10.9704120

C -6.5003550 9.9697520 -4.3659960 0 -8.8710820 25.3857640 -11 .2415350

C -6.0848890 10.3032780 -5.6325320 C -6.7155800 28.0922870 -10.21 18870

S -7.1001400 11 .3910720 -3.5444730 0 -8.3482800 28.1166300 -11 .9760080

C -6.2182280 11 .6847250 -5.9303370 C -10.2243270 25.7783690 -11 .0068950

0 -5.5647780 9.4256630 -6.5393680 C -6.2148590 29.4409650 -10.3529150

C -6.7426980 12.4196460 -4.9020530 C -8.0306010 27.6492940 -13.2875550

0 -5.8916050 12.2183190 -7.1416650 s -6.8855900 30.5744520 -11 .4904150

C -6.4186840 9.1612650 -7.6536310 c -5.1963460 30.0217740 -9.6472390 c -6.9978460 13.8424750 -4.8880440 c -5.7536540 31 .8238660 -11 .0292590 c -4.4894810 12.2822230 -7.4043420 c -4.9379470 31 .3658900 -10.0229040 s -6.7869710 14.8451020 -6.2948090 0 -4.5194930 29.3862920 -8.6488800 c -7.4339920 14.5930760 -3.8302580 c -5.7046960 33.1285130 -11 .6832820 c -7.2556230 16.2895470 -5.4296640 0 -3.9464460 32.0928130 -9.4298210

5 TABLE ELEVEN (cont'd) TABLE ELEVEN (cont'd)

pDDDBT neutral pDDDBT neutral

X Y Z X Y Z

c -3.1666810 29.0556900 -8.9647390 H -6.6430750 10.0805200 -8.1960160 c -4.6267120 33.9704880 -11 .5750620 H -5.8760300 8.4735000 -8.2990910 c -6.7778660 33.6225780 -12.5010090 H -7.3476340 8.6937840 -7.3179230 c -4.2265750 32.4707410 -8.0811040 H -4.3836620 12 .7335820 -8.3883950 c -4.5633490 35.2433970 -12.1991140 H -3.9904300 12 .9084910 -6.6610100 c -6.7153880 34.9237320 -13.1315280 H -4.0510020 11 .2832930 -7.4020040

N -7.8976160 32.9705600 -12.7736660 H -7.1732500 13 .9155450 -0.6711020

C -5.5639950 35.7693560 -12.9716010 H -5.8135850 14 .0503860 -1.8124710

N -7.7966210 35.1907710 -13.8530280 H -6.7957740 15 .4910200 -1.4208140

S -8.7929860 33.9149900 -13.7418320 H -7.2831770 18 .6962140 -4.2169380

C -5.4762540 37.1033730 -13.5899950 H -9.5694760 15 .7470640 -2.4180440

C -6.5730970 37.8922740 -13.8096600 H -9.5492100 17 .4930310 -2.0535440

C -4.2236280 37.6756530 -14.0034530 H -10.0144870 16 .9305850 -3.6794610

C -6.5161810 39.1895420 -14.3844760 H -7.2248370 20 .9068310 -5.1833330

C -4.1663650 38.9950260 -14.5941060 H -8.1541400 21 .1918690 -9.5765640

N -3.0301490 37.1001440 -13.9299920 H -8.1735710 23 .4118900 -10.5226850

C -5.3486890 39.7882170 -14.7808610 H -10.3853790 26 .8132160 -11 .31 16260

N -2.9386570 39.3541870 -14.9376940 H -10.8443350 25 .1150170 -11 .6066390

S -1.9439360 38.1324940 -14.5513470 H -10.4764850 25 .6604300 -9.9501490

C -5.3081250 41 .1305060 -15.3595350 H -8.6233470 28 .2472250 -13.9763170

C -6.2898850 42.0905500 -15.3125150 H -6.9686950 27 .7968930 -13.4982540

S -3.9528180 41 .7256450 -16.2858380 H -8.2858100 26 .5939790 -13.3931680

C -5.9634670 43.2827070 -16.0284560 H -2.7643270 28 .5490010 -8.0902860

0 -7.4844310 41 .9449260 -14.6680650 H -3.1295280 28 .3827120 -9.8246970

C -4.7401730 43.2173900 -16.6083290 H -2.5883850 29 .9567430 -9.1739010

0 -6.7855730 44.3699000 -16.0801470 H -3.7768600 33 .6556360 -10.9879000

C -7.6221850 42.7577080 -13.5020180 H -4.3912220 31 .5902500 -7.4587830

C -7.9549740 44.1816200 -16.8718530 H -3.3534660 33 .0156720 -7.7277430

H -4.9834030 -2.4933430 1 .1563610 H -5.1046510 33 .1201550 -8.0430550

H -9.1537170 -2.7625910 2.6028050 H -3.6593210 35 .8168330 -12.0553780

H -7.7477340 -1.8541810 3.2117350 H -7.5493350 37 .5143340 -13.5436070

H -8.9952550 -1.0228740 2.2431970 H -7.4453150 39 .7255500 -14.5102690

H -9.2679580 -1.5647440 -0.6466810 H -4.2557070 43 .9865590 -17.1897630

H -10.2729610 -0.1041010 -0.8427310 H -7.5166130 43 .8140920 -13.7522100

H -8.8469050 -0.3470350 -1.8836630 H -8.6199240 42 .5674310 -13.11 15280

H -8.1 165380 2.3967960 -0.1915500 H -6.8761900 42 .4784380 -12.7537820

H -8.1774660 4.6254550 -1.1206310 H -8.5141 170 45 .1139190 -16.8208050

H -4.9536280 5.6208300 -4.0948860 H -7.6843400 43 .9757790 -17.91 12480

H -5.0802580 7.8048020 -5.1 135030 H -8.5649030 43 .3630850 -16.4848620 TABLE TWELVE TABLE TWELVE (cont'd)

pDDDBT +1 pDDDBT +1

X Y Z X Y Z

c -5, .5575050 -1.6837160 0.7417140 C -5, .7887030 17 .5865060 -6.0904860 c -6, .7978500 -1.2430080 1 .0667720 0 -5, .8769580 16 .9859250 -3.1339960 s -4, .6827860 -0.5319360 -0.1818510 C -4, .6470190 14 .3349380 -1.7871780 c -7, .0536260 0.0715560 0.5706410 C -5, .6188300 18 .7762790 -5.3880500

0 -7, .7200010 -1.9729430 1 .7557550 C -5, .9232160 17 .7572160 -7.5167660 c -5, .9986490 0.6145180 -0.1242920 C -7, .0286460 16 .9748040 -2.2783690

0 -8, .2364600 0.7107870 0.7983580 C -5, .5943940 20 .0323170 -5.9942460 c -7, .9693390 -1.5041630 3.0785830 C -5, .9201660 19 .0604340 -8.1452850 c -5, .9179970 1 .9494440 -0.7115410 N -6, .0563700 16 .7675230 -8.3812460 c -9, .3563940 0.1370170 0.1207410 C -5, .7499320 20 .2640120 -7.3599960 c -6, .7730760 2.9633930 -0.3627700 N -6, .0496240 18 .9781650 -9.4611660 c -4, .9304490 2.2994000 -1.6947090 S -6, .1669290 17 .4091280 -9.8645680 c -6, .7162140 4.2612840 -0.9333940 C -5, .7553200 21 .5898850 -7.9267070 c -4, .8779720 3.6195050 -2.2823740 C -6, .2442530 21 .8556390 -9.2081660

N -3, .9846980 1 .4934490 -2.1531040 C -5, .2640800 22 .7633460 -7.2296890 c -5, .8103310 4.6397200 -1.8882050 C -6, .3069850 23 .1181520 -9.7862320

N -3, .8910420 3.7465640 -3.1605100 C -5, .3104490 24 .0725960 -7.8412890

S -3, .1059500 2.3277280 -3.2293180 N -4, .7024260 22 .7964480 -6.0313290

C -5, .7967710 5.9863600 -2.4820750 C -5, .8644380 24 .2858120 -9.1554470

C -5, .3956400 6.2236640 -3.7702680 N -4, .7932290 25 .0192470 -7.0806630 c -6, .2103930 7.1530720 -1.7492650 S -4, .2808300 24 .3269920 -5.7032900 c -5, .3997600 7.5058280 -4.3764250 C -5, .9316370 25 .5698550 -9.7599090 c -6, .2054260 8.4616070 -2.3638540 C -6, .5567680 25 .9107520 -10.9784430

N -6, .5988280 7.1907860 -0.4811410 S -5, .2128550 26 .9960190 -9.0372480

C -5, .8034770 8.6470980 -3.7291940 C -6, .4095400 27 .2481410 -11 .3236680

N -6, .5883120 9.4228630 -1.5373400 0 -7, .2279890 25 .0246030 -11 .74871 10

S -6, .9250280 8.7329920 -0.1066180 C -5, .7037810 27 .9999730 -10.3758730

C -5, .8094620 9.9563320 -4.3752480 0 -6, .9134340 27 .8142360 -12.4436680

C -5, .7086840 10.2208410 -5.7244140 C -8, .6284840 25 .2934010 -11 .9237700

S -5, .9256340 11 .4440320 -3.4753270 C -5, .4015050 29 .3736360 -10.46271 10

C -5, .6908440 11 .6022830 -6.0286400 C -6, .3628800 27 .3418500 -13.6824210

0 -5, .6206820 9.2732720 -6.7010750 S -5, .9351 190 30 .3970040 -11 .7766140

C -5, .7915690 12.4102440 -4.9204710 C -4, .6555270 30 .1125430 -9.5461840

0 -5, .6325830 12.0971830 -7.2910420 C -5, .1280220 31 .7858930 -11 .1054880

C -6, .8132000 9.1 195480 -7.4754630 C -4, .5162150 31 .4622180 -9.8978810 c -5, .8130710 13.8439040 -4.9060650 0 -4, .1788460 29 .5528870 -8.4168240 c -4, .4190300 11 .8254870 -8.0008910 C -5, .1251310 33 .0745510 -11 .7709750 s -5, .8117700 14.7929270 -6.3605140 0 -3, .8455560 32 .3479400 -9.1 124250 c -5, .8354780 14.6572960 -3.7904590 c -2 .7627000 29 .6442880 -8.1942670 c -5, .8182820 16.3001130 -5.4612480 c -4, .2870370 34 .1035730 -11 .3967700 c -5, .8523850 16.0299700 -4.0937650 c -5, .9769770 33 .3623790 -12.8903550

0 -5, .8629610 14.1650790 -2.5226820 c -4, .5542560 32 .7384540 -7.9295630 TABLE TWELVE (cont'd) TABLE TWELVE (cont'd)

pDDDBT +1 pDDDBT +1

X Y Z X Y Z

c -4.2632460 35.3621230 -12.0381500 H -7 .6406600 8.7961570 -6.8399850 c -5.9631680 34.6543810 -13.5357450 H -4, .5338030 12 .2836540 -8.9801530

N -6.8257040 32.5135950 -13.4477850 H -3, .5699040 12 .2759670 -7.4820800

C -5.0777190 35.7003240 -13.0922240 H -4, .2640400 10 .7520330 -8.1034790

N -6.8070910 34.7168940 -14.5571260 H -4, .8056420 13 .8560480 -0.8242090

S -7.5458480 33.28241 10 -14.6850160 H -3, .8178830 13 .8486490 -2.3051240

C -5.0472770 37.0247950 -13.7241580 H -4, .4256960 15 .3942140 -1.6465740

C -6.1492000 37.5882680 -14.3167390 H -5, .4909770 18 .7303810 -4.3181860

C -3.8592370 37.8336830 -13.7537170 H -7, .1259790 16 .0180780 -1.7680510

C -6.1606230 38.8723430 -14.9143380 H -6, .8718420 17 .7715410 -1.5554610

C -3.8680930 39.13861 10 -14.3748460 H -7, .9289410 17 .1775390 -2.8621050

N -2.6654480 37.5065370 -13.2753970 H -5, .4458190 20 .8801280 -5.3449730

C -5.0571310 39.6884510 -14.9669160 H -6, .6018590 21 .0278060 -9.7986350

N -2.6859380 39.7340300 -14.3374120 H -6, .7125310 23 .1937220 -10.7827390

S -1.6536010 38.7371800 -13.5872580 H -8, .7840880 26 .2671630 -12.3863850

C -5.0825970 41 .0090410 -15.5845620 H -9, .0043490 24 .5064530 -12.5721690

C -6.1921310 41 .7477920 -15.9296220 H -9, .1386140 25 .2543500 -10.95971 10

S -3.6359140 41 .8732220 -16.0458060 H -6, .8526250 27 .9154340 -14.4644390

C -5.8796150 42.9819400 -16.5755360 H -5, .2874480 27 .5256080 -13.7094250

0 -7.4763110 41 .3522940 -15.7082500 H -6, .5615090 26 .2783780 -13.8139600

C -4.5427090 43.1691300 -16.7075450 H -2 .5801540 29 .1428390 -7.2479840

0 -6.8260890 43.8748340 -16.9787640 H -2 .2277120 29 .1295440 -8.9942720

C -8.1966340 42.1629960 -14.7751220 H -2 .4436570 30 .6832320 -8.1423330

C -7.5772450 43.4602240 -18.1179030 H -3, .6029170 33 .9469060 -10.5763820

H -5.1260610 -2.6423850 0.9852650 H -4, .7601990 31 .8722730 -7.2984620

H -8.7191330 -2.1684120 3.5034620 H -3, .9063650 33 .4341540 -7.4019910

H -7.0572740 -1.5525060 3.6796350 H -5, .4905380 33 .2339520 -8.1938470

H -8.3460430 -0.4794140 3.0686320 H -3, .5529630 36 .0892790 -11 .6750150

H -9.4912020 -0.9055820 0.4096720 H -7, .0728340 37 .0291150 -14.3423710

H -10.2254000 0.7200400 0.4185930 H -7, .0857470 39 .2183180 -15.3499880

H -9.2206960 0.2065940 -0.9613400 H -4, .0497390 44 .0212430 -17.1497960

H -7.5320290 2.7724790 0.381 1540 H -8, .2251820 43 .2012030 -15.1051320

H -7.4344430 4.9855680 -0.5778170 H -9, .2052880 41 .7575970 -14.7348170

H -5.0461250 5.3957550 -4.3690110 H -7, .7354030 42 .1012030 -13.7865190

H -5.0649670 7.5771870 -5.4006460 H -8, .2872520 44 .2583120 -18.3240340

H -7.0738200 10.0548360 -7.9735080 H -6, .9197270 43 .3255560 -18.9807820

H -6.5998620 8.3530630 -8.2171770 H -8, .1 137010 42 .5301990 -17.9186760 TABLE THIRTEEN TABLE THIRTEEN (cont'd)

pDDDBT -1 pDDDBT -1

X Y Z X Y Z

c -5.9757270 -1.8329790 0.6458570 c -5.6109080 17.5239690 -6.1706350 c -7.0464270 -1.2386640 1 .2255540 0 -5.4294570 16.8813310 -3.1676570 s -5.1712150 -0.7788980 -0.4481560 c -4.3051620 14.3012280 -1.9061720 c -7.2206040 0.1 114320 0.7928180 c -5.3093920 18.7074120 -5.4938200

0 -7.8980010 -1.8582400 2.0943310 c -5.8800700 17.6935930 -7.5638770 c -6.2775190 0.5304190 -0.1 131760 c -6.6803580 17.2276100 -2.5839460

0 -8.2378240 0.8883960 1 .2723790 c -5.2949090 19.9621130 -6.0886590 c -7.8221480 -1.3734650 3.4309760 c -5.8703300 19.0102550 -8.2035060 c -6.1434700 1 .8587550 -0.7121050 N -6.1548780 16.7069640 -8.3996040 c -9.5234710 0.5373980 0.7634360 C -5.5770750 20.2139390 -7.4428130 c -6.7650310 2.9675050 -0.1993540 N -6.1468320 18.9289700 -9.4938390 c -5.3419360 2.1008070 -1.8770640 S -6.3926150 17.3584500 -9.8829940 c -6.6651250 4.2603100 -0.7763710 C -5.5723270 21 .5363400 -8.0135170 c -5.2402000 3.4194540 -2.4684140 C -5.8348560 21 .7855780 -9.3719910

N -4.6167770 1 .1914570 -2.5105710 C -5.2955030 22.7420940 -7.2498830 c -5.9391600 4.5455090 -1.9034900 C -5.8605920 23.0438820 -9.9586550

N -4.4360930 3.4384010 -3.5232840 C -5.3239950 24.0622980 -7.8818540

S -3.8670220 1 .9357720 -3.7438810 N -4.9934720 22.8214650 -5.9651990

C -5.8821770 5.8901240 -2.4964490 C -5.6283550 24.2344670 -9.2675020

C -5.6820850 6.1041720 -3.8381890 N -5.0401450 25.0485030 -7.0486480 c -6.0554410 7.0851610 -1.7178140 S -4.7598490 24.3934190 -5.5742330 c -5.6607700 7.3776440 -4.4515900 C -5.6797640 25.5323870 -9.8993470 c -6.0248180 8.3935520 -2.3430370 C -6.0984940 25.8441030 -11 .1819660

N -6.2307200 7.1551020 -0.4041450 S -5.1791990 27.0018120 -9.0844610

C -5.8394370 8.5579610 -3.7624180 C -5.9923850 27.2115770 -11 .5077370

N -6.1765700 9.3807630 -1.4760210 0 -6.5928430 24.9490420 -12.0988050

S -6.3428420 8.7263920 -0.0016240 C -5.4961340 27.9923610 -10.4932020

C -5.8408660 9.8586180 -4.4042390 0 -6.3974540 27.7267650 -12.7048440

C -5.8712500 10.1253240 -5.7574110 C -8.0140640 24.8749690 -12.0987810

S -5.7822910 11 .3727820 -3.5167050 C -5.2701550 29.4096690 -10.5204430

C -5.8258240 11 .501 1670 -6.0751740 C -5.6197550 27.3140740 -13.8255220

0 -5.9192480 9.1717230 -6.7342960 S -5.7051410 30.4019820 -11 .8858060

C -5.7666470 12.3254240 -4.9764690 c -4.7069370 30.1866500 -9.5360680

0 -5.8658580 11 .9598580 -7.3620650 c -5.0949400 31 .8631730 -11 .1265480

C -7.1346660 9.1591720 -7.4826850 c -4.6123640 31 .5560230 -9.8711270 c -5.7039360 13.7594340 -4.9626010 0 -4.2953380 29.6949860 -8.3289350 c -4.6315190 11 .8400680 -8.0645790 c -5.1026310 33.16021 10 -11 .7758210 s -5.8145300 14.7330750 -6.4136270 0 -4.0629080 32.4626860 -9.0097530 c -5.5745300 14.5743740 -3.8651610 c -2.8831310 29.5427720 -8.2105820 c -5.6405550 16.2331880 -5.5230510 c -4.4307490 34.2564190 -11 .2789440 c -5.5409030 15.9502260 -4.1710910 c -5.8146260 33.4076870 -13.0038230

0 -5.5381910 14.0915370 -2.5892550 c -4.8244300 32.6817270 -7.8225030 TABLE THIRTEEN (cont'd) TABLE THIRTEEN (cont'd)

pDDDBT -1 pDDDBT -1

X Y Z X Y Z

c -4.4452440 35.5276380 -11 .8973630 H -7.9796440 8.9212510 -6.8309770 c -5.8355590 34.7153630 -13.6308420 H -4.7907490 12.2870180 -9.0438080

N -6.5015160 32.5025570 -13.6808300 H -3.8393910 12.3841340 -7.5450970

C -5.1244540 35.8224020 -13.0539300 H -4.3505290 10.7899290 -8.1730960

N -6.5419010 34.7277750 -14.7543260 H -4.4215550 13.8518980 -0.9215200

S -7.1207680 33.2272810 -14.9927450 H -3.4860950 13.8070730 -2.4359240

C -5.1415910 37.1675020 -13.6483600 H -4.0945500 15.3664850 -1.8105470

C -6.1889030 37.6358550 -14.3982670 H -5.0552830 18.6489350 -4.4452720

C -4.0559150 38.1000760 -13.4839990 H -7.1592170 16.3468440 -2.1489620

C -6.2443190 38.9365460 -14.9635320 H -6.4689980 17.9543120 -1.8003720

C -4.1 131450 39.4265810 -14.0634540 H -7.3426880 17.6772490 -3.3282080

N -2.9149360 37.8775690 -12.8450220 H -5.0466330 20.7992330 -5.4590510

C -5.2504700 39.8690140 -14.8176470 H -6.0299930 20.9430520 -10.0129040

N -3.0209870 40.1398580 -13.8340850 H -6.0574540 23.0960100 -11 .0197490

S -2.0064310 39.2156140 -12.9658380 H -8.4502030 25.8465650 -12.3439010

C -5.3357240 41 .2102060 -15.3963970 H -8.2890430 24.1470220 -12.8611550

C -6.4560410 41 .8490380 -15.8680230 H -8.3833630 24.5402990 -11 .1259540

S -3.9406500 42.2346660 -15.6292370 H -6.0545220 27.8028180 -14.6956420

C -6.1942860 43.1375450 -16.4263570 H -4.5814680 27.6367450 -13.7092570

0 -7.7189920 41 .3269990 -15.8393390 H -5.6602930 26.2312130 -13.9441050

C -4.8810700 43.4667160 -16.3728810 H -2.7026750 29.0991310 -7.2335270

0 -7.1756820 43.9504360 -16.9162270 H -2.5026380 28.8735380 -8.9855850

C -8.5780520 41 .9435310 -14.8816750 H -2.3841760 30.5121890 -8.2799640

C -7.7587340 43.4928070 -18.1320300 H -3.8573320 34.1441490 -10.3716540

H -5.6386370 -2.8478750 0.7894600 H -4.9521250 31 .7526580 -7.2672140

H -8.5514330 -1.9412940 4.0061060 H -4.2610010 33.3970480 -7.2257570

H -6.8229680 -1.5415700 3.8432670 H -5.8026860 33.1021370 -8.0706370

H -8.0615730 -0.3096010 3.4783850 H -3.8733780 36.3089870 -11 .4185390

H -9.7685760 -0.4964250 1 .0126890 H -7.0259700 36.9806300 -14.5870270

H -10.2363420 1 .2104130 1 .2362170 H -7.1228750 39.1980280 -15.5351640

H -9.5554490 0.6735140 -0.3204980 H -4.4267770 44.3854920 -16.7101470

H -7.3698670 2.8607640 0.6892900 H -8.6780970 43.0113200 -15.0835860

H -7.1918030 5.0624460 -0.2816010 H -9.5467310 41 .4566760 -14.9780300

H -5.5247450 5.2508790 -4.4814780 H -8.1923510 41 .7933920 -13.8701460

H -5.4938350 7.4207450 -5.5169090 H -8.5231990 44.2201420 -18.3996750

H -7.3013090 10.1213580 -7.9667500 H -7.0060440 43.4477900 -18.9245070

H -7.0229540 8.3793610 -8.2341310 H -8.2133470 42.5086320 -18.0049320 TABLE FOURTEEN TABLE FOURTEEN (cont'd)

EDOT-b-BT neutral EDOT-b-BT neutral

X Y Z X Y Z

c -6.9263820 -19.3320680 -0.1653680 c 1 .0993690 -3.0285170 1 .0936710 c -7.6038240 -18.4851330 0.6452190 0 -0.5928780 -2.1044010 2.5344900 s -5.5231040 -18.5818360 -0.8340640 c -2.5450340 -3.5008540 2.7879440 c -6.9892110 -17.2024220 0.7369020 c 1 .9782060 -1.8909950 1 .001 1280

0 -8.7405160 -18.7953780 1 .3291770 c -1.5856490 -2.5413420 3.4580280 c -5.8462920 -17.07801 10 -0.0032400 c 3.1578420 -1.8082640 0.3119150

0 -7.5167090 -16.1963790 1 .4897620 s 1 .6422730 -0.3751100 1 .7914410 c -9.4264060 -17.6392680 1 .7967510 c 3.8004120 -0.5532850 0.4234230 c -4.9895080 -15.9220220 -0.1 185470 0 3.6682650 -2.8336050 -0.4288880 c -8.4617070 -16.6692260 2.4441150 c 3.1215800 0.3544860 1 .2030010 c -3.8468420 -15.8065190 -0.8584200 0 4.9897830 -0.3080830 -0.1943860 s -5.3025860 -14.4252390 0.7286940 c 5.0484490 -2.6626920 -0.7211830 c -3.2204840 -14.5404230 -0.7550410 c 3.5352120 1 .7068100 1 .5383560

0 -3.3468630 -16.8031720 -1.6420940 c 5.3021550 -1.2556390 -1.2126370 c -3.8743850 -13.6634330 0.0650240 c 4.7898550 2.1950090 1 .2606560

0 -2.0625280 -14.2477690 -1.4113790 c 2.6575800 2.6425710 2.1891830 c -1.9884850 -16.5839720 -2.0084940 c 5.1993120 3.5162950 1 .5700450 c -3.5034430 -12.3049230 0.3717190 c 3.0740380 3.9950770 2.4932260 c -1.7904670 -15.1569810 -2.4724050 N 1 .4185350 2.3858690 2.5769870 c -4.1615000 -11 .4231530 1 .1835780 c 4.3968840 4.4507280 2.1688120 s -2.0783480 -11 .5434720 -0.2979300 N 2.1236440 4.6961040 3.0979170 c -3.5433640 -10.1524320 1 .2734460 s 0.8289150 3.7313570 3.2657630

0 -5.3021 190 -11 .7262700 1 .8652200 c 4.8448090 5.8262310 2.4439310 c -2.3981820 -10.0384740 0.5345780 c 3.9986290 6.9002920 2.4125300

0 -4.0657950 -9.1420570 2.0240250 c 6.2152300 6.1366200 2.7538380 c -5.9883200 -10.5678990 2.3272380 c 4.4173700 8.2389490 2.6394800 c -1.5340160 -8.8910740 0.4228170 c 6.6418200 7.5009540 2.9852590 c -5.0187710 -9.6034300 2.9756400 N 7.2030720 5.2615690 2.8898800 c -0.3805020 -8.7848630 -0.3044920 C 5.7092570 8.5930760 2.9140240 s -1.8478030 -7.3874680 1 .2592500 N 7.9314020 7.5912900 3.2837510 c 0.2521640 -7.5232520 -0.1978710 S 8.5433730 6.0890710 3.2742910

0 0.1234220 -9.7871220 -1.0787530 C 6.1297020 9.9930990 3.1061310 c -0.4060090 -6.6379170 0.6106910 C 7.3655650 10.4472300 2.7377330

0 1 .4203370 -7.2399130 -0.8390670 C 5.2580000 10.9840250 3.6777310 c 1 .4895230 -9.5805880 -1.4200870 C 7.7842230 11 .7969490 2.8850590 c -0.0274650 -5.2822000 0.9172160 C 5.6919280 12.3550720 3.8465610 c 1 .7067380 -8.1580010 -1.8889690 N 4.021 1780 10.7816170 4.1 129530 c -0.6962550 -4.3876980 1 .7073740 C 7.0012940 12.7765850 3.4287820 s 1 .4225770 -4.5432070 0.2792040 N 4.7601510 13.1239460 4.3951850 c -0.0657910 -3.1243660 1 .8050650 S 3.4607630 12.1948810 4.6758050

0 -1.8577560 -4.6723210 2.3608150 C 7.4662370 14.1659590 3.5941330

5 TABLE FOURTEEN (cont'd) TABLE FOURTEEN (cont'd)

EDOT-b-BT neutral EDOT-b-BT neutral

X Y Z X Y Z

c 7.0842410 14.9522460 4.6450070 H -1.7689010 -17.2916310 -2.8069200 c 8.3708290 14.7828140 2.6620580 H -2.4512960 -14.9413360 -3.3186860 c 7.541 1190 16.2842360 4.8364020 H -0.7576830 -14.9800750 -2.7699660 c 8.81901 10 16.1468630 2.8456360 H -6.4961600 -10.0828660 1 .4868260

N 8.8709710 14.2221590 1 .5684320 H -6.7323290 -10.9175300 3.0419320

C 8.3923030 16.9226160 3.9782420 H -4.4996280 -10.0934910 3.8061280

N 9.6412780 16.5498750 1 .8855620 H -5.5335810 -8.7182730 3.3470870

S 9.8233360 15.3181910 0.8468470 H 2.1209740 -9.7905760 -0.5502280

C 8.8306730 18.3155000 4.1835270 H 1 .7191180 -10.2944270 -2.2101850

C 9.0777720 19.1725400 3.1478830 H 1 .0636630 -7.9430160 -2.7489040

C 9.0158080 18.8697300 5.4973490 H 2.7462280 -7.9895620 -2.1675650

C 9.4739870 20.5261290 3.3254540 H -3.0194310 -3.0195230 1 .9261940

C 9.4185540 20.2482130 5.6778660 H -3.3159550 -3.8338940 3.4815830

N 8.8779730 18.2212520 6.6466260 H -1.1013750 -3.0274010 4.3113170

C 9.6478890 21 .10861 10 4.5493100 H -2.0994790 -1.6442190 3.8004880

N 9.5651220 20.5762650 6.9552470 H 5.6438470 -2.8630140 0.1761470

S 9.2263300 19.2609190 7.8410720 H 5.2951940 -3.3978160 -1.4861 180

C 10.0335820 22.5246440 4.7077180 H 4.6929430 -1.0508980 -2.0988460

C 9.5938410 23.2906030 5.7523640 H 6.3527790 -1.1036300 -1.4567780

C 10.8878720 23.1873020 3.7559730 H 5.5104790 1 .5499250 0.7823540

C 9.9348690 24.6671660 5.9120220 H 6.2136640 3.7874290 1 .3154370

C 11 .2363810 24.5767050 3.9290200 H 2.9516300 6.7365060 2.2034880

N 11 .4499370 22.6513500 2.6787300 H 3.6624440 9.0095680 2.5864020

C 10.7362970 25.3180770 5.0327930 H 8.0751910 9.7517600 2.3144510

N 12.0422660 25.0404880 2.9818070 H 8.7762330 12.0488400 2.5398560

S 12.3318220 23.8117810 1 .9632310 H 6.3951560 14.5539970 5.3752370

H -7.1784220 -20.3532140 -0.4025800 H 7.1922040 16.8064080 5.7152950

H -9.9412240 -17.1522970 0.961 1170 H 8.9721560 18.8153630 2.1340720

H -10.1668550 -17.9919860 2.5140610 H 9.6464300 21 .1132920 2.4352820

H -7.9343800 -17.1577900 3.2704700 H 8.9615860 22.8385190 6.5025560

H -8.9816750 -15.7895150 2.8212060 H 9.5324470 25.1949450 6.7691330

H -1.3394310 -16.7943090 -1.1518800 H 11 .0051800 26.3606930 5.1432350

TABLE FIFTEEN TABLE FIFTEEN (cont'd)

EDOT-b-BT +1 EDOT-b-BT +1

X Y Z X Y Z

c -6.7790650 -19.2658590 -0.2917490 c 1 .1 184800 -3.0335630 0.9644750 c -7.4721460 -18.4207120 0.5119570 0 -0.5933460 -2.1 172920 2.3997690 s -5.3746350 -18.5254850 -0.9543240 c -2.5317340 -3.5256550 2.6852240 c -6.8640430 -17.1390460 0.6035270 c 1 .9756020 -1.9003130 0.8886340

0 -8.6133020 -18.7295950 1 .1791590 c -1.5609840 -2.5709810 3.3452480 c -5.7117480 -17.0167840 -0.1345250 c 3.1674810 -1.8119750 0.2020060

0 -7.3869410 -16.1361970 1 .3467430 s 1 .6343280 -0.3850240 1 .6908370 c -9.3205100 -17.5690160 1 .6067290 c 3.8004190 -0.5594490 0.3198820 c -4.8702670 -15.8620920 -0.2401700 0 3.6771770 -2.8322270 -0.5259550 c -8.3811580 -16.5881620 2.2731450 c 3.1098850 0.3396950 1 .1064990 c -3.7094840 -15.7487730 -0.9742030 0 4.9835570 -0.3021090 -0.3007270 s -5.2102270 -14.3715290 0.5987920 c 5.0471480 -2.6395480 -0.8881840 c -3.0944200 -14.4937520 -0.8694310 c 3.5105430 1 .6961140 1 .4479820

0 -3.1964850 -16.7518080 -1.7323730 c 5.2667300 -1.2192310 -1.3554180 c -3.7680530 -13.6044470 -0.0475890 c 4.7583210 2.1965140 1 .1626490

0 -1.9479540 -14.1856800 -1.5097470 c 2.6284240 2.6096560 2.1 176440 c -1.8198700 -16.5449100 -2.0422090 c 5.1603460 3.5176900 1 .4825760 c -3.3978210 -12.2728640 0.2417090 c 3.0352510 3.9599910 2.4318410 c -1.5997530 -15.1300860 -2.5310560 N 1 .3975130 2.3334790 2.5189620 c -4.0824870 -11 .3710720 1 .0522130 c 4.3504740 4.4348210 2.0980770 s -1.9617810 -11 .5209030 -0.4190770 N 2.0864400 4.6423570 3.0593800 c -3.4819190 -10.1223610 1 .1403390 s 0.8049960 3.6668390 3.2334190

0 -5.2350730 -11 .6795760 1 .6933220 c 4.7864490 5.8100650 2.3913780 c -2.3025110 -10.0022660 0.3995740 c 3.9294610 6.8758930 2.3719070

0 -3.9866780 -9.1 131280 1 .8773520 c 6.1539430 6.1251260 2.7025800 c -5.9436790 -10.5166130 2.1239020 c 4.3350160 8.2152320 2.6157120 c -1.4795060 -8.8753290 0.3094330 c 6.5657220 7.4886250 2.9559910 c -4.9986160 -9.5443020 2.7963530 N 7.1501140 5.2568290 2.8228490 c -0.2859350 -8.7645660 -0.4134690 C 5.6240030 8.5745460 2.8983490 s -1.8141520 -7.3630830 1 .1389500 N 7.85391 10 7.5854880 3.25841 10 c 0.3273610 -7.5276460 -0.3073570 S 8.4817120 6.0925150 3.2234320

0 0.2220430 -9.7795550 -1.1434530 C 6.0318570 9.9744020 3.1 153560 c -0.3582370 -6.6186410 0.5033970 C 7.2638210 10.4453400 2.7546670

0 1 .4833940 -7.2219450 -0.9378440 C 5.1490230 10.9461960 3.7007660 c 1 .5909480 -9.5684750 -1.5063680 C 7.6705120 11 .7958930 2.9243760 c 0.0155570 -5.2959690 0.7872850 C 5.5714230 12.3169390 3.8936990 c 1 .7967800 -8.1465260 -1.9827880 N 3.9121170 10.7260210 4.1276120 c -0.6804500 -4.3830650 1 .5757830 C 6.8778410 12.7578290 3.4855420 s 1 .4714510 -4.5412220 0.1546060 N 4.6312500 13.0685190 4.4517450 c -0.0690620 -3.1332850 1 .6722340 S 3.33901 10 12.1261630 4.7124580

0 -1.8410080 -4.6820880 2.1918940 C 7.3285830 14.1488370 3.6736460

5 TABLE FIFTEEN (cont'd) TABLE FIFTEEN (cont'd)

EDOT-b-BT +1 EDOT-b-BT +1

X Y Z X Y Z

c 6.9413120 14.9122300 4.7394200 H -1.5668240 -17.2680670 -2.8152360 c 8.2255810 14.7890570 2.7508020 H -2.2091700 -14.9322900 -3.4168620 c 7.3853400 16.2449620 4.9536720 H -0.5522610 -14.9496280 -2.7646190 c 8.6593940 16.1540050 2.9571960 H -6.4246440 -10.0484640 1 .2600610

N 8.7308890 14.2514650 1 .6478460 H -6.7075720 -10.8623410 2.8175330

C 8.2272400 16.9063340 4.1037230 H -4.5154960 -10.0126810 3.6578680

N 9.4768400 16.581 1880 2.0034970 H -5.5190770 -8.6444990 3.1 179770

S 9.6714070 15.3701240 0.9444680 H 2.2234170 -9.7778140 -0.6394400

C 8.6538870 18.2991490 4.3321720 H 1 .8104390 -10.2847450 -2.2954970

C 8.8868810 19.1769600 3.3107680 H 1 .161 1760 -7.9361140 -2.8475000

C 8.8410810 18.8301510 5.6548770 H 2.8369570 -7.9676080 -2.2473780

C 9.2724760 20.5304250 3.5104840 H -3.0415850 -3.0379970 1 .8502910

C 9.2344010 20.2079530 5.8578610 H -3.2697950 -3.8946090 3.3946410

N 8.7142310 18.1597130 6.7928480 H -1.0492700 -3.0604430 4.1793670

C 9.4497650 21 .091 1790 4.7440400 H -2.0733520 -1.6828210 3.7096850

N 9.3863370 20.5133810 7.1401920 H 5.6804850 -2.8601690 -0.0241900

S 9.0623010 19.1805210 8.0039900 H 5.2558930 -3.3554890 -1.6811 190

C 9.8267420 22.5066970 4.9261300 H 4.6247660 -0.9959030 -2.2131750

C 9.3896000 23.2497400 5.9883250 H 6.3061600 -1.0535840 -1.6332430

C 10.6685750 23.1925780 3.9799680 H 5.4807860 1 .5637170 0.6705040

C 9.7220730 24.6254850 6.1710860 H 6.1699790 3.8022660 1 .2255890

C 11 .0088310 24.5806270 4.1766130 H 2.8843770 6.7068960 2.1564960

N 11 .2254000 22.6809490 2.8881940 H 3.5742480 8.9804080 2.5733010

C 10.5123240 25.2978070 5.2978820 H 7.9798870 9.7645880 2.3182360

N 11 .8039000 25.0676570 3.2319420 H 8.6593720 12.0638050 2.5826790

S 12.0937610 23.861 1020 2.1881240 H 6.2589810 14.4941850 5.4650560

H -7.0290640 -20.2881460 -0.5282590 H 7.0349850 16.7481380 5.8429170

H -9.8106230 -17.1000930 0.7470150 H 8.7774340 18.8380470 2.2910440

H -10.0811670 -17.9139670 2.3052680 H 9.4349260 21 .1353550 2.6304880

H -7.8848720 -17.0564580 3.1280460 H 8.7660690 22.7795370 6.7346860

H -8.9105140 -15.6973970 2.6066680 H 9.3227660 25.1345440 7.0407940

H -1.2136400 -16.7411480 -1.1524390 H 10.7749760 26.3400260 5.4255870

TABLE SIXTEEN TABLE SIXTEEN (cont'd)

EDOT-b-BT -1 EDOT-b-BT -1

X Y Z X Y Z

c -6.7611580 -19.3777230 -0.5013700 c 1 .2792160 -3.1006510 1 .0837060 c -7.4441630 -18.5409880 0.3149690 0 -0.3670970 -2.2419010 2.6192950 s -5.3480010 -18.6207440 -1.1428640 c -2.2845320 -3.6707340 2.9203240 c -6.8265830 -17.2618770 0.4334960 c 2.1452240 -1.9524010 0.9918430

0 -8.5894010 -18.8583490 0.9822960 c -1.2986500 -2.7284300 3.5766290 c -5.6750160 -17.1290620 -0.2914810 c 3.2816820 -1.8286050 0.2413600

0 -7.3603070 -16.2656190 1 .1960930 s 1 .8501800 -0.471 1410 1 .8668440 c -9.2752000 -17.7078590 1 .4636780 c 3.9190040 -0.5709680 0.3648180 c -4.8128720 -15.9746980 -0.3788340 0 3.7549610 -2.8182590 -0.5708470 c -8.3128670 -16.7515940 2.1348420 c 3.2837750 0.2972140 1 .2202440 c -3.6644980 -15.8492550 -1.1079640 0 5.0710480 -0.2904140 -0.3162320 s -5.1244100 -14.4926350 0.4960200 c 5.1053600 -2.6108720 -0.9624280 c -3.0333770 -14.5881780 -0.9755170 c 3.6987680 1 .6444470 1 .5861760

0 -3.1633120 -16.8329340 -1.9075770 c 5.3041010 -1.1775720 -1.4017700 c -3.6888200 -13.7239850 -0.1432220 c 4.9141620 2.1780970 1 .2246250

0 -1.8687990 -14.2884620 -1.6186890 c 2.8713360 2.5233750 2.361 1210 c -1.8033590 -16.6101050 -2.2663410 c 5.3279580 3.4890230 1 .5534410 c -3.3160700 -12.3727850 0.1918250 c 3.2908090 3.8731310 2.6966480 c -1.5991420 -15.1740030 -2.6986550 N 1 .6842280 2.2107130 2.8550760 c -3.9708500 -11 .5084770 1 .0245800 c 4.5693860 4.3905310 2.2665860 s -1.8942520 -11 .5942560 -0.4679260 N 2.3921940 4.5063310 3.4367050 c -3.3535070 -10.2392780 1 .1388660 s 1 .1394640 3.5029680 3.6802520

0 -5.1085840 -11 .8273090 1 .7040700 c 5.0123510 5.7547940 2.5532470 c -2.2114970 -10.1078280 0.3979820 c 4.1357870 6.7936270 2.8021890

0 -3.8750280 -9.2453820 1 .9137620 c 6.3989670 6.1369770 2.5688570 c -5.7900010 -10.6812550 2.2033930 c 4.5180120 8.1242530 3.0256350 c -1.3485350 -8.9579160 0.3058810 c 6.8057580 7.5199740 2.8072100 c -4.8139590 -9.7319670 2.8645640 N 7.4306910 5.3195010 2.4161870 c -0.2065190 -8.8304490 -0.4355510 C 5.8322440 8.5754650 3.0239660 s -1.6456590 -7.4773520 1 .1912270 N 8.1212450 7.6560120 2.8297980 c 0.4288010 -7.5724520 -0.3034040 S 8.7940810 6.1989040 2.5685330

0 0.2836000 -9.8108190 -1.2461400 C 6.1956620 9.9662770 3.2075510 c -0.2149880 -6.7095560 0.5401790 C 7.4503800 10.4758230 2.8692730

0 1 .5878990 -7.2722640 -0.9571550 C 5.2883280 10.9630730 3.7270430 c 1 .6396810 -9.5894610 -1.6183080 C 7.8268690 11 .8078320 2.9890340 c 0.1656480 -5.3617800 0.8775300 C 5.6936620 12.3645990 3.8871580 c 1 .84291 10 -8.1514090 -2.0449040 N 4.0456490 10.7485730 4.1267370 c -0.4790380 -4.4988420 1 .7202390 C 7.0120850 12.8261790 3.4956300 s 1 .5837210 -4.5843270 0.2081680 N 4.7252650 13.1096130 4.3913180 c 0.1435140 -3.2325160 1 .8351400 S 3.4227580 12.1625180 4.6536870

0 -1.6121 160 -4.8169490 2.4073940 C 7.4466040 14.1967180 3.6200180

5 TABLE SIXTEEN (cont'd) TABLE SIXTEEN (cont'd)

EDOT-b-BT -1 EDOT-b-BT -1

X Y Z X Y Z

c 6.7457050 15.1584740 4.3531580 H -1.5843200 -17.3015070 -3.0791600 c 8.6539630 14.7147230 3.0001440 H -2.2577810 -14.9377670 -3.5413760 c 7.1463940 16.4828240 4.5100080 H -0.5651810 -14.9950620 -2.9911020 c 9.0509060 16.1190590 3.1409280 H -6.3072630 -10.1754580 1 .381 1730

N 9.4979440 14.0323900 2.2458870 H -6.5259020 -11 .0499730 2.9170590

C 8.2821100 17.0444570 3.9344630 H -4.2846390 -10.2425350 3.6763780

N 10.1686300 16.3982490 2.4889420 H -5.3259860 -8.8578400 3.2650360

S 10.6862650 15.0350010 1 .7561160 H 2.2949080 -9.8259770 -0.7732080

C 8.6399430 18.4452640 4.0920470 H 1 .8481300 -10.2770870 -2.4372150

C 9.4948130 19.1107800 3.2307790 H 1 .1753070 -7.9090680 -2.8789320

C 8.1266070 19.2770450 5.1637000 H 2.8739690 -7.9733280 -2.3482060

C 9.8255740 20.4749320 3.3402120 H -2.8080450 -3.1589440 2.1059000

C 8.4689470 20.6909710 5.2666420 H -3.0145190 -4.0412150 3.6391490

N 7.3495100 18.8767970 6.1573870 H -0.7638170 -3.2446670 4.3812600

C 9.3444480 21 .3178400 4.3158960 H -1.8024560 -1.8536460 3.9857100

N 7.921 1550 21 .2763500 6.3226970 H 5.7723270 -2.8426260 -0.1249100

S 7.0621270 20.1493130 7.1251370 H 5.2994090 -3.3062040 -1.7785750

C 9.6771340 22.7483980 4.3682260 H 4.6213990 -0.9401140 -2.2249530

C 8.8348600 23.6841900 4.9157510 H 6.3294960 -1.0017220 -1.7256710

C 10.9148660 23.2723260 3.8345410 H 5.6009730 1 .5737740 0.6515510

C 9.1238410 25.0783870 4.9538320 H 6.3087160 3.7918500 1 .2215300

C 11 .2014570 24.6905370 3.8825070 H 3.0769040 6.5832920 2.8162180

N 11 .9043150 22.5773120 3.2878560 H 3.7314970 8.8401220 3.1978340

C 10.2720710 25.6000620 4.4522140 H 8.1915430 9.7959520 2.4820660

N 12.3817530 25.011 1500 3.3676930 H 8.8215040 12.0639260 2.6655750

S 13.0727780 23.6252340 2.8716750 H 5.8296670 14.8637660 4.8362900

H -7.0138330 -20.3941190 -0.7574180 H 6.5188940 17.1090280 5.1242050

H -9.7814710 -17.2050140 0.6321650 H 9.9364130 18.5589280 2.4171760

H -10.0228120 -18.0701340 2.1688430 H 10.4979040 20.8744950 2.5951330

H -7.7935870 -17.2558780 2.9570270 H 7.9045900 23.3509620 5.3497750

H -8.8335990 -15.8771370 2.5230850 H 8.3858030 25.7353190 5.4018200

H -1.1569830 -16.8406130 -1.4128730 H 10.5014460 26.6576360 4.4767680

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Claims

1 . An electropolymenzable monomer of formula (A):

wherein:

(A) X is S, O, Se, Te, NH, N(C_1-30-alkyl) or -CR^5'CR^6'- and the fused rings

together form a bicyclic aromatic system;

(B) Z is S, O, Se, Te, NH, or N(Ci_-30-alkyl);

(C) (i) each of R¹, R², R³, R⁴, R⁵, R^5', R⁶ and R^6' is, independently of the other, selected from the group consisting of:

hydrogen,

optionally substituted Ci-3o-alkyl,

optionally substituted C₂-3o-alkenyl,

optionally substituted C₂-3o-alkynyl,

optionally substituted C3-₂o-cycloalkyl,

(CH₂CH₂0)a-(CH₂)_b-CH₃ for a = 1 -100 and b = 0-100, optionally substituted aryl,

wherein each said optional substitution is made independently and up to six times for each R¹, R², R³, R⁴, R⁵ and R⁶, and substituents are selected from:

halogen,

-CN,

-N0₂,

-OH,

C-i-io-alkoxy, -0-CH₂CH₂0-Ci.io-alkyl_I

-O-COX¹,

-S-C-i-io-alkyl,

-NH₂,

-NHX¹ ,

-NX¹X²,

-NHC(0)X¹,

-C(0)OH,

-C(0)OR⁷S,

-C(0)NH₂,

-C(0)NHX¹,

-C(0)NX¹X²,

-C(0)H,

C(0)X¹ ,

Ci-io-alkyl,

C₂-io-alkenyl,

C_2-io-alkynyl,

C3-i₄-cycloalkyl, including bicycloalkyl,

3-14 membered cycloheteroalkyl,

5-14 membered heteroaryl,

wherein each X¹ and X² is independently of the other C-I.-IO- alkyl, C_2-io-alkenyl, C_2-io-alkynyl, C_{3- 0}-cycloalkyl, C_{5- 0}- cycloalkenyl, 3-14 membered cycloheteroalkyl, C_6-i₄- aryl or 5-14 membered heteroaryl;

(ii) R¹ and R² are as defined in (i) and R³ and R⁴ together, are -CH₂CH₂-, or -CH₂CH₂CH₂-, or -CH₂C(R⁸)₂CH₂- where R⁸ is a group defined in (i); or

(iii) R¹ and R² together, and R³ and R⁴ together, are -CH₂CH₂-, or

-CH₂CH₂CH₂-, or -CH₂C(R⁸)₂CH₂- where R⁸ is a group defined in (i); and

(D) n = 1 or 2, or 3, or 4, or 5; and

including salts of the foregoing.

2. A conjugated polymer containing units having structural formula (B):

wherein R¹ , R², R³, R⁴, R⁵, R^5', R⁶ and R^6', X, Z and n are each defined as in claim 1 , and m is an integer from 2 to 1000.

3. The conjugated polymer of claim 2, wherein m is between 10 and 900.

4. A polymer having a fully conjugated backbone, the polymer being the

electropolymerization product of a monomer as defined by claim 1 .

5. An electrically conductive polymer comprising conjugated polybenzothiadiazole and polythiophene segments.

6. The polymer of claim 5, wherein the thiophene units of the polythiophene segments are as defined in claim 1 .

7. The polymer of claim 5 or 6, wherein the benzothiadiazole units of the

polybenzothiadiazole segments are as defined in claim 1 where X = S.

8. The polymer of any one of claims 5 to 7, wherein the mole ratio of

thiophene:benzothiadiazole units is from 2: 1 to 1 : 1 .

9. The polymer of claim 8, wherein the benzothiadiazole units are unsubstituted.

10. The polymer of claim 8 or 9, wherein the thiophene units are 3,4- dimethoxythiophene or 3,4-ethylenedioxythiophene.

1 1 . An electrically conductive polymer comprising: conjugated polybenzotriazole and polythiophene segments; conjugated polybenzoxadiazole and polythiophene segments; conjugated polybenzoselenadiazole and polythiophene segments; or conjugated polybenzotelluradiazole and polythiophene segments.

12. The polymer of claim 1 1 , wherein the thiophene units of the polythiophene segments are as defined in claim 1 .

13. The polymer of claim 1 1 or 12, wherein the benzotriazole units of the

polybenzotriazole segments are as defined in claim 1 where X = NH or N(Ci-3o-alkyl).

14. The polymer of any one of claims 1 1 to 13, wherein the mole ratio of

thiophene:benzotriazole units is from 2: 1 to 1 :1 .

15. The polymer of claim 14, wherein the benzotriazole units are unsubstituted.

16. The polymer of claim 1 1 or 12, wherein the benzoxadiazole units of the polybenzoxadiazole segments are as defined in claim 1 where X = O.

17. The polymer of any one of claims 1 1 , 12 or 16, wherein the mole ratio of thiophene:benzoxadiazole units is from 2: 1 to 1 :1 .

18. The polymer of claim 17, wherein the benzoxadiazole units are unsubstituted.

19. The polymer of claim 1 1 or 12, wherein the benzoselenadiazole units of the polybenzoselenadiazole segments are as defined in claim 1 where X = Se.

20. The polymer of any one of claims 1 1 , 12 or 19, wherein the mole ratio of thiophene:benzoselenadiazole units is from 2: 1 to 1 :1 .

21 . The polymer of claim 20, wherein the benzoselenadiazole units are

unsubstituted.

22. The polymer of claim 1 1 or 12, wherein the benzotelluradiazole units of the polybenzotelluradiazole segments are as defined in claim 1 where X = Te.

23. The polymer of any one of claims 1 1 , 12 or 22, wherein the mole ratio of thiophene:polybenzotelluradiazole units is from 2: 1 to 1 : 1 .

24. The polymer of claim 23, wherein the benzotelluradiazole units are

unsubstituted.

25. The polymer of any one of claims 14 to 24, wherein the thiophene units are 3,4- dimethoxythiophene or 3,4-ethylenedioxythiophene.

26. A method of polymerization, the method comprising electropolymerizing a monomer (D-A-D) comprising a quinoxaline acceptor unit (A) covalently linked to two alkoxythiophene donor units (D), wherein the polymer formed has the structure poly(D-A-D) in which the acceptor and donor units are conjugated with each other.

27. A method of polymerization, the method comprising electropolymerizing a monomer (D-A-A-D) comprising a pair of benzothiadiazole acceptor units (A-A), each covalently linked to an alkoxythiophene donor unit (D), wherein the polymer formed has the structure poly(D-A-A-D) in which the acceptor and donor units are conjugated with each other.

28. The method of claim 26 or 27, wherein the monomer is contained in a nonaqueous solution and the polymer is electropolymerized onto an electrically conductive substrate.

29. The method of claim 28, wherein the substrate is a metal electrode or carbon.

30. The method of claim 28 or 29, wherein the product is for use as a component of an electrical device.

31 . The method of claim 30, wherein the device is a supercapacitor, preferably a Type I II supercapacitor.

32. The method of any one of claims 26 to 31 , wherein the polymer is formed to a thickness of at least 0.001 μιη.

33. The method of claim 32, wherein said thickness is 0.001 and 10,000 μιη.

34. A method of preparing a monomer from precursors having formulas (A1 ) and

(A1 ) (D1 )

wherein the method comprises:

in an anaerobic environment, combining a palladium catalyst having an organic ligand, and precursors A1 and D1 , and obtaining a conjugated monomer containing quinoxaline and thiophene units with the formula D1 -A1 -D1 : O / O

(D1 -A1-D1 )

wherein each of X, Z and R¹ , R², R⁵, R^5', R⁶ and R^6' are defined as in claim 1 ; and each Y is a halogen atom, tosylate, or mesylate and can be the same or different from each other.

35. The method of claim 34, wherein the catalyst comprises palladium acetate.

36. The method of claim 34 or 35, wherein the combined mixture further comprises an organic acid.

37. The method of any one of claims 34 to 36, wherein the organic acid is pivalic acid.

38. The method of any one of claims 34 to 37, further comprising heating the combined mixture to above 25°C.

39. The method of claim 38, wherein the mixture is heated for at least one hour.

40. The method of any one of claims 34 to 39, wherein the combined mixture further comprises a base.

41 . The method of claim 40, wherein the base is potassium carbonate.

42. An electrode comprising a polymer as defined by any one of claims 2 to 25, the polymer being electropolymerized onto a supporting metal or carbon fiber or other conductive substrate, wherein the specific power of the polymer is at least 0.1 kW/kg, when measured in a Type III supercapacitor.

43. An electrode comprising a polymer that is the electropolymerization product of a monomer as defined by claim 1 , wherein the specific power of the polymer is at least 0.1 kW/kg, when measured in a Type III supercapacitor.

44. An electrode comprising a polymer as defined by any one of claims 2 to 25, the polymer being electropolymerized onto a supporting metal, carbon fiber or other conductive substrate, wherein the specific energy of the polymer is at least 0.76 Wh/kg, when measured in a Type III supercapacitor.

45. An electrode comprising a polymer that is the electropolymerization product of a monomer as defined by claim 1 , wherein the specific energy of the polymer is at least 0.76 Wh/kg, when measured in a Type III supercapacitor.

46. An electrode comprising a polymer as defined by any one of claims 2 to 25, the polymer being electropolymerized onto a supporting metal or carbon fiber or other conductive substrate, wherein the power density of the polymer is at least 0.01 kW/L, when measured in a Type II I supercapacitor.

47. An electrode comprising a polymer that is the electropolymerization product of a monomer as defined by claim 1 , wherein the power density of the polymer is at least 0.01 kW/L, when measured in a Type I II supercapacitor.

48. An electrode comprising a polymer as defined by any one of claims 2 to 25, the polymer being electropolymerized onto a supporting metal or carbon fiber or other conductive substrate, wherein the energy density of the polymer is at least 0.1 Wh/L, when measured in a Type III supercapacitor.

49. An electrode comprising a polymer that is the electropolymerization product of a monomer as defined by claim 1 , wherein the energy density of the polymer is at least 0.1 Wh/L, when measured in a Type III supercapacitor.

50. An electrode comprising a polymer as defined by any one of claims 2 to 25, the polymer being electropolymerized onto a supporting metal or carbon fiber or other conductive substrate, wherein the electrode has an average capacitance calculated from the discharge measurement of a galvanostatic charge-discharge experiment at 0.5 A/g of at least 17 F/g.

51 . The electrode of any one of claims 42 to 50, wherein the electrode is a component of a supercapacitor.