Borylated compounds

Abstract

Borylated compounds are disclosed, as well as their methods of preparation and their applications. The disclosed borylated compounds are highly stable, and have reduced band gap properties, thereby making them attractive candidates for incorporation into semiconducting materials for use in a variety of electronic, optical or electro-optical devices or components.

Claims

1. A compound comprising one or more moieties of formulae (I)-(V): ##STR00063## wherein: R.sub.1, R.sub.2, R.sub.3 and R.sub.4 are each independently selected from the group consisting of hydrogen, fluoro, chloro, bromo, substituted or unsubstituted (1-10C)alkyl, substituted or unsubstituted (2-10C)alkenyl, substituted or unsubstituted (2-10C)alkynyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted amino, substituted or unsubstituted (1-10C)alkoxy, substituted or unsubstituted arylalkoxy, and hydroxyl; each .sub.a independently is a -conjugated -donor ring system formed from one, two, three or four rings selected from the group consisting of 6-membered aryl rings and 5 to 6-membered heteroaryl rings; when taken in combination, each .sub.b and .sub.c independently forms a moiety .sub.bc selected from the group consisting of: ##STR00064## wherein moieties .sub.bc1 and .sub.bc4 are directly bonded to 1 or 2 boron atoms via either or both nitrogen atoms respectively; moieties .sub.bc1 and .sub.bc4 are directly bonded to 1 or 2 .sub.a moieties via either or both C*; any or all of the rings forming .sub.a and .sub.bc may be independently optionally substituted with one more ring substituents selected from the group consisting of halo, (1-20C)alkyl, (2-20C)alkenyl, (2-20C)alkynyl, aryl, heteroaryl, cycloalkyl, heterocyclyl, carboxyl, phosphoryl, sulfonyl, hydroxyl, (1-20C)alkoxy, nitro, amino, mercapto, silyl, siloxy, azido, boronic acid group, sulfonic acid group, hydroxamic acid group, cyanoacrylate group, and dioxocyclobutenyl group having at least one functional group selected from the group consisting of a carboxyl, phosphoryl, sulfonyl, hydroxyl, alkoxy, nitro, amino, mercapto, silyl, siloxy, azido, boronic acid group, sulfonic acid group, hydroxamic acid group and cyanoacrylate group, and the bond linking B to N in the moieties of formulae (I)-(V) is covalent or coordinate covalent.

2. The compound of claim 1, wherein any or all of the rings forming .sub.a and .sub.bc may be independently optionally substituted with one more ring substituents selected from the group consisting of halo, (1-10C)alkyl, (2-10C)alkenyl, (2-10C)alkynyl, aryl, heteroaryl, cycloalkyl, heterocyclyl, carboxyl, hydroxyl, (1-10C)alkoxy and amino.

3. The compound of claim 1, wherein any or all of the rings forming .sub.a and .sub.bc may be independently optionally substituted with one more ring substituents selected from the group consisting of halo, (1-10C)alkyl, (2-10C)alkenyl, (2-10C)alkynyl, aryl, heteroaryl, cycloalkyl and heterocyclyl.

4. The compound of claim 1, wherein any or all of the rings forming .sub.a may be independently optionally substituted with one or more ring substituents selected from the group consisting of bromo and (1-8C)alkyl.

5. The compound of claim 1, wherein R.sub.1, R.sub.2, R.sub.3 and R.sub.4 are each independently selected from the group consisting of hydrogen, fluoro, chloro, bromo, substituted or unsubstituted (1-10C)alkyl, substituted or unsubstituted (2-10C)alkenyl, substituted or unsubstituted (2-10C)alkynyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, and hydroxyl.

6. The compound of claim 1, wherein R.sub.1, R.sub.2, R.sub.3 and R.sub.4 are each independently selected from the group consisting of hydrogen, fluorine, substituted or unsubstituted (1-10C)alkyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, and hydroxyl.

7. The compound of claim 1, wherein when taken in combination, each .sub.b and .sub.c independently forms the moiety .sub.bc1 shown below: ##STR00065## wherein each moiety .sub.bc1 is independently optionally substituted with one or more ring substituents selected from the group consisting of halo, (1-20C)alkyl, (2-20C)alkenyl, (2-20C)alkynyl, aryl, heteroaryl, cycloalkyl, heterocyclyl, carboxyl, phosphoryl, sulfonyl, hydroxyl, (1-20C)alkoxy, nitro, amino, mercapto, silyl, siloxy, azido, boronic acid group, sulfonic acid group, hydroxamic acid group, cyanoacrylate group, and dioxocyclobutenyl group having at least one functional group selected from the group consisting of a carboxyl, phosphoryl, sulfonyl, hydroxyl, alkoxy, nitro, amino, mercapto, silyl, siloxy, azido, boronic acid group, sulfonic acid group, hydroxamic acid group and cyanoacrylate group.

8. The compound of claim 1, wherein each .sub.a is independently formed from one, two or three rings selected from the group consisting of 6-membered aryl rings and 5 to 6-membered heteroaryl rings, and wherein any or all of the rings are optionally substituted with one or more ring substituents as claimed in claim 1.

9. The compound of claim 1, wherein each .sub.a is a moiety independently selected from the group consisting of: ##STR00066## wherein moieties .sub.a1, .sub.a2, .sub.a3, .sub.a4, .sub.a5 and .sub.a6 are independently optionally substituted with one or more ring substituents as claimed in claim 1.

10. The compound of claim 1, wherein each .sub.a is a moiety independently selected from the group consisting of: ##STR00067## wherein i) moieties .sub.a1, .sub.a2, .sub.a3 and .sub.a6 are directly bonded to 1 or 2 .sub.b moieties via either or both of C1; and moieties .sub.a1, .sub.a2, .sub.a3 and .sub.a6 are directly bonded to 1 or 2 boron atoms via either or both of C2; or ii) moieties .sub.a1, .sub.a2, .sub.a3 and .sub.a6 are directly bonded to 1 or 2 .sub.b moieties via either or both of C2; and moieties .sub.a1, .sub.a2, .sub.a3 and .sub.a6 are directly bonded to 1 or 2 boron atoms via either or both of C1; and moieties .sub.a1, .sub.a2, .sub.a3 and .sub.a6 are independently optionally substituted with one or more ring substituents as claimed in claim 1.

11. The compound of claim 1, wherein the compound comprises one or more moieties selected from the group consisting of: ##STR00068## ##STR00069## wherein R.sub.1, R.sub.2, R.sub.3 and R.sub.4 are independently as defined in claim 1; R.sub.a, R.sub.b, R.sub.c and R.sub.d are independently selected from the group consisting of hydrogen, (1-20C)alkyl, (2-20C)alkenyl and (2-20C)alkynyl; and each X is hydrogen, or is independently: (i) bromo, (1-10C)alkyl, (2-10C)alkenyl or (2-10C)alkynyl; or (ii) another moiety having one of the structural formulae defined above.

12. The compound of claim 11, wherein R.sub.1, R.sub.2, R.sub.3 and R.sub.4 are each independently selected from the group consisting of hydrogen, fluoro, chloro, bromo, substituted or unsubstituted (1-10C)alkyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, and hydroxyl; R.sub.a, R.sub.b, R.sub.c and R.sub.d are independently selected from the group consisting of hydrogen and (1-10C)alkyl; and each X is hydrogen, or is independently: (i) bromo or (1-10C)alkyl; or (ii) another moiety having one of the structural formulae (I)-(V).

13. The compound of claim 1, wherein the compound is a polymer or oligomer comprising two or more moieties of formulae (I)-(V).

14. A method of preparing a compound comprising one or more moieties of any of formulae (I)-(V) as claimed in claim 1, the method comprising the steps of: a) reacting a moiety of any of formulae (I)-(V) shown below with a reagent BX.sub.3: ##STR00070## wherein moieties .sub.a, .sub.b and .sub.c are independently as defined in claim 1; and each X is selected from the group consisting of Cl, Br, aryl and heteroaryl; b) reacting the product of step a) with a weak nucleophile in the presence or absence of a halophilic Lewis acid: and c) performing one or more subsequent steps on the product of step b) to functionalise the boron atom with or more R.sub.1, R.sub.2, R.sub.3 and R.sub.4 groups as defined in claim 1.

15. The method of claim 14, wherein the weak nucleophile is 2,4,6-tri-tert-butylpyridine.

16. The method of claim 14, wherein each X is selected from the group consisting of Cl and Br, and the halophilic Lewis acid is a halophilic main group Lewis acid.

17. The method of claim 14 wherein the reaction of step b) is additionally performed in the presence of a chloride donor.

18. The method of claim 14, further comprising the step d) of linking the product of step c) with one or more other moieties of formulae (I)-(V).

19. A method of preparing a compound comprising one or more moieties of formula (I) as claimed in claim 1, the method comprising the steps of: a) reacting a compound comprising one or more moieties of formula (I) shown below with a reagent BX.sub.3: ##STR00071## wherein moieties .sub.a, .sub.b and .sub.c are independently as defined in claim 1; and each X is selected from the group consisting of Cl, Br, aryl and heteroaryl; and b) performing one or more subsequent steps on the product of step b) to functionalise the boron atom with or more R.sub.1, R.sub.2, R.sub.3 and R.sub.4 groups as defined in claim 1.

20. The method of claim 19, furthering comprising the step c) of linking the product of step b) with one or more other moieties of formulae (I)-(V).

21. The method claim 14, wherein the compound comprising one or more moieties of formulae (I)-(V) is a polymer or oligomer.

22. A semiconducting material comprising a compound as claimed in claim 1.

23. An electro, optical or electro-optical device or component comprising a semiconducting material as claimed in claim 22.

Description

EXAMPLES

(1) One or more examples of the invention will now be described, by way of illustrations only, with reference to the accompanying figures, in which:

(2) FIG. 1 shows absorption and emission spectra for the unborylated BT-F8-BT.

(3) FIG. 2 shows absorption and emission spectra for borylated compound 29.

(4) FIG. 3 shows absorption and emission spectra for borylated compound 30.

(5) FIG. 4 shows a comparison of the absorption and emission spectra for unborylated BT-F8-BT and compounds 29 and 30.

(6) FIG. 5 shows absorption and emission spectra for borylated compound 26.

(7) FIG. 6 solid state photoluminescence spectra of thin films from a 5 wt % mixture of borylated compounds 45, 29 and 30 dispersed in PF8-BT polymer (poly(9,9-dioctylfluorene-alt-benzothiadiazole) spin coated from toluene, excited at 468 nm.

(8) FIG. 7 shows absorption and emission spectra for borylated compounds 41, 42 and 43 dissolved in toluene.

(9) FIG. 8 shows the X-ray structure for the unborylated BT-F8-BT.

(10) FIG. 9 shows the X-ray structure for the borylated compound 29

(11) FIG. 10 shows the X-ray packing structure of compounds 29.

(12) FIG. 11 shows the X-ray structure for the borylated compound 30.

(13) FIG. 12 shows the X-ray packing structure of compounds 30.

(14) FIG. 13 shows the X-ray structure for the borylated compound 22.

(15) FIG. 14 shows the X-ray packing structure of compounds 22.

(16) FIG. 15 shows the X-ray packing structure of compounds 35.

(17) FIG. 16 shows computational modelling of the molecular orbital of compound 29.

(18) FIG. 17 shows the cyclic voltammogram for compound 22.

(19) FIG. 18 shows the cyclic voltammograms for compounds 2, 9, 11, 39, and 12.

EXAMPLE 1PREPARATION OF COMPOUNDS

(20) Synthesis of 1

(21) ##STR00019##

(22) 4,7-dibromobenzo[c][1,2,5]thiadiazole (2.54 g, 8.65 mmol), trimethyl(5-methylthiophen-2-yl)stannane (4.57 g, 17.3 mmol) and Pd(PPh.sub.3).sub.4 (1.00 g, 0.86 mmol) were mixed in dry toluene (50 ml) under an nitrogen atmosphere and stirred for 24 h at 100 C. under reflux. The mixture was cooled to room temperature and then diluted with DCM (150 mL). The reaction mixture was then washed with brine (1100 mL), water (3100 mL), and then dried over MgSO.sub.4. After evaporating the solvent, the residue was purified by column chromatography on silica gel [eluent: hexane/DCM (3/2)] to afford 1 as a red powder. Yield: 0.981 g, 34%.

(23) .sup.1H NMR (400 MHz, CDCl.sub.3) =7.91 (d, J=3.6 Hz, 2H), 7.78 (s, 2H), 6.87 (dd, J=1.2, 4.6 Hz, 2H), 2.59 (s, 3H) ppm.

(24) Synthesis of 2

(25) ##STR00020##

(26) 4,7-dibromobenzo[c][1,2,5]thiadiazole (2.00 g, 6.80 mmol), tri.sup.nbutyl(5-octylthiophen-2-yl)stannane (7.26 g, 14.96 mmol) and PdCl.sub.2(PPh.sub.3).sub.2 (0.48 g, 0.68 mmol) were mixed in dry THF (60 ml) under an nitrogen atmosphere and stirred for 22 h at 80 C. under reflux. The mixture was cooled to room temperature and then diluted with DCM (200 mL). The reaction mixture was then washed with saturated NaHCO.sub.3 solution (1100 mL), brine (1200 mL), water (1200 mL), and then dried over MgSO.sub.4. After evaporating the solvent, the residue was purified by column chromatography on silica gel [eluent: hexane/chloroform (4/1)] to afford 2 as an orange powder. Yield: 1.08 g, 30%.

(27) .sup.1H NMR (400 MHz, CDCl.sub.3) =7.94 (d, J=3.6 Hz, 2H), 7.79 (s, 2H), 6.88 (d, J=3.6 Hz, 2H), 2.90 (t, J=7.6, 4H), 1.76 (m, 4H), 1.47-1.22 (m, 20H), 0.89 (t, J=7.2, 6H);

(28) .sup.13C NMR (101 MHz, CDCl.sub.3) =152.62, 147.80, 136.84, 127.32, 125.75, 125.22, 125.12, 31.90, 31.70, 30.33, 29.39, 29.28, 29.20, 22.70, 14.16;

(29) MALDI-TOF: calc. for C.sub.36H.sub.44BN.sub.2S.sub.3.sup.+ 524.2, found 523.9.

(30) Synthesis of 3

(31) ##STR00021##

(32) 4,7-dibromobenzo[c][1,2,5]thiadiazole (1.36 g, 4.6 mmol), tri.sup.nbutyl(9,9-dioctyl-9H-fluoren-2-yl)-stannane, (6.70 g, 10.2 mmol) and PdCl.sub.2(PPh.sub.3).sub.2 (0.33 g, 0.047 mmol) were mixed in dry THF (80 ml) under an nitrogen atmosphere and stirred for 36 h at 80 C. under reflux. The mixture was cooled to room temperature and then diluted with ethyl acetate (100 mL). The reaction mixture was then washed with brine (2100 mL), water (2200 mL), and then dried over MgSO.sub.4. After evaporating the solvent, the residue was purified by column chromatography on silica gel [eluent: hexane/DCM (9/1)] to afford 3 as a yellow viscous oil. Yield: 1.73 g, 41%.

(33) .sup.1H NMR (500 MHz, CDCl.sub.3) =8.04 (dd, J=1.5, 8 Hz, 2H), 7.96 (d, J=1.0 Hz, 2H), 7.90 (s, 2H), 7.88 (d, J=8 Hz, 2H), 7.79 (dd, J=1.0, 6.5, 2H), 7.41-7.33 (m, 6H), 2.05 (m, 8H), 1.25-1.07 (m, 40H), 0.81 (t, J=7.0, 6H), 0.79 (m, 8H);

(34) .sup.13C NMR (126 MHz, CDCl.sub.3) =154.4, 151.3, 151.1, 141.3, 140.7, 136.2, 133.6, 128.1, 127.9, 127.2, 126.8, 123.9, 123.0, 119.9, 119.7, 55.2, 40.3, 31.8, 30.1, 29.2, 29.2, 23.9, 22.6, 14.0;

(35) MALDI-TOF: calc. for C.sub.64H.sub.84N.sub.2S.sup.+ 913.4, found 913.4.

(36) Synthesis of 4

(37) ##STR00022##

(38) 4,7-dibromobenzo[c][1,2,5]thiadiazole (2.7 g, 9.3 mmol), tri.sup.nbutyl(9,9-dioctyl-9H-fluoren-2-yl)-stannane, (75 g, 11 mmol) and PdCl.sub.2(PPh.sub.3).sub.2 (0.64 g, 0.092 mmol) were mixed in dry THF (80 ml) under an nitrogen atmosphere and stirred for 36 h under reflux. The mixture was cooled to room temperature and then diluted with ethyl acetate (100 mL). The reaction mixture was then washed with brine (2100 mL), water (2200 mL), and then dried over MgSO.sub.4. After evaporating the solvent, the residue was purified by column chromatography on silica gel [eluent: hexane/DCM (9/1)] to afford 4 as a yellow viscous oil. Yield: 2.27 g, 54%.

(39) .sup.1H NMR (400 MHz, CDCl.sub.3) =7.96 (d, J=7.6 Hz, 1H), 7.94-7.90 (m, 1H), 7.89-7.81 (m, 2H), 7.80-7.73 (m, 1H), 7.66 (d, J=7.6 Hz, 1H), 7.42-7.31 (m, 3H), 2.02 (td, J=7.0, 9.7 Hz, 4H), 1.26-1.00 (m, 20H), 0.85-0.63 (m, 10H);

(40) .sup.13C NMR (126 MHz, CDCl.sub.3) =154.0, 153.3, 151.3, 151.2, 141.7, 140.4, 135.2, 134.6, 132.3, 128.1, 127.9, 127.4, 126.9, 123.8, 123.0, 120.0, 119.8, 112.6, 55.2, 40.2, 31.8, 30.0, 29.2, 23.8, 22.6, 14.0;

(41) MALDI-TOF: calc. for C.sub.35H.sub.43N.sub.2SBr.sup.+ [M+H].sup.+ 604.7, found 604.7.

(42) Synthesis of 5

(43) ##STR00023##

(44) BCl.sub.3 (1M solution in Heptanes) (0.15 mL, 0.15 mmol) was added to a bright red solution of 1 (0.050 g, 0.015 mmol) in DCM (0.7 mL) in a Young's NMR tube resulting in large amounts of dark blue precipitate forming. 2,6-dichloropyridine (0.022, 0.15 mmol) was added to the reaction mixture followed by the addition of AlCl.sub.3 after rotating for 20 minutes. After rotating for 16 hours, the sparingly soluble desired product was extracted with C.sub.6D.sub.6 (1.5 mL) for NMR examination. The low solubility frustrated attempts to record a .sup.13C{.sup.1H} NMR spectrum.

(45) .sup.1H NMR (400 MHz, C.sub.6D.sub.6) =7.58 (d, J=3.6 Hz, 1H), 7.86 (s, 1H), 7.04 (d, J=7.6, 1H), 6.86 (d, J=7.2 Hz, 1H), 6.59 (dd, J=1.0, 3.8, 1H), 2.18 (s, 3H), 2.15 (s, 3H) ppm;

(46) .sup.11B NMR (128.4 MHz, CD.sub.2Cl.sub.2) =4 (broad) ppm.

(47) Synthesis of 6:

(48) ##STR00024##

(49) BBr.sub.3 (1M solution in Heptanes) (0.10 mL, 0.10 mmol) was added to a bright red solution of 1 (0.033 g, 0.010 mmol) in DCM (0.7 mL) in a Young's NMR tube resulting in large amounts of dark blue precipitate forming. A second equivalent of BBr.sub.3 (1M solution in Heptanes) (0.10 mL, 0.10 mmol) was then added (0.022, 0.15 mmol) to the reaction mixture followed by the addition of Hnigs base (0.017 mL, 0.010 mmol). The reaction mixture was then rotated for 20 minutes and then heated at 60 C. for 16 hours. After rotating for 16 hours the sparingly soluble desired product was extracted with dry THF (1.5 mL) for NMR examination. The low solubility frustrated attempts to record a .sup.13C{.sup.1H} NMR spectrum.

(50) .sup.1H NMR (400 MHz, THF) =8.00 (d, J=4.0 Hz, 1H), 7.92 (d, J=7.6, 1H), 7.64 (d, J=7.6, 1H), 6.886 (s, 1H), 6.81 (d, 3.6, 1 H), 2.51 (s, 3H), 2.50 (s, 3H) ppm;

(51) .sup.11B NMR (128.4 MHz, THF) =17 ppm

(52) Synthesis of 7:

(53) ##STR00025##

(54) BCl.sub.3 (1M solution in heptanes) (0.60 mL, 0.6 mmol) was added to a bright orange solution of 2 (0.312 g, 0.060 mmol) in DCM (10 mL) in a Schlenk flask resulting in a colour change to dark blue and the reaction mixture was stirred for 16 hours (addition of a base was unnecessary as in the open system of a Schlenk flask gaseous HCl is lost from solution under the flow of nitrogen). The solvent was removed under reduced pressure and 7 was isolated as a dark blue powder (322 mg, 89%).

(55) .sup.1H NMR (400 MHz, C.sub.6D.sub.6): =7.65 (d, J=3.8 Hz, 1H), 7.54 (s, 1H), 7.11 (d, J=7.6 Hz, 1H), 6.97 (d, J=7.6 Hz, 1H), 6.73 (d, J=3.8 Hz, 1H), 2.68 (q, J=8.0 Hz, 4H), 1.72-1.52 (m, 4H), 1.38-1.14 (m, 20H), 0.92 (t, J=6.9 Hz, 6H);

(56) .sup.13C NMR (101 MHz, DCM) =151.3, 150.8, 150.0, 145.0, 134.7, 131.7, 129.2, 128.8, 127.9, 126.2, 126.0, 125.7, 122.2, 32.0, 31.7, 31.7, 30.6, 30.4, 29.4, 29.4, 29.2, 22.8, 14.0;

(57) All CH.sub.2 resonances were not distinctly observed due to similar magnetic environments, some CH environments are obscured by solvent.

(58) .sup.11B NMR (128.4 MHz, C.sub.6D.sub.6) =3 (broad) ppm.

(59) Synthesis of 8:

(60) ##STR00026##

(61) BBr.sub.3 (1M solution in Heptanes) (0.20 mL, 0.20 mmol) was added to a bright orange solution of 2 (0.026 g, 0.005 mmol) in DCM (0.7 mL) in a Young's NMR tube resulting in a colour change to dark blue and the formation of precipitate. 2,6-Lutidine (0.011 mL, 0.1 mmol) was added to the reaction mixture. The reaction mixture was heated at 60 C. for 24 hours and upon slowly cool crystals of 8 precipitated from the reaction mixture.

(62) .sup.1H NMR (500 MHz, C.sub.6D.sub.6) =7.64 (d, J=3.2 Hz, 1H), 7.55 (s, 1H), 7.09 (d, J=7.6 Hz, 1H), 6.94 (d, J=7.6 Hz, 1H), 6.73 (d, J=3.0, 1 H), 2.69 (t, J=7.57 Hz, 2H), 2.65 (t, J=7.72 Hz, 2H), 1.54-1.70 (m, 4H), 1.37-1.18 (m, 20H), 0.92 (t, J=6.94 Hz, 6H) ppm;

(63) .sup.11B NMR (128.4 MHz, C.sub.6D.sub.6) =6 (broad) ppm.

(64) Synthesis of 9:

(65) ##STR00027##

(66) A solution of AlMe.sub.3 (2M solution in heptanes) (0.4 mL, 0.080 mmol) in dry toluene (3 mL) was slowly added a stirred solution of 7 (0.20 g, 0.33 mmol) in dry toluene (3 mL). After stirring for 20 minutes the excess AlMe.sub.3 and solvent were removed under reduced pressure. Compound 9 was isolated as a dark blue/purple powder without further purification (178 mg, 96%).

(67) .sup.1H NMR (400 MHz, C.sub.6D.sub.6) =7.84 (d, J=3.8 Hz, 1H), 7.35 (d, J=7.6 Hz, 1H), 7.11 (s, 1H), 7.05 (d, J=7.3 Hz, 1H), 6.78 (d, J=3.5 Hz, 1H), 2.81 (t, J=7.7 Hz, 2H), 2.72 (t, J=7.6 Hz, 2H), 1.76-1.61 (m, 4H), 1.38-1.17 (m, 20H), 0.92 (t, J=7.2, 3 H), 0.91 (t, J=7.2, 3 H), 0.72 (s, 6H) ppm;

(68) .sup.13C NMR (101 MHz, C.sub.6D.sub.6) =152.46, 149.50, 148.09, 147.56, 136.97, 130.76, 130.73, 130.24, 127.75, 127.72, 126.47, 126.03, 123.77, 120.63, 32.61, 32.49, 32.38, 31.29, 30.93, 30.11, 30.00, 29.84, 23.43, 17.85, 14.73, 14.71 ppm;

(69) All CH.sub.2 resonances were not distinctly observed due to similar magnetic environments.

(70) No peak was observable in the .sup.11B NMR spectrum at 20 C. in C.sub.6H.sub.6.

(71) MALDI-TOF: calc. for C.sub.31H.sub.42BN.sub.2S.sub.3.sup.+ [MCH.sub.3].sup.+ 549.7, found 549.6.

(72) Synthesis of 10:

(73) ##STR00028##

(74) A solution of Al(octyl).sub.3 (0.477M solution in heptanes) (0.15 mL, 0.070 mmol) in dry toluene (2 mL) was slowly added a stirred solution of 7 (0.020 g, 0.033 mmol) in dry toluene (3 mL). After stirring for 3 hours the reaction was quenched with water (5 mL), extracted with chloroform (320 mL), dried (MgSO.sub.4) and the solvents were removed under reduced pressure. The crude product was purified by chromatography on base treated (5% NEt.sub.3 in hexane) silica gel by using hexane as eluent. Compound 10 was isolated as a dark blue/purple oil. Yield (14 mg, 57%).

(75) .sup.1H NMR (400 MHz, CDCl.sub.3): =7.87 (d, J=4.0, 1H), 7.78 (d, J=7.6, 1H), 7.37 (d, J=7.6, 1H), 6.87 (d, J=4.0, 1H), 6.80 (s, 1H), 2.89 (t, J=7.6, 2H), 2.88 (t, J=7.6, 2H), 1.81-1.69 (m, 4H), 1.46-107 (m, 40H), 0.89 (2 overlapping triplets, 10H), 0.88 (t, J=6.8, 6H), 0.78-0.63 (m, 4H);

(76) No peak was observable in the .sup.11B NMR.

(77) Synthesis of 11

(78) ##STR00029##

(79) PhBCl.sub.2 (0.013 mL, 0.1 mmol) was added to a bright orange solution of 2 (0.52 g, 0.010 mmol) in DCM (0.7 mL) in a Young's NMR tube resulting in a colour change to dark green and the reaction mixture was rotated for 16 hours. 2,6-Lutidine (0.011 mL, 0.1 mmol) was added to the reaction mixture and after rotating for 16 hours the solvent was removed under reduced pressure to leave a dark blue/green residue. The residue was dissolved in benzene (0.7 mL) and AlMe.sub.3 (2M solution in heptanes) (0.05 mL, 0.01 mmol) was added. After the reaction mixture had been rotated for 16 hour the excess AlMe.sub.3 and solvent were removed under reduced pressure. The crude product was purified by chromatography on base treated (5% NEt.sub.3 in hexane) silica gel by using hexane as eluent and Compound 11 was isolated as a dark blue residue (22 mg, 35%).

(80) .sup.1H NMR (400 MHz, C.sub.6D.sub.6) =7.84 (d, J=3.8 Hz, 1H), 7.79 (d, J=7.6 Hz, 1H), 7.5 (d, J=7.57 Hz, 1H), 7.36-7.28 (m, 2H), 7.22 (t, J=7.2 Hz, 2H), 7.47 (tt, J=1.4, 7.2, 1 H), 6.86 (d, J=3.5 Hz, 1H), 6.74 (s, 1H), 2.88 (t, J=7.7 Hz, 2H), 2.83 (t, J=7.7 Hz, 2H), 1.79-1.56 (m, 4H), 1.45-1.24 (m, 20H), 0.90 (t, J=6.8, 6 H), 0.69 (s, 3H) ppm;

(81) .sup.13C NMR (101 MHz, CDCl.sub.3) =151.86, 149.06, 147.69, 147.34-147.37 (m, 1C) 135.53, 131.73, 130.20, 129.85, 128.18, 127.67, 127.10, 126.03, 125.38, 125.32, 123.51, 120.98, 31.83, 31.58, 31.52, 30.92, 30.50, 30.25, 29.31, 29.25, 29.21, 29.12, 22.65, 14.09 ppm;

(82) All CH.sub.2 resonances were not distinctly observed due to similar magnetic environments.

(83) No peak was observable in the .sup.11B NMR.

(84) MALDI-TOF: calc. for C.sub.36H.sub.44BN.sub.2S.sub.3.sup.+ [MC.sub.6H.sub.5].sup.+ 611.8, found 611.8.

(85) Synthesis of 12:

(86) ##STR00030##

(87) Zn(C.sub.6F.sub.5).sub.2 (152 mg, 0.4 mmols) was added to a toluene (5 mL) solution of 7, the reaction mixture was stirred for 3 hours and then after the addition of wet toluene the solution was passed through a plug of silica. Solvent was removed under reduced pressure to afford a dark blue residue (Yield 151 mg, 92%).

(88) .sup.1H NMR (400 MHz, CDCl.sub.3) =7.88 (d, J=3.8 Hz, 1H), 7.83 (d, J=7.6 Hz, 1H), 7.61 (d, J=7.6 Hz, 1H), 6.89 (d, J=3.5 Hz, 1H), 6.78 (s, 1H), 2.89 (t, J=7.6, 2 H), 2.82 (t, J=7.6, 2H), 1.81-1.64 (m, 4H), 1.49-1.20 (m, 22H), 0.89 (t, J=6.8, 3H), 0.88 (t, J=6.8, 3 H).

(89) .sup.13C NMR (126 MHz, CDCl.sub.3) =150.4, 148.9, 147.8, 146.0, 133.8, 128.8, 127.0, 127.0, 124.6, 123.4, 122.7, 122.6, 30.8, 30.8, 30.5, 30.5, 29.4, 29.3, 28.3, 28.3, 28.2, 28.1, 28.1, 21.6, 21.6, 13.0, 13.0

(90) .sup.19F NMR (376 MHz, CDCl.sub.3) =132.43 (dd, J=22.56, 7.90, 4F), 156.58 (t, 20.30, 2F), 162.40 (m, 8F)

(91) MALDI-TOF: calc. for C.sub.42H.sub.39BN.sub.2SF.sub.10.sup.+ 868.7, found 868.7.

(92) Synthesis of 13:

(93) ##STR00031##

(94) A 0.25M solution of Zn(p-Tolyl).sub.2 dissolved in THF (1.4 mL) was evaporated to dryness then suspended in dry toluene (3 mL). 7 (20 mg, 0.033 mmol) was added to the suspension and the reaction mixture was stored at room temperature for 12 hours. The crude product was purified by chromatography on base treated (5% NEt.sub.3 in hexane) silica gel by using hexane as eluent. Solvent was removed under reduced pressure to afford a dark blue residue (Yield 5.5 mg, 23%).

(95) .sup.1H NMR (400 MHz, CDCl.sub.3) =7.82 (d, J=3.5 Hz, 1H), 7.76 (d, J=7.6 Hz, 1H), 7.47 (d, J=7.6 Hz, 1H), 7.17 (d, J=8.1 Hz, 4H), 7.07 (d, J=7.8 Hz, 4H), 6.85 (d, J=3.8 Hz, 1H), 6.79 (s, 1H), 2.88 (t, J=7.6 Hz, 2H), 2.81 (t, J=7.6 Hz, 2H), 2.32 (s, 6H), 1.81-1.64 (m, 4H), 1.48-1.38 (m, 4H), 1.38-1.21 (m, 20H), 0.91 (t, J=5.2 Hz, 6H)

(96) .sup.13C NMR (126 MHz, CDCl.sub.3) =151.7, 150.8, 148.9, 147.9, 147.5, 135.5, 133.2, 131.0, 130.2, 128.5, 128.1, 127.3, 125.5, 125.1, 123.7, 121.5, 31.9, 31.6, 31.5, 30.6, 30.3, 29.4, 29.3, 29.3, 29.2, 22.7, 22.7, 21.2, 14.1

(97) Synthesis of 14

(98) ##STR00032##

(99) BCl.sub.3 1M solution in DCM) (0.15 mL, 0.12 mmol) was added to a bright orange solution of 3 (0.078 g, 0.085 mmol) in DCM (3 mL) in a Schlenk flask. The reaction mixture was stirred for 16 hours where upon a colour change to dark blue was observed. The solvent and excess BCl.sub.3 was removed under reduced pressure to yield a dark blue residue.

(100) .sup.1H NMR (500 MHz, CD.sub.2Cl.sub.2) =8.61 (d, J=7.5 Hz, 1H), 8.40 (s, 1H), 8.16 (d, J=7.2 Hz, 1H), 8.02 (s, 1H), 8.01 (d, J=7.6, 1 H), 7.94-7.89 (m, 2H), 7.82 (d, J=5.7 Hz, 1H), 7.35-7.47 (m, 6H), 2.17-2.03 (m, 8H), 1.25-1.02 (m, 40H), 0.85-0.66 (m, 20H) ppm;

(101) .sup.13C NMR (126 MHz, CD.sub.2Cl.sub.2) =154.09, 152.22, 152.03, 152.00, 151.93, 146.17, 143.84, 143.22, 140.93, 140.78, 134.36, 134.07, 131.53, 128.77, 128.58, 128.44, 128.23, 127.62, 127.59, 127.07, 125.53, 124.50, 123.72, 123.57, 121.20, 120.78, 120.68, 116.92, 55.99, 55.81, 41.10, 40.77, 32.37, 30.65, 30.56, 29.82, 29.78, 24.53, 24.50, 23.18, 23.17, 14.40 ppm;

(102) All CH.sub.2 or CH resonances were not distinctly observed due to similar magnetic environments.

(103) .sup.11B NMR (128.4 MHz, CD.sub.2Cl.sub.2): =10.0 (s) ppm.

(104) Synthesis of 15

(105) ##STR00033##

(106) AlMe.sub.3 2M in heptanes (0.11 mL, 0.22 mmol) was added to a toluene (3 mL) solution of 14 (935 mg, 0.10 mmols). After 10 minutes the excess AlMe.sub.3 was removed under reduced pressure. The reaction mixture was then filtered through base treated silica (5% NEt.sub.3/95% Hexane) and solvent was removed under reduced pressure to afford a dark purple residue.

(107) .sup.1H NMR (500 MHz, DCM) =8.37 (d, J=7.9 Hz, 1H), 8.10-7.98 (m, 4H), 7.96 (s, 1H), 7.90 (d, J=7.6 Hz, 1H), 7.86-7.78 (m, 2H), 7.46-7.30 (m, 6H), 2.07 (m., 8H), 1.04-1.24 (m., 40H), 0.83-0.68 (m, 20H), 0.47 (s, 6H) ppm;

(108) .sup.13C NMR (101 MHz, DCM) =154.3, 151.7, 151.5, 148.5, 148.3, 142.0, 141.9, 141.3, 140.6, 134.7, 131.9, 130.9, 129.4, 129.2, 128.0, 127.7, 127.3, 127.1, 126.9, 123.7, 123.2, 123.1, 123.1, 120.2, 120.2, 120.0, 116.6, 55.5, 54.9, 32.0, 30.3, 30.2, 29.4, 29.4, 24.2, 24.1, 22.8, 17.9, 14.0.

(109) Synthesis of 16

(110) ##STR00034##

(111) Zn(p-Tolyl).sub.2 (240 mg, 1 mmol) was added to a toluene (5 mL) solution of 14, the reaction mixture was stirred for 3 hours and then after the addition of wet toluene the solution was purified via silica gel chromatography (eluent hexane) to afford a dark purple residue. (Yield 152 mg, 57.3%).

(112) .sup.1H NMR (500 MHz, CDCl.sub.3) =8.43 (d, J=7.9 Hz, 1H), 8.08 (s, 1H), 8.04 (d, J=7.5, 1 H), 7.98-7.92 (m, 2H), 7.88 (d, J=7.5, 1H), 7.85 (s, 1H), 7.80-7.78 (m, 1H), 7.65-7.62 (m, 1H), 7.44-7.33 (m, 4H), 7.31-7.21 (m, 6H), 7.09 (d, J=7.6 Hz, 4H), 2.33 (s, 6H), 2.12-1.99 (m, 8H), 1.25-1.07 (m, 40H), 0.83 (t, J=7.5, 6H), 0.82 (t, J=7.5, 6H), 0.77 (m, 8H).

(113) Synthesis of 17

(114) ##STR00035##

(115) Zn(C.sub.6F.sub.5).sub.2 (97 mg, 0.242 mmol) was added to a toluene (5 mL) solution of 14 made in-situ (110 mg, 0.11 mmol), the reaction mixture was stirred for 3 hours and then after the addition of wet toluene (unpurified toluene used as received) to quench unreacted diaryl zinc reagent the solution was purified via silica gel chromatography (eluent hexane) to afford 17 as a dark purple residue. (Yield 131 mg, 94%).

(116) .sup.1H NMR (400 MHz, CDCl.sub.3) =8.58 (d, J=8.1 Hz, 1H), 8.21-8.07 (m, 2H), 8.03 (s, 1H), 7.94 (m., 2H), 7.89-7.78 (m, 2H), 7.74 (br. s., 1H), 7.49-7.30 (m, 6H), 2.11 (m., 8H), 1.13 (m 40H), 0.89-0.66 (m, 20H);

(117) .sup.13C NMR (101 MHz, CDCl.sub.3) =153.7, 151.5, 151.3, 151.3, 150.2, 147.8, 143.0, 142.4, 140.4, 140.2, 133.6, 133.0, 131.0, 128.1, 128.1, 127.9, 127.8, 127.7, 127.0, 126.9, 125.8, 124.3, 123.8, 123.0, 122.9, 120.4, 120.2, 120.1, 116.3, 55.3, 55.0, 40.7, 40.3, 31.8, 30.1, 30.0, 29.2, 29.2, 29.2, 23.9, 23.8, 22.6, 22.6, 14.0, 14.0;

(118) .sup.19F NMR (376 MHz, CDCl.sub.3) =131.55 (dd, J=23.31, 8.65, 4F), 156.65 (t, 20.68, 2F), 162.62 (m, 4F) ppm;

(119) .sup.11B NMR (128.4 MHz, CD.sub.2Cl.sub.2): =4.0 (Broad).

(120) MALDI-TOF: calc. for C.sub.70H.sub.83BF.sub.5N.sub.2S.sup.+ [MC.sub.6F.sub.5].sup.+1090.3, found 1090.4.

(121) Synthesis of 18

(122) ##STR00036##

(123) 18 was isolated from the reaction mixture of 1 via column chromatography on silica gel [eluent: hexane/DCM (3/2)] to afford a yellow powder. (Yield: 0.252 g, 10%).

(124) .sup.1H NMR (400 MHz, CDCl.sub.3) =7.91 (d, J=3.5 Hz, 1H), 7.86-7.80 (m, J=7.8 Hz, 1H), 7.66-7.61 (m, J=7.8 Hz, 1H), 6.87 (dd, J=1.0, 3.5 Hz, 1H), 2.58 (d, J=1.0 Hz, 3H)

(125) Synthesis of 19

(126) ##STR00037##

(127) BCl.sub.3 (ca. 0.8M solution in DCM) (0.3 mL, 0.24 mmol) was added to a bright yellow solution of 18 (0.031 g, 0.1 mmol) in DCM (3 mL) in a Schlenk flask. The reaction mixture instantly turned a dark purple colour and was stirred for 16 hours at room temperature. The solvent and excess BCl.sub.3 was removed under reduced pressure. To afford compound 19.

(128) Synthesis of 20

(129) ##STR00038##

(130) The reaction mixture containing 19 was then redissolved in dry toluene (8 mL) and a solution of AlMe.sub.3 (2M solution in heptanes) (0.12 mL, 0.24 mmol) in toluene (1.0 mL) was slowly added. After 10 minutes the excess AlMe.sub.3 and solvent were removed under reduced pressure. The crude product was purified by chromatography on base treated (5% NEt.sub.3 in hexane) silica gel by using pentane as eluent. Compound 20 was isolated as a dark/purple air stable solid (11 mg, yield 32.6%).

(131) .sup.1H NMR (400 MHz, CD.sub.2Cl.sub.2) =7.86 (d, J=7.56 Hz, 1H), 7.27 (d, J=7.6 Hz, 1H), 6.80 (d, J=0.8 Hz, 1H), 2.53 (s, 3H), 0.28 (s, 6H) ppm;

(132) .sup.13C NMR (101 MHz, CD.sub.2Cl.sub.2) =153.47, 147.86, 144.25, 136.18, 131.55, 129.50, 127.60, 120.60, 107.84, 15.94 ppm;

(133) .sup.11B NMR (128.4 MHz, CD.sub.2Cl.sub.2): =1 (s) ppm.

(134) Synthesis of 21

(135) ##STR00039##

(136) BCl.sub.3 1M solution in DCM) (2 mL, 2 mmol) was added to a bright yellow solution of 4 (200 mg, 0.33 mmol) in DCM (3 mL) in a Schlenk flask. The reaction mixture was stirred for 16 hours whereupon the colour change to the dark purple was observed. The solution was degassed and solvent was removed under reduced pressure to yield a dark purple residue. The reaction mixture was then dissolved in toluene (3 mL) and Zn(C.sub.6F.sub.5).sub.2 (265 mg, 0.66 mmol) was added. The reaction mixture was stirred for 2 hours and then after the addition of wet toluene the solution was passed through a plug of silica. The solvent was removed under reduced pressure to afford a dark purple residue. (Yield 296 mg, 95%).

(137) .sup.1H NMR (500 MHz, CDCl.sub.3) =8.32 (d, J=7.9 Hz, 1H), 8.15 (d, J=7.8 Hz, 1H), 8.05 (s, 1H), 7.80 (s, 1H), 7.75-7.65 (m, 1H), 7.46-7.28 (m, 3H), 2.08 (t, J=8.3 Hz, 4H), 1.24-1.02 (m, 20H), 0.88-0.61 (m, 10H);

(138) .sup.11B NMR (128.4 MHz, CDCl.sub.3) =4 (broad) ppm.

(139) .sup.19F NMR (376 MHz, CDCl.sub.3) =131.48 (dd, J=22.56, 7.90, 4F), 156.17 (d, J=20.68, 2F), 162.31 (m, 4F);

(140) Synthesis of 22

(141) ##STR00040##

(142) A mixture of compound 21 (150 mg, 0.16 mmol), 2,5-Bis(tributylstannyl)-thieno[3,2-b]thiophene (56 mg, 0.8 mmol) and Pd(PPh.sub.3).sub.4 (17 mg, 0.016 mmol) was dissolved in toluene (4 mL) and heated at 100 C. for 40 hours. After evaporating the solvent, the residue was purified by column chromatography on silica gel [eluent: hexane/DCM (6/4)] to afford 22 as a dark green residue. (yield 51 mg, 35%).

(143) .sup.1H NMR (400 MHz, CDCl.sub.3) =8.53-8.43 (m, 4H), 8.16 (d, J=7.8 Hz, 2H), 8.03 (s, 2H), 7.78 (s, 2H), 7.74-7.65 (m, 2H), 7.40-7.29 (m, 6H), 2.06 (t, J=8.2 Hz, 8H), 1.23-1.01 (m, 40H), 0.85-0.62 (m, 20H);

(144) .sup.19F NMR (376 MHz, CDCl.sub.3) =131.52 (dd, J=24.06, 8.65, 4F), 156.32 (t, 20.30, 2F), 162.42 (m, 8F)

(145) Synthesis of 23

(146) ##STR00041##

(147) 23 was isolated from the reaction mixture of 22.

(148) .sup.1H NMR (400 MHz, CDCl.sub.3) =8.45-8.38 (m, 2H), 8.08 (d, J=7.8 Hz, 1H), 8.02 (s, 1H), 7.78 (s, 1H), 7.73-7.64 (m, 1H), 7.51 (d, J=5.3 Hz, 1H), 7.40-7.28 (m, 3H), 2.06 (t, J=8.2 Hz, 4H), 1.23-1.01 (m, 20H), 0.85-0.60 (m, 10H);

(149) .sup.13C NMR (101 MHz, CDCl.sub.3) =152.0, 151.3, 150.3, 147.7, 143.1, 140.6, 140.3, 140.1, 139.0, 129.5, 128.5, 128.0, 127.9, 127.7, 126.9, 125.9, 125.6, 124.3, 122.9, 121.0, 120.4, 119.6, 116.3, 55.0, 40.6, 31.8, 30.0, 29.2, 29.1, 23.8, 22.5, 14.0

(150) .sup.19F NMR (376 MHz, CDCl.sub.3) =131.51 (dd, J=22.56, 8.65, 4F), 156.32 (t, 20.30, 2F), 162.49 (m, 8F)

(151) Synthesis of 24

(152) ##STR00042##

(153) A mixture of compound 21 (80 mg, 0.84 mmol), trimethyl(5-methyl-2-thienyl)-stannane (25 mg, 0.95 mmol) and Pd(PPh.sub.3).sub.4 (4 mg, 0.004 mmol) was dissolved in THF (1 mL) and heated at 80 C. for 20 hours. After evaporating the solvent, the residue was purified by preparative silica gel TLC [eluent: hexane/DCM (8/2)] to afford 24 as a dark blue residue. Yield 75 mg, 92%.

(154) .sup.1H NMR (400 MHz, CDCl.sub.3) =8.41 (d, J=7.8 Hz, 1H), 8.01 (s, 1H), 8.01 (d, J=7.6 Hz, 1H), 7.95 (d, J=3.8 Hz, 1H), 7.77 (s, 1H), 7.74-7.65 (m, 1H), 7.43-7.30 (m, 3H), 6.91 (d, J=3.5 Hz, 1H), 2.61 (s, 3H), 2.06 (t, J=8.3 Hz, 4H), 1.27-1.01 (m, 20H), 0.86-0.62 (m, 10H);

(155) .sup.13C NMR (101 MHz, CDCl.sub.3) =152.1, 151.3, 150.2, 147.6, 143.2, 142.8, 140.4, 135.0, 128.7, 128.1, 127.9, 127.6, 127.1, 127.0, 126.8, 125.9, 125.8, 124.2, 122.9, 120.3, 116.2, 55.0, 40.6, 31.8, 30.0, 29.2, 29.1, 23.7, 22.5, 15.5, 14.0

(156) .sup.19F NMR (376 MHz, CDCl.sub.3) =131.55 (dd, J=22.56, 8.65, 4F), 156.32 (t, 20.68, 2F), 162.60 (m, 8F)

(157) Synthesis of 25

(158) ##STR00043##

(159) BCl.sub.3 (1M solution in hexane) (0.015 mL, 0.015 mmol) was added to a solution of poly(9,9-dioctylfluorene-co-benzothiadiazole) poly-F8BT (8 mg, 0.015 mmols) in DCM (1 mL) in a Young's NMR tube resulting in a colour change from yellow to dark blue after rotating for 3 hours. NMR examination suggested the reaction was successful. The solvent was removed under reduced pressure to afford a dark blue residue.

(160) .sup.1H NMR (500 MHz, DCM) =8.71-8.63 (broad), 8.60-8.55 (broad), 8.53-8.47 (broad), 8.25-8.97 (m, broad), 2.30-2.04 (broad), 1.33-1.03 (m, broad), 0.91-0.74 (m, broad) ppm;

(161) No peak was observable in the .sup.11B NMR.

(162) Synthesis of 26

(163) ##STR00044##

(164) A solution of AlMe.sub.3 (2M in heptanes) (0.11 mL, 0.22 mmol) in dry toluene (1 mL) was added to a stirred solution of 25 in dry toluene (4 mL). The solution changed colour from dark blue to purple and after 20 minutes the solvent and excess AlMe.sub.3 was removed under reduced pressure this product was then precipitated in methanol. Yield 38 mg.

(165) .sup.1H NMR (400 MHz, CD.sub.2Cl) =8.53-8.35 (m, 1H), 8.19-7.93 (m, 7H), 2.18 (br. s., 4H), 1.25-1.06 (m, 26H), 0.79 (t, J=6.3 Hz, 8H), 0.51 (br. s., 6H).

(166) Synthesis of 27:

(167) ##STR00045##

(168) AlCl.sub.3 (6 mg, 0.04 mmol) was added to a solution of 7 (25 mg, 0.04 mmol) in DCM (0.7 mL). The solution colour changed from dark blue to dark red.

(169) .sup.1H NMR (400 MHz, DCM): =8.66 (d, J=8.0, 1H), 8.37 (s, 1H), 8.14 (d, J=6.8, 1H), 7.14 (s, 1H), 7.14 (s, 1H), 3.09-2.92 (m, 4H), 1.86-1.73 (m, 4H), 1.49-1.19 (m, 20H), 0.87 (t, 6H) ppm;

(170) .sup.27Al NMR (104.3 MHz, DCM): =103 (broad) ppm.

(171) No peak was observable in the .sup.11B NMR.

(172) Synthesis of 28

(173) ##STR00046##

(174) BCl.sub.3 (1M solution in DCM) (0.40 mL, 0.40 mmol) was added to a bright yellow solution of 4,4-(9,9-dioctyl-9H-fluorene-2,7-diyl)bis(benzo[c][1,2,5]thiadiazole) (BT-F8-BT) (66 mg, 0.01 mmol) in DCM (0.7 mL) in a Young's NMR tube. The solution instantly changed colour to a dark red. 2,4,6-Tri.sup.tbutylpyridine (50 mg) and AlCl.sub.3 (40 mg, 0.3 mmol) was added to the reaction mixture. After rotating for 16 hours, AlCl.sub.3 (14 mg, 0.1 mmol) was added and the solution was rotated for a further 16 hours whereupon the solution had turned dark green. N.sup.nBu.sub.4Cl (48 mg, 0.2 mmol) was then added to the reaction mixture and the solution turned dark purple. NMR examination indicated the desired product had been formed.

(175) .sup.1H NMR (400 MHz, DCM) =8.71 (d, J=7.2 Hz, 2H), 8.46 (s, 2H), 8.04 (m, 2H), 8.31 (d, J=8.8 Hz, 2H), 8.16 (s, 2H), 2.22 (m, 4H), 0.72 (t, J=6.8 Hz, 6H) ppm;

(176) Synthesis of 29

(177) ##STR00047##

(178) A reaction mixture containing 28 (0.45 mmol) and the ionic by-products from borylation (e.g., ammonium[AlCl.sub.4]) was dissolved in DCM (15 mL) and ZnPh.sub.2 (400 mg, 1.82 mmol) was added. The reaction mixture was then stirred for 16 hours after which it was passed through a plug of silica. The solvent was then removed under reduced pressure and the product was isolated by column chromatography on base treated [hexane/NEt.sub.3 (95:5)] silica gel [eluent: hexane/DCM (8:2)] Yield (236 mg, 53%).

(179) .sup.1H NMR (400 MHz, CD.sub.2Cl.sub.2) =8.39 (d, J=7.1 Hz, 2H), 8.18 (s, 2H), 7.90-7.77 (m, 6H), 7.31-7.15 (m, 20H), 2.32-2.13 (m, 4H), 1.18 (m, 20H), 0.97 (m, 4H), 0.82 (t, J=6.7 Hz, 6H);

(180) .sup.13C NMR (101 MHz, CD.sub.2Cl.sub.2) =155.8, 155.3, 152.7, 150.4, 148.2, 142.4, 134.0, 133.7, 131.0, 130.4, 128.1, 126.5, 126.4, 123.9, 119.5, 117.3, 55.1, 41.3, 32.4, 30.7, 29.8, 24.7, 23.2, 14.4;

(181) .sup.11B NMR (128.4 MHz, CD.sub.2Cl.sub.2): =2.0 (Broad);

(182) MALDI-TOF: calc. for C.sub.59H.sub.59B.sub.2N.sub.4S.sub.2.sup.+ [MC.sub.6H.sub.5].sup.+ 909.9, found 910.0.

(183) Synthesis of 30

(184) ##STR00048##

(185) A reaction mixture of 28 (0.45 mmol) also containing the ionic by-products from borylation (e.g., ammonium[AlCl.sub.4]) was dissolved in DCM (15 mL) and Zn(C.sub.6F.sub.5).sub.2 (728 mg, 1.82 mmol) was added. The reaction mixture was then stirred for 16 hours after which it was passed through a plug of silica. The solvent was then removed under reduced pressure and the product was isolated by column chromatography on base treated [hexane/NEt.sub.3 (95:5)] silica gel [eluent: hexane/DCM (8:2)] Yield (435 mg, 71%).

(186) .sup.1H NMR (400 MHz, CD.sub.2Cl.sub.2) =8.48 (d, J=6.8 Hz, 2H), 8.10 (s, 2H), 8.02-7.85 (m, 4H), 7.67 (s, 2H), 2.25-2.05 (m, 4H), 1.20-1.00 (m, 20H), 0.78-0.68 (m, 10H);

(187) .sup.13C NMR (101 MHz, CDCl.sub.3) =154.9, 150.7, 147.0, 142.2, 133.5, 129.7, 128.7, 125.0, 125.0, 119.4, 116.5, 55.0, 40.9, 31.8, 30.0, 29.2, 29.1, 22.5, 14.0;

(188) .sup.19F NMR (376 MHz, CDCl.sub.3) =132.23 (dd, J=22.56, 8.27, 8F), 157.83 (t, 20.68, 4F), 163.77 (m, 8F);

(189) .sup.11B NMR (128.4 MHz, CDCl.sub.3): =3.0 (Broad);

(190) MALDI-TOF: calc. for C.sub.59H.sub.44B.sub.2F.sub.15N.sub.4S.sub.2.sup.+ [MC.sub.6F.sub.5].sup.+1179.8, found 1179.7.

(191) Synthesis of 31

(192) ##STR00049##

(193) 4,4-(9,9-dioctyl-9H-fluorene-2,7-diyl)bis(benzo[c][1,2,5]thiadiazole) (BT-F8-BT) (512 mg, 0.78 mmol) was dissolved in chloroform (5 mL) and bromine (0.9 mL, 1.7 mmols) was added. The reaction mixture was then stirred for 18 hours after which the reaction mixture was quenched with Na.sub.2S.sub.2O.sub.3 solution, washed with brine (50 mL) then water (50 mL), and dried (MgSO.sub.4), The crude product was the purified via silica gel chromatography [eluent:hexane/EtOAc (98/2)] to afford 31 and a yellow solid. Yield (612 mg, 97%)

(194) .sup.1H NMR (400 MHz, CD.sub.2Cl.sub.2) =8.05-7.84 (m, 8H), 7.65 (d, J=7.6 Hz, 2H), 2.25-1.98 (m, 4H), 1.22-1.02 (m., 20H), 1.00-0.82 (m, 4H), 0.76 (t, J=6.7 Hz, 6H);

(195) .sup.13C NMR (101 MHz, CDCl.sub.3) =153.7, 153.0, 151.6, 140.9, 135.4, 134.1, 132.1, 128.2, 127.8, 123.8, 120.1, 112.6, 55.3, 40.0, 31.6, 29.9, 29.1, 23.9, 22.5, 22.5, 14.0;

(196) Synthesis of 32

(197) ##STR00050##

(198) BCl.sub.3 (1M in DCM) (4.5 mL, 4.5 mmols) was added to a solution of 31 (430 mg, 0.53 mmols) in DCM (5 mL). The reaction was stirred under the dynamic flow of nitrogen for 20 hours after which it was degassed and the solvent was removed under reduced pressure. The reaction mixture residue was dissolved in DCM (5 mL), ZnPh.sub.2 (574 mg, 2.61 mmols) was then added to the reaction mixture. The reaction mixture was left to stir for 4 hours were it was diluted with DCM (5 mL) and the solution was passed through a plug of silica. The solvent was then removed under reduced pressure and the product was isolated via column chromatography on silica gel [eluent: Chloroform/hexane (7/3)] to afford 32 as a dark purple residue. (Yield 347 mg, 58%).

(199) .sup.1H NMR (400 MHz, CD.sub.2Cl.sub.2) =8.22 (d, J=7.95 Hz, 2H) 8.01-8.12 (m, 4H) 7.76 (s, 2H) 7.15-7.32 (m, 21H) 2.04-2.20 (m, 4H) 1.23 (br. s., 5H) 1.16 (br. s., 16H) 0.86-0.99 (m, 5H) 0.83 (t, J=6.72 Hz, 6H);

(200) .sup.13C NMR (101 MHz, CDCl.sub.3) =154.3, 153.0, 152.1, 149.9, 147.7, 142.2, 135.3, 133.5, 130.0, 129.2, 127.6, 126.6, 126.1, 123.6, 116.4, 110.6, 54.3, 40.8, 31.8, 30.1, 29.2, 29.2, 24.1, 22.6, 14.1;

(201) .sup.11B NMR (128.4 MHz, CDCl.sub.3): =2.0 (Broad);

(202) Synthesis of 33

(203) ##STR00051##

(204) 9-(heptadecan-9-yl)-2,7-bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-9H-carbazole (0.62 g, 0.94 mmol. 1 eq) and bromobenzothiadiazole (0.46 g, 2.13 mmol, 2.2 eq) were degassed and dissolved in dry THF (10 mL). K.sub.3PO.sub.4.H.sub.2O (1.30 g, 5.62, 6 eq), Pd.sub.2(dba).sub.3 (42.9 mg, 0.047 mmol, 0.05 eq) and S-PHOS (38.5 mg, 0.094 mmol, 0.1 eq) were added to the reaction mixture; the red-brown solution turned green after mixing at r.t for 20 mins. Upon the addition of degassed H.sub.2O the reaction mixture turned brown-orange then yellow. The reaction was stirred at 70 C. for 24 h. The cooled mixture was extracted with CH.sub.2Cl.sub.2, washed with brine water, then water, and dried with MgSO.sub.4. After evaporation of solvents, the orange residue oil was purified by base treated silica gel (5% triethylamine, 95% hexane) chromatography (hexane followed by chloroform:hexane, 2:8) obtained yellow crystals. Yield (0.4857 g, 77%).

(205) .sup.1H NMR (400 MHz, CDCl.sub.3) =0.78 (t, .sup.3J.sub.HH=8 Hz, 6H), 1.16 (m, br, 18H), 1.30 (m, br, 6H), 2.01 (m, br, 2H), 2.45 (m, br, 2H), 4.82 (m, br, 1H), 7.78 (m, .sup.3J.sub.HH=8 Hz, 4H), 7.85 (dd, br, 2H), 8.04 (dd, br, 2H), 8.10 (s, br, 1H), 8.29 (t, br, 2H);

(206) .sup.13C NMR (100 MHz, CDCl.sub.3) =14.0, 22.5, 26.8, 29.2, 29.3, 29.4, 31.7, 33.8, 56.5, 110.3, 113.1, 120.1, 120.3, 120.5, 122.3, 123.6, 127.8, 129.7, 134.3, 134.9, 135.5, 139.4, 142.8, 153.8, 155.7;

(207) Synthesis of 34

(208) ##STR00052##

(209) 33 (100 mg, 0.1484 mmol, 1 eq) and tri-tert-butylpyridine (TBP) (73.4 mg, 0.2967 mmol, 2 eq) were dissolved in CH.sub.2Cl.sub.2 (3 mL), followed by the addition of BCl.sub.3 in CH.sub.2Cl.sub.2 (0.6 mL, 1M, 4 eq). AlCl.sub.3 (40 mg, 0.2967 mmol, 2 eq) was added and stirred for 2 h at r.t.; the red solution turned blue. An additional 2 eq of AlCl.sub.3 was added and stirred for 2 h. Following the removal of excess BCl.sub.3, the reaction mixture was redissolved in CH.sub.2Cl.sub.2 (5 mL) and NMe.sub.4Cl (32.5 mg, 0.2967 mmol, 2 eq) was added. The solution instantly turned pink-purple. Subsequently, after the removal of CH.sub.2Cl.sub.2, the reaction mixture was redissolved in toluene (20 mL) and Zn(C.sub.6F.sub.5).sub.2 (237.4 mg, 0.5936 mmol, 4 eq) was added. The reaction was left to stir overnight at 60 C. which resulted in a purple solution. After evaporation, purification by a base treated (5% triethylamine 95% hexane) preparative TLC (Hexane:CH.sub.2Cl.sub.2, 7:3) a purple solid was obtained. Yield (47.7 mg, 0.035 mmol, 24%).

(210) .sup.1H NMR (400 MHz, CDCl.sub.3) =0.76 (t, .sup.3J.sub.HH=8 Hz, 6H), 1.15 (m, br, 18H), 1.32 (m, br, 6H), 2.10 (m, br, 2H), 2.41 (m, br, 2H), 4.69 (m, br, 1H), 7.91 (br, 2H), 7.97 (br, 2H), 8.03 (br, 3H), 8.20 (s, br, 1H), 8.45 (br, 1H), 8.50 (br, 1H).

(211) .sup.13C NMR (100 MHz, CDCl.sub.3) =14.0, 22.5, 27.0, 29.2, 29.3, 29.5, 31.7, 33.9, 56.5, 102.0, 104.7, 119.4, 121.6 (br), 124.4, 124.9, 125.2, 125.4, 125.7, 127.1, 127.5, 130.2, 133.4, 136.2 (br), 138.7 (br), 139.8, 141.4 (br), 143.1, 146.4 (br), 147.1, 148.8 (br), 155.0;

(212) .sup.19F NMR (376 MHz, CDCl.sub.3)=162.8 (m, 2F), 156.7 (m, 1F), 131.8 (d, .sup.3J.sub.FF=18.8 Hz, 2F).

(213) Synthesis of 35

(214) ##STR00053##

(215) BCl.sub.3 (1M in DCM) (0.4 mL, 0.4 mmol) was added to a stirred solution of 3-(7-bromobenzo[c][1,2,5]thiadiazol-4-yl)-10-(2-ethylhexyl)-1 OH-phenothiazine (33 mg, 0.06 mmols) in DCM (2 mL). The solution instantly changed colour from orange to dark blue. After 3 hours 2,4,6-tri-tert-butylpyridine (16 mg, 0.06 mmols) was added to the reaction mixture and the solution instantly changed colour from dark blue to dark green. After stirring for 16 hours the solvent and excess BCl.sub.3 were removed under reduced pressure and the reaction mixture was redissolved in DCM (2 mL). Zn(Ph).sub.2 (31 mg, 0.14 mmols) was added to the reaction mixture and this was stirred for 3 hours. The reaction mixture was filtered through silica gel and purified by preparative silica gel TLC [eluent: hexane/DCM (8/2)] to afford 35 as a dark blue/green residue. Yield (17 mg, 39%)

(216) .sup.1H NMR (400 MHz, CDCl.sub.3) =7.87 (d, J=7.8 Hz, 1H), 7.80 (d, J=7.9 Hz, 1H), 7.70 (s, 1H), 7.24-6.96 (m, 12H), 6.85-6.77 (m, 2H), 6.74 (d, J=8.1 Hz, 1H), 3.50 (d, J=6.7 Hz, 2H), 1.68 (td, J=6.1, 12.2 Hz, 1H), 1.25-0.95 (m, 8H), 0.72 (t, J=7.0 Hz, 3H), 0.63 (t, J=7.5 Hz, 3H);

(217) .sup.13C NMR (100 MHz, CDCl.sub.3) =153.0, 147.5, 145.7, 145.6, 135.6, 133.6, 133.5, 128.9, 127.7, 127.4, 127.3, 126.2, 126.2, 124.6, 124.6, 124.2, 122.5, 122.3, 121.6, 121.3, 116.1, 109.9, 50.9, 35.6, 30.4, 28.3, 23.7, 23.0, 14.0, 10.3;

(218) .sup.11B NMR (128.4 MHz, CDCl.sub.3): =2.0 (Broad);

(219) Synthesis of 36

(220) ##STR00054##

(221) 2,5-dibromo-3,4-dinitro-thiophene (1.01 g, 3.0 mmols), tri.sup.nbutyl(9,9-dioctyl-9H-fluoren-2-yl)-stannane (5.0 g, 7.3 mmols), Pd.sub.2(dba).sub.3 (140 mg, 0.15 mmols) and S-Phos (264 mg, 0.6 mmols) were dissolved in THF (30 mL) and the reaction mixture was stirred at 70 C. for 20 hours. After cooling the reaction mixture was evaporated to dryness and purified using silica gel chromatography [eluent: Hexane/DCM (8/2)] to afford 36 as a light yellow solid. Yield (1.72 g, 59%)

(222) .sup.1H NMR (400 MHz, CDCl.sub.3) =7.82 (d, J=7.6 Hz, 2H), 7.78 (dt, J=1.5, 3.9 Hz, 2H), 7.58-7.49 (m, 4H), 7.46-7.35 (m, 6H), 2.14-1.92 (m, 8H), 1.28-1.03 (m, 40H), 0.84 (t, J=7.1 Hz, 12H), 0.78-0.59 (m, 8H);

(223) .sup.13C NMR (101 MHz, CDCl.sub.3) =151.6, 151.3, 143.9, 141.2, 139.6, 136.7, 128.3, 127.9, 127.1, 126.3, 123.6, 123.0, 120.4, 120.2, 77.3, 76.7, 55.4, 40.1, 31.7, 29.9, 29.2, 23.8, 22.6, 14.0;

(224) Synthesis of 37

(225) ##STR00055##

(226) 35 (300 mg, 0.32 mmols) was dissolved in a mixture of ethanol (18 mL) and toluene (6 mL). Tin powder (0.5 g, 2.5 mmols) was added to this solution and concentrated HCl (37%) (6 mL) was added drop wise to the suspension. The reaction mixture was then heated at 50 C. for 6 hours. The reaction mixture was then neutralised with aqueous NaOH (2M) and extracted with DCM (320 mL). The organic layers were combined and evaporated to dryness under reduced pressure. The reaction mixture was dissolved in DCM (10 ml) and trimethylamine (2 mL) was added. Glyoxal (40 wt. % in H.sub.2O) (0.5 mL, 3.4 mmols) was added drop wise to the reaction mixture and was stirred for 16 hours. The reaction mixture was dried (MgSO.sub.4) and evaporated to dryness under reduced pressure and purified using silica gel chromatography [eluent: hexane/DCM (8/2)] to afford 37 as a dark red residue. Yield (232 mg, 79%)

(227) .sup.1H NMR (400 MHz, CDCl.sub.3) =8.59 (s, 2H), 8.31 (d, J=9.0 Hz, 2H), 8.11 (s, 2H), 7.84 (d, J=7.9 Hz, 2H), 7.77 (d, J=7.1 Hz, 2H), 7.44-7.31 (m, 6H), 2.17-1.96 (m, 8H), 1.26-1.02 (m, 40H), 0.87-0.65 (m, 20H);

(228) Synthesis of 38

(229) ##STR00056##

(230) BCl.sub.3 (1M in DCM) (0.1 mL, 0.1 mmols) was added to a stirred solution of 37 (57 mg, 0.06 mmols) in DCM (2 mL). The dark red solution instantly turned green and the solution was stirred for 10 minutes and then the excess BCl.sub.3 and solvent was removed under reduced pressure. The resulting residue was dissolved in DCM (2 mL) and AlMe.sub.3 (2M in heptanes) (0.1 mL, 0.2 mmols) was added to the reaction mixture. After 10 minutes the excess AlMe.sub.3 and solvent was removed under reduced pressure. The resulting residue was purified by preparative silica gel TLC [eluent: hexane/DCM (8/2)] to afford 38 as a dark green residue. Yield (42 mg, 68%)

(231) .sup.1H NMR (400 MHz, CDCl.sub.3) =8.76 (d, J=2.3 Hz, 1H), 8.31-8.18 (m, 2H), 8.08 (s, 1H), 7.89-7.72 (m, 4H), 7.60 (s, 1H), 7.43-7.28 (m, 6H), 2.17-1.91 (m, 8H), 1.24-1.13 (m, 14H), 1.09 (br. s., 29H), 0.80 (t, J=6.9 Hz, 22H), 0.34 (s, 6H);

(232) Synthesis of 39

(233) ##STR00057##

(234) BCl.sub.3 (1M solution in DCM) (0.12 mL, 0.12 mmol) was added to a bright orange solution of 2 (0.50 g, 0.1 mmol) in DCM (3 mL) in a Schlenk flask. The reaction mixture was stirred for 16 hours under a dynamic flow of nitrogen, where upon a colour change to dark blue was observed. The solvent and excess BCl.sub.3 was removed under reduced pressure to yield a dark blue residue. The residue was redissolved in toluene and Zn(Ph).sub.2 (50 mg, 0.23 mmol) was then added to the reaction mixture and stirred for 3 hours the solution was then filtered through silica gel and the solvent was removed under reduced pressure to afford 39 as a dark blue residue. (Yield 46 mg, 69%).

(235) .sup.1H NMR (400 MHz, CDCl.sub.3) =7.76 (d, J=3.7 Hz, 1H), 7.65 (d, J=7.6 Hz, 1H), 7.38 (d, J=7.7 Hz, 1H), 7.31-7.14 (m, 10H), 6.84-6.76 (m, 2H), 2.87 (t, J=7.6 Hz, 2H), 2.81 (t, J=7.6 Hz, 2H), 1.73 (quind, J=7.6, 15.1 Hz, 4H), 1.49-1.20 (m, 20H), 0.98-0.83 (m, 6H);

(236) .sup.13C NMR (101 MHz, CDCl.sub.3) =160.7 (broad), 154.0 (broad), 151.5, 148.9, 147.8, 147.4, 135.4, 133.2, 130.9, 130.3, 127.9, 127.6, 127.3, 126.0, 125.4, 124.9, 123.6, 121.6, 31.9, 31.8, 31.6, 31.5, 30.5, 30.2, 29.3, 29.3, 29.2, 29.2, 29.1, 22.7, 14.1;

(237) A number of the CH.sub.2 resonances were not distinctly observed due to similar magnetic environments.

(238) .sup.11B NMR (128.4 MHz, CDCl.sub.3) =Not observed

(239) MALDI-TOF: calc. for C.sub.36H.sub.44BN.sub.2S.sub.3.sup.+ [MC.sub.6H.sub.5].sup.+ 611.8, found 611.7.

(240) Synthesis of 40

(241) ##STR00058##

(242) BCl.sub.3 1M solution in DCM) (0.15 mL, 0.12 mmol) was added to a bright orange solution of 3 (0.095 g, 0.1 mmol) in DCM (3 mL) in a Schlenk flask. The reaction mixture was stirred for 16 hours where upon a colour change to dark blue was observed. The solvent and excess BCl.sub.3 was removed under reduced pressure to yield a dark blue residue. 5-trimethylstannyl-2-methylthiophene (81 mg, 0.3 mmols) and AlCl.sub.3 (1 mg) was added to the reaction mixture. The reaction mixture instantly changed from blue to purple. After stirring for 16 hours the reaction mixture was evaporated to dryness under reduced pressure and the residue was purified using base treated (5% NEt.sub.3 in hexane) preparative silica gel TLC [eluent:hexane] to afford 40 as a purple residue. Yield (75 mg, 64%)

(243) Synthesis of 41-43

(244) ##STR00059##

(245) BCl.sub.3 (1M in DCM) (X equivalents) and 2,4,6-tritertbutylpyridine (X equivalents) were added to a stirred solution of poly-F8BT in toluene. The reaction mixture was then stirred in a closed system for 16 hours. Zn(Ph).sub.2 (2.2 equivalents) was then added to the reaction mixture and the reaction mixture was stirred for 3 hours. The reaction mixture was then passed through a plug of silica and precipitated by drop wise addition of methanol.

(246) 41=80% borylated. Yield (390 mg)

(247) .sup.1H NMR (400 MHz, CDCl.sub.3) =8.55-8.39 (m, 1H), 8.16-7.70 (m, 7.6H), 7.41-7.14 (m, 12H), 2.11 (br. s., 5.4H), 1.24-1.04 (m, 27H, 1.04-0.73 (m, 11H);

(248) Mn=16000

(249) 42=42% borylated

(250) 43=25% borylated

(251) Synthesis of 44

(252) ##STR00060##

(253) BCl.sub.3 (1M in DCM) (0.3 mL, 0.3 mmols) was added to a solution of poly((9,9-dioctylfluorene)-2,7-diyl-alt-[4,7-bis(3-hexylthien-5-yl)-2,1,3-benzothiadiazole]-2,2-diyl) (100 mg, 0.11 mmols) in toluene (10 mL) were the reaction mixture instantly changed colour from dark red to dark green. The reaction mixture was stirred under a dynamic flow of nitrogen for 16 hours. The reaction mixture was then degassed and AlMe.sub.2 (2M in heptanes) (0.2 mL, 0.4 mmols) was added. The reaction mixture was stirred for 30 minutes and then degassed. The reaction mixture was then passed through a plug of silica and precipitated by addition of methanol. The resulting dark green powder was then purified by Soxhlet extraction using hexane, acetone and finally chloroform. The chloroform solution was then precipitated by addition of methanol and the resulting dark green powder was collected by filtration and dried. Yield (31 mg, 31%)

(254) .sup.1H NMR (400 MHz, CDCl.sub.3) =8.03 (br. s., 1H), 7.92 (br. d., 1H), 7.80 (br. t., 2H), 7.64-7.49 (m, 5H), 2.90 (br. s., 2H), 2.82 (br. s., 2H), 2.05 (br. s., 4H), 1.54-1.03 (m, 48H), 0.96-0.69 (m, 20H), 0.51 (br, s, 6H);

(255) Mn=33000

(256) Synthesis of 45

(257) ##STR00061##

(258) Zn(Ph).sub.2 (110 mg, 0.5 mmol) was added to a DCM (5 mL) solution of 14 (212 mg, 0.213 mmol, made in-situ as described above), the reaction was stirred for 3 hours and then the solution was filtered through silica gel and the solvent removed under reduced pressure to afford 45 as a dark purple residue. (Yield 231 mg, 0.213 mmol 99%).

(259) .sup.1H NMR (400 MHz, CDCl.sub.3) =8.52 (d, J=7.8 Hz, 1H), 8.18 (s, 1H), 8.12 (d, J=7.6 Hz, 1H), 8.06 (s, 1H), 8.01 (d, J=7.9 Hz, 1H), 7.95 (d, J=8.0 Hz, 1H), 7.95 (s, 1H), 7.87 (dd, J=2.4, 5.4 Hz, 1H), 7.76-7.68 (m, 1H), 7.53-7.24 (m, 16H), 2.27-2.03 (m, 8H), 1.36-1.20 (m, 40H), 1.00-0.76 (m, 20H);

(260) .sup.13C NMR (101 MHz, CDCl.sub.3) =154.3, 153.0, 152.2, 151.3, 149.1, 147.8, 142.4, 140.7, 135.3, 133.6, 130.1, 128.9, 127.6, 127.4, 126.7, 126.1, 125.8, 123.5, 122.7, 120.6, 116.4, 110.5, 54.8, 40.6, 31.7, 30.0, 29.2, 29.1, 23.9, 22.5, 14.0

(261) .sup.11B NMR (128.4 MHz, CD.sub.2Cl.sub.2): =2.0 (Broad singlet);

(262) A number of the CH.sub.2 or CH resonances were not distinctly observed due to similar magnetic environments.

(263) MALDI-TOF: calc. for C.sub.70H.sub.88BN.sub.2S.sup.+ [MC.sub.6H.sub.5]+1000.4, found 1000.5.

(264) Synthesis of 46

(265) ##STR00062##

(266) 32 (70 mg, 0.06 mmols), 9,9-dioctylfluorene-2,7-diboronic acid (40 mg, 0.06 mmols) and bis(tri-tert-butylphosphine)palladium (8 mg, 0.016 mg) were dissolved in THF (5 mL) and 2M K.sub.3PO.sub.4 (0.62 mL, 0.12 mmols) was then added to the solution. The reaction mixture was stirred for 30 minutes at room temperature and then washed with water (30 mL) and dried (MgSO.sub.4). The solution was concentrated under reduced pressure was precipitated in methanol. The resulting dark blue solid was collected by filtration and then dried. Yield (47 mg, 55%);

(267) .sup.1H NMR (400 MHz, CDCl.sub.3) =8.47 (br. s., 2H), 8.24-7.87. (br. m., 10H), 7.76 (br. s., 3H), 7.32 (br. s., 11H), 7.24 (br. s., 17H), 2.25-1.96 (m, 7H), 1.31-0.68 (br. m., 80H);

(268) Mn=32000

EXAMPLE 2ABSORPTION & EMISSION STUDIES

(269) The UV-Vis absorption spectra for solution ranging 0.5-210.sup.5 were recorded on a Varian Cary 5000UV-Vis-NIR spectrophotometer, in DCM at room temperature. Fluorescence spectra were recorded on a Varian Cary Eclipse fluorometer for solution ranging 0.5-210.sup.5 in DCM at room temperature. Fluorescence quantum yield was measured on toluene solutions and estimated by using cresyl violet as standard (QY=54% in methanol). Solid state fluorescence and absolute quantum yields were measured on spin coated films of polymer host/5 wt % emitter using a Hamamatsu C9920-02 Absolute quantum yield measurement system.

(270) FIG. 1 shows absorption and emission spectra for the unborylated BT-F8-BT. The compound was characterised as follows:

(271) Extinction coefficient=23329 M.sup.1 cm.sup.1

(272) .sub.max=392 nm

(273) Absorption Onset=436 nm

(274) Band-gap=2.83 eV

(275) Emission .sub.max=518 nm

(276) FIG. 2 shows absorption and emission spectra for borylated compound 29. The compound was characterised as follows

(277) Extinction coefficient=20303 M.sup.1 cm.sup.1

(278) .sub.max=539 nm

(279) Absorption Onset=613 nm

(280) Band-gap=2.02 eV

(281) Emission .sub.max=707 nm

(282) FIG. 3 shows absorption and emission spectra for borylated compound 30. The compound was characterised as follows:

(283) Extinction coefficient=10427 M.sup.1 cm.sup.1

(284) .sub.max=541 nm

(285) Absorption Onset=617 nm

(286) Band-gap=2.00 eV

(287) Emission .sub.max=717 nm

(288) FIG. 4 and Table 1 below show a comparison of the absorption and emission spectra for unborylated BT-F8-BT and compounds 29 and 30.

(289) TABLE-US-00001 TABLE 1 Comparison of absorption and emission data for unborylated BT-F8-BT and compounds 29 and 30 .sub.abs .sub.onset Band-Gap (nm) (nm) (M.sup.1cm.sup.1) (eV) .sub.em QY BT-F8-BT 392 436 23329 2.83 593 29 539 613 20303 2.02 707 0.18 30 541 617 10427 2.00 717 0.12
The above data show a significant reduction in optical band-gap and a large bathochromic shift in emission upon diborylation and formation a ladder structure. Whilst replacing C.sub.6F.sub.5 substituents on the boron for phenyl groups result little change in the UV-Vis absorbance spectra and emission .sub.max, the phenyl substituted compound demonstrates much stronger fluorescence.

(290) FIG. 5 shows absorption and emission spectra for borylated compound 26. The compound was characterised as follows:

(291) Extinction coefficient=13254 M.sup.1 cm.sup.1

(292) .sub.max=592 nm

(293) Absorption Onset=660 nm

(294) Band-gap=1.88 eV

(295) Emission .sub.max=715 nm

(296) The above data show a significant reduction in optical band-gap and a large bathochromic shift in emission upon borylation of F8BT. This polymer also exhibits some fluorescence in the solid state.

(297) FIG. 6 shows the solid state photoluminescence spectra of thin films from a 5 wt % mixture of borylated compounds 45, 29 and 30 dispersed in PF8-BT polymer spin coated from toluene, excited at 468 nm.

(298) TABLE-US-00002 Film Transmittance PLQY % CIE X CIE Y PF8-BT: 45 (95:5 wt %) 0.36 33.5 0.660 0.338 PF8-BT: 29 (95:5 wt %) 0.36 32.9 0.633 0.360 PF8-BT: 30 (95:5 wt %) 0.36 19.9 0.628 0.368

(299) FIG. 7 shows absorption and emission spectra for borylated compounds 41, 42 and 43 dissolved in toluene.

EXAMPLE 3X-RAY ANALYSIS

(300) Data for all compounds were recorded on either an Oxford Xcalibur Sapphire2 diffractometer, with Mo K radiation (graphite monochromator, =0.71073). The CrysAlisPro.sup.[5] software package was used for data collection, cell refinement and data reduction. Empirical absorption corrections were applied using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm or a Bruker APEX-II diffractometer, with Cu K radiation (graphite monochromator, =1.54178). The Bruker APEX2 software package was used for data collection, and the Bruker SAINT.sup.[6] software package was used for cell refinement and data reduction. Empirical absorption corrections were applied using SADABS-2008/1Bruker AXS area detector scaling and absorption correction. All structures were solved using direct methods.sup.[7] and refined against F.sup.2 using the Crystals.sup.[8] software package. Non-hydrogen atoms were refined anisotropically. Hydrogen atoms were all located in a difference map and repositioned geometrically.

(301) FIG. 8 shows the X-ray structure for the unborylated BT-F8-BT. The structure shows significant twisting between the neighbouring -donor and -acceptor units indicating unfavourable steric interactions.

(302) FIG. 9 shows the X-ray structure for the borylated compound 29, wherein the .sup.noctyl R substituents have been removed for clarity. FIG. 10 shows the X-ray packing structure of compounds 29. It is seen that proximal quaternary centres prevent core close packing, whilst peripheral BPh.sub.2 - stack with the backbone, allowing 3D packing through close - contacts.

(303) FIG. 11 shows the X-ray structure for the borylated compound 30. It can be seen that the torsion angle of adjacent -donor and -acceptor units is significantly reduced in relation to the unborylated BT-F8-BT. FIG. 12 shows the X-ray packing structure of compounds 30 wherein the .sup.noctyl R substituents have been removed for clarity. It can be seen that CFCF interactions dominate solid state packing, whilst no - stacking is observed due to the presence of proximal quaternary centres.

(304) FIG. 13 shows the X-ray structure for the borylated compound 22. FIG. 14 shows the X-ray packing structure of compounds 22. This compound is seen to have a similar packing structure to that of the C.sub.6F.sub.5 substituted ladder compound (compound 30) with CFCF interactions dominating the solid state packing. No - stacking was observed.

(305) FIG. 15 shows the X-ray structure for the borylated compound 35. - stacking interactions were observed.

EXAMPLE 4COMPUTATIONAL ANALYSIS

(306) Samples were optimised at the M06-2x/6311G(dp) level using Gaussian 09 and confirmed to have zero imaginary frequencies.

(307) FIG. 16 shows computational modelling of the molecular orbital of compound 29. It can be seen that the HOMO is located mainly on fluorene, with no HOMO character on the peripheral phenyl groups. The LUMO is seen to be located exclusively on benzothiadiazole, with no LUMO character observed on the peripheral phenyl groups.

EXAMPLE 5CYCLIC VOLTAMMETRY

(308) Cyclic voltammetry was performed using a CH-Instrument 1110C Electrochemical/Analyzer potentiostat under a nitrogen flow. Measurements were made using a 0.001 M analyte solution with 0.1 M tetrabutylammonium hexafluorophosphate (Fluka 99.0%) as the supporting electrolyte in distilled methylene chloride that had been degassed prior to use and obtained from a dry solvent system. A glassy carbon served as the working electrode and a platinum wire as the counter electrode. An Ag/AgNO.sub.3 non-aqueous reference electrode was used. All scans were calibrated against the ferrocene/ferrocenium (Fc/Fc.sup.+) redox couple, which in this work is taken to be 5.39 eV below vacuum .sup.[9]. The half-wave potential of the ferrocene/ferrocenium (Fc/Fc.sup.+) redox couple (E.sub.1/2, Fc,Fc+) was estimated from E.sub.1/2, Fc,Fc+=(E.sub.ap+E.sub.cp)/2, where E.sub.ap and E.sub.cp are the anodic and cathodic peak potentials, respectively.

(309) FIG. 17 shows the cyclic voltammogram for compound 22. Data extracted from the scan is provided in Table 2 below.

(310) TABLE-US-00003 TABLE 2 Cyclic voltammogram for compound 22 E.sub.red.sup.onset E.sub.ox.sup.onset HOMO LUMO Gap.sub.HOMO-LUMO (V) (V) (eV) (eV) (eV) Compound 0.946 0.630 6.02 4.44 1.58 vs Fc/Fc.sup.+

(311) Cyclic voltammetry measurement of this molecule show 2 reversible oxidation peaks and at least 1 reversible reduction peak. This molecule demonstrates an extremely low LUMO of 4.44 eV.

(312) FIG. 18 and Table 3 show the cyclic voltammograms for compounds 2, 9, 11, 39, and 12. This series shows the modulation of the frontier molecular orbital energies possible by varying the substituents on boron.

(313) TABLE-US-00004 TABLE 3 Cyclic voltammograms for compounds 2, 9, 11, 39, and 12 Optical Electroche Band mical max.sub.abs Gap E.sub.ox.sup.onset E.sub.red.sup.onset HOMO LUMO Band Compound (nm).sup.a (M.sup.1 cm.sup.1).sup.a (eV).sup.b (V).sup.c (V).sup.c (eV).sup.c (eV).sup.c Gap (eV) 2 471 15700 2.29 0.60 1.66 6.00 3.73 2.27 9 602 9700 1.73 0.46 1.33 5.85 4.06 1.79 11 611 9800 1.72 0.52 1.30 5.91 4.09 1.82 39 617 12600 1.70 0.57 1.24 5.96 4.15 1.81 12 641 7800 1.60 0.67 1.05 6.07 4.34 1.73 .sup.a1 10.sup.5M solution in toluene. .sup.bBand gap estimated from onset of absorption. .sup.cMeasured in DCM, (1 nM), with [nBu.sub.4N][PF.sub.6] (0.1M) as the supporting electrolyte at a scan rate of 50 mV/s, potentials are given relative to Fc/Fc.sup.+ redox couple which is taken to be 5.39 eV below vacuum.

EXAMPLE 6OLED DEVICE STUDIES

(314) A series of un-optimised OLED devices (devices 1-4, Table 4) were fabricated by solution processing. The emission layer (EmL) was deposited from a toluene solution containing 5 wt % of the appropriate borylated compound in 80 wt % PF8-BT/15 wt % PF8TFB (PF8TFB=Poly[(9,9-dioctylfluorenyl-2,7-diyl)-co-(4,4-(N-(4-sec-butylphenyl) diphenylamine)]), with the latter used to improve hole transport. The devices were constructed as follows, ITO (45 nm)/Plexcore OC (65 nm)/PF8-TFB (22 nm)/EmL (100 nm)/Ba (3.5 nm) An additional device was fabricated where the EmL was deposited from a solution containing only 5 wt % of 45 and 95% of PF8-BT (i.e. in the absence of hole transport material PF8TFB, device 4).

(315) TABLE-US-00005 TABLE 4 Summary of OLED device performance PL Compound max/nm EL X (QY/%).sup.a Device.sup.b max/nm.sup.c V.sub.on.sup.d/V EQE.sup.e(%) 45 696 (34) 1 678 2.3 0.46 29 651 (33) 2 634 2.1 0.14 30 673 (20) 3 643 2.2 0.13 45 696 (34) 4.sup.f 679 2.5 0.48 .sup.a= Photoluminescence of a film deposited from a 5/95 wt % solution of compound X/PF8-BT. Excitation at 468 nm and quantum yields determined using an integrating sphere. .sup.bOLED device structure: ITO (45 nm)/Plexcore OC (65 nm)/PF8-TFB (22 nm)/emissive layer (100 nm 85% PF8-BT/15% PF8-TFB/5% Compound X)/Ba (3.5 nm). .sup.c= electroluminescence emission maxima. .sup.dTurn-on voltage. .sup.emaximum external quantum efficiency. .sup.femissive layer 95:5 wt % PF8BT/2-BPh.sub.2.

(316) All devices possessed low turn-on voltages and showed electroluminescence spectra similar to their photoluminescence data in PF8-BT hosts, albeit with slightly blue shifted emission maxima (18-30 nm). Devices 1 and 4, both containing 45 as the emitter, showed the highest maximum EQE values (0.46 and 0.48%, respectively) of the series of compounds with a .sub.max of 678 nm and a broad emission stretching into the NIR. All devices showed minimal green emission from the F8-BT host except device 2 where this emission was significant.

(317) While specific embodiments of the invention have been described herein for the purpose of reference and illustration, various modifications will be apparent to a person skilled in the art without departing from the scope of the invention as defined by the appended claims.

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