WO2010075512A1

WO2010075512A1 - Polymers with bodipy-based backbone for solar cells

Info

Publication number: WO2010075512A1
Application number: PCT/US2009/069412
Authority: WO
Inventors: Biwu Ma; Haiying Liu
Original assignee: Michigan Technological University
Priority date: 2008-12-23
Filing date: 2009-12-23
Publication date: 2010-07-01

Abstract

The present application discloses the preparation of BODIPY-based backbone polymers for use in solar cell devices. Embodiments provide efficient solution-processed bulk heterojunction ("BHJ") polymer/PCBM solar cells with BODIPY-based backbone polymers (pBodipy and pBodipy-T) as the polymer electron donor. In some embodiments of the present application, solar cells exhibit highly efficient light harvesting of the solar spectrum up to ~1.6eV. CV data suggest these BODIPY-based backbone polymers have an optimal energy level alignment for charge separation in contact with PCBM, and deep HOMO levels that result in the high Voc of 0.8 V and efficiency of about 2%.

Description

POLYMERS WITH BODIPY-BASED BACKBONE FOR SOLAR CELLS

CROSS-REFERENCE TO RELATED APPLICATIONS

[0001] This application claims the benefit of co-pending U.S. Provisional Application Serial No. 61/140,529, filed December 23, 2008, which is incorporated by reference herein.

STATEMENT OF GOVERNMENT SUPPORT

[0002] This invention was made with United States government support from the U.S. Department of Energy under Contract No. DE-AC02-05CH11231. The United States government has certain rights in this invention.

BACKGROUND

[0003] Solution processed bulk heterojunction ("BHJ") polymer /fullerene solar cells have attracted great attention during the past decade for their substantial future prospects as low-cost 3rd generation photovoltaic ("PV") technology. The high performance of these types of solar cells is generally attributed to the high absorption coefficient of the composites for efficient light harvesting and exciton generation, and their ability of self- assembly to form bicontinuous nanophase separated morphology between polymer (donor) and fullerene (acceptor) for efficient charge separation and transport. The most- investigated poly(3-hexylthiophene) (P3HT)/[6,6]-phenyl C₆₁ butyric acid methyl ester ("PCBM") system, is able to harvest most of photons of the solar spectrum from 400 nm to 675 nm and generate nanophase separation between P3HT and PCBM with domain size of 10-20 nm upon thermal or solvent annealing, resulting in power conversion efficiencies ("PCEs") of 4-5%. However, the intrinsic properties of this P3HT/PCBM system, i.e. (i) the relatively large bandgap of P3HT (~1.85 eV) and (ii) the small energy difference between the highest occupied molecular orbitals ("HOMO") of P3HT and the lowest unoccupied molecular orbitals ("LUMO") of PCBM, have limited the light harvesting of solar irridation only up to 1.85 eV and the open circuit voltage ("V_oc") of 0.6 V.

[0004] A number of unique features of BODIPY dyes, including high absorption coefficients and luminescence quantum yields, delocalized molecular orbitals, as well as excellent photochemical and thermal stability, make them of great interest for PV application. Recently, a few organic solar cells using small molecular BODIPY derivatives as electron donor and PCBM as acceptor have been reported (the PCE of 1.3% from -small molecular BODIPY dye/PCBM blends and 1.7% from multi-BODIPY dyes/PCBM).

SUMMARY

[0005] The present application discloses a new class of low bandgap polymers bearing borondipyrromethene ("BODIPY") dyes incorporated into solar cell devices.

.[0006] In one aspect, the invention provides a solar cell comprising an anode; a hole injection layer; an active layer; and a cathode;wherein the active layer comprises a BODIPY-based backbone polymer. In another aspect, the BODIPY-based backbone polymer may be one according to formulas (I) to (IV).

BRIEF DESCRIPTION OF THE DRAWINGS [0007] FIG. 1 shows various carbohydrate residues. [0008] FIG. 2 shows various aryl groups.

[0009] FIG. 3 shows a synthetic route to conjugated polymers with BODIPY backbone.

[0010] FIG. 4 shows UV-visible absorption and emission spectra of BODIPY derivatives and polymer II.

[0011] FIG. 5 shows a synthetic route to fluorescent BODIPY-based conjugated copolymers.

[0012] FIG. 6 shows normalized UV-Visible absorption and fluorescent spectra of compounds 9 and 10, and polymer III in methylene chloride solution.

[0013] FIG. 7 shows an ORTEP representation of the molecular structure of compound 18. The non-H atoms are represented by thermal ellipsoids displayed at the 50% probability level and the H-atoms are indicated by circles of arbitrary radii.

[0014] FIG. 8 shows normalized UV-Visible absorption and fluorescent spectra of compounds 9 and 10, and polymer III in DMF solution.

[0015] FIG. 9 shows normalized UV-Visible absorption and fluorescent spectra of compounds 14 and 15, and polymer IV in methylene chloride solution. [0016] FIG. 10 shows normalized UV- Visible absorption and fluorescent spectra of compounds 14 and 15, and polymer IV in DMF solution.

[0017] FIG. 11 shows normalized UV-Visible absorption and fluorescent spectra of compounds 18 and 19, and polymer V in methylene chloride solution.

[0018] FIG. 12 shows normalized UV-Visible absorption and fluorescent spectra of compounds 18 and 19, and polymer V in DMF solution.

[0019] FIG. 13 shows chemical structures of BODIPY-based conjugated glycopolymers.

[0020] FIG. 14 shows chemical Structures of BODIPY-based conjugated glycol- copolymers.

[0021] FIG. 15 shows a synthetic route to fluorescent conjugated glyopolymers XIX and XX.

[0022] FIG. 16 shows a synthetic route to fluorescent conjugated glycopolythiophenes.

[0023] FIG. 17 shows a synthetic route to highly water-soluble fluorene-based β- glucose-bearing and α-mannose bearing conjugated glycopolymers with poly(ethylene glycol) tethered spacers (polymers XXIII and XXIV₁ respectively).

[0024] FIG. 18 shows a synthetic route to bromide-bearing poly(BODIPY- ethylene)(polymer I) and ester-bearing poly(BODIPY-ethynylene)s (Polymers XXVI and XXVII).

[0025] FIG. 19 shows a synthetic route to BODIPY-based copolymers (polymers XXVIII and XXIX).

[0026] FIG. 20 shows a synthetic route to BODIPY dyes.

[0027] FIG. 21 shows a synthetic route to BODIPY dyes.

[0028] FIG. 22 shows a synthetic route to BODIPY dyes.

[0029] FIG. 23 shows a synthetic route to BODIPY dyes.

[0030] FIG. 24 shows a synthetic route to BODIPY dyes. [0031] FIG. 25 shows chemical structures of BODIPY polymeric and copolymeric dyes.

[0032] FIG. 26 shows a synthetic route to BODIPY dyes.

[0033] FIG. 27 shows a synthetic route to BODIPY copolymeric dyes.

[0034] FIG. 28 shows a synthetic route to BODIPY copolymeric dyes.

[0035] FIG. 29 shows a synthetic route to BODIPY copolymeric dyes.

[0036] FIG. 30 shows absorption spectra of BODIPY dyes and polymeric dyes.

[0037] FIG. 31 shows fluorescence spectra of BODIPY dyes and polymeric dyes.

[0038] FIG. 32 shows absorption and fluorescence spectra of BODIPY copolymeric dyes.

[0039] FIG. 33 shows TGA curves for BODIPY based polymers.

[0040] FIG. 34 shows chemical structures of conjugated polymers with BODIPY backbone.

[0041] FIG. 35 shows a synthetic route to a BODIPY based polymer. [0042] FIG. 36 shows a synthetic route to a BODIPY based polymer. [0043] FIG. 37 shows synthetic route to a BODIPY based polymer.

[0044] FIG. 38 shows absorption and fluorescence spectra for BODIPY dyes and ■polymers.

[0045] FIG. 39 shows absorption and fluorescence spectra for BODIPY dyes and polymers.

[0046] FIG. 40 shows absorption and fluorescence spectra for BODIPY dyes and polymers.

[0047] FIG. 41 shows TGA curves for BODIPY based polymers.

[0048] FIG. 42 shows chemical structures of conjugated polymers with BODIPY backbone

[0049] FIG. 43 shows a synthetic route to a BODIPY based polymer. .[0050] FIG. 44 shows a synthetic route to a BODIPY based polymer. [0051] FIG. 45 shows absorption spectra for BODIPY dyes and polymers. [0052] FIG. 46 shows fluorescence spectra for BODIPY dyes and polymers.

[0053] FIG. 47 shows UV- Vis abosorption spectra of pBodipyand pBodipy-T in films. Extinction coefficient is determined by dividing absorption by film thickness.

[0054] FIG. 48 shows (a) J-V characteristics of solar cells with the configuration shown under 100 mW/cm² AM 1.5 G illumination (the mass ratio of polymer/PCBM is 1 :4 and 1 :3 for pBodipy/PCBM and pBodipy-T/PCBM, respectively), and (b) external quantum efficiency as a function of wavelength, measured at 0 V.

[0055] FIG. 49 shows tapping mode AFM topography images of the polymer blend of (a) pBodipy/PCBM (1 :4) and (b) pBodipy-T/PCBM (1 :3). Image size is 4 * 4 μm².

[0056] FIG. 50 shows CV curves of (a) pBodipy and (b) pBodipy-T.

DETAILED DESCRIPTION

.[0057] Before any embodiments of the present application are explained in detail, it is to be understood that the invention is not limited in its application to the details of construction and the arrangement of components set forth in the following description or illustrated in the following drawings. The invention is capable of other embodiments and of being practiced or of being carried out in various ways.

■Introduction

[0058] Solution processed bulk heterojunction ("BHJ") polymer /fullerene solar cells are known in the art. (See, e.g., Yu er a/., Science, 1995, 270, 1789-1791 ; Thompson et al., Angew. Chem. Int. Ed., 2008, 47, 58-77; Dennler et al., Adv. Mater, 2009, 21, 1323- 1338; Li et al., Adv. Mater, 2008, 20, 2952-2958, Hoppe ef al., J. Mater. Chem., 2006, 16, 45-61; Ma, et al., Adv. Fυnct. Mater, 2005, 15, 1617-1622; Li et al., Nat. Mater, 2005, 4, 864-868; Blouin er a/., Adv. Mater, 2007, 19, 2295-2300; Chen et al., Ace. Chem. Res., 2009, ASAP; Kroon et al., Poly. Rev., 2008, 48, 531-582; Liang et al., J. Am. Chem. Soc, 2009, 131, 56-57; Park ef al., Nat. Photon., 2009, 3, 297-303; Peet ef al., Nat. Mater, 2007, 6, 497-500; Wakim ef al., J. Mater. Chem., 2009, 19, 5351-5358; Wienk ef al., Adv. Mater, 2008, 20, 2556-2560; and Zou et al., Macromolecules, 2009, 42, 2891-2894. [0059] The terms "bulk heterojunction layer" ("BHJ layer") and "active layer" are used interchangeably in the present application.

[0060] Commonly, solar cells, such as those disclosed in the references above, can be made of several components, including, for example: electrodes {i.e., anodes and cathodes), a hole injection layer, and a BHJ or "active layer". Suitably, the anode can include, for example, indium tin oxide ("ITO"). The ITO anode may be supported on a substrate, such as, for example, glass. The cathode can include, for example, aluminum. The hole injection layer may commonly include PEDOT:PSS as known in the art.

[0061] The active layer can comprise at least one electron acceptor material and at least one electron donor material. The electron acceptor material can include, for example, PCBM (Scheme 1). The electron donor material may include at least one active polymer, wherein the active polymer can comprise a BODIPY-based backbone polymer. In some embodiments, the at least one active polymer can include "pBodipy" (Scheme 1). In some embodiments, the at least one active polymer can include "pBodipy-T" (Scheme 1) Desirably, active polymers possess a high absorption coefficient with a bandgap of about 1.6 eV.

[0062]

pBodipy pBodipy-T PCBM

Scheme 1. Structures of BODIPY-based backbone polymers and PCBM.

[0063] The active layer (e.g., polymer/PCBM) thickness in a solar cell can typically be between about 40 nm and about 300 nm, commonly between about 55nm and 200 nm, and desirably between about 60 nm and about 100 nm. In some embodiments, the active polymer/PCBM layer thickness can be about 70 nm.

[0064] Various weight ratios of active polymer to PCBM can be used in preparing active layers for solar cells of the present application. In some embodiments, the weight ratio of active polymer to PCMB can suitably be about 1:1 to about 1 :6, commonly about 1 :2 to about 1 :5, or desirably about 1 :2.5 to about 1 :4.5. In some embodiments, the weight ratio of active polymer to PCBM can be about 1 :3 to about 1 :4. In one embodiment, the weight ratio of pBodipy polymer to PCBM can be about 1 :4. In another embodiment, the weight ratio of pBodipy-T to PCBM can be about 1 :3.

[0065] In some embodiments, BHJ solar cells including a blend of BODIPY-based backbone polymer and PCBM can have PCEs of up to at least about 1.0%, up to at least about 1.2%, up to at least about 1.4%, up to at least about 1.6%, up to at least about1.8%, up to at least about 2%, up to at least about 3%, up to at least about 4%, up to at least about 5%, up to at least about 6%, or up to at least about 10%.

[0066] In some embodiments, BHJ solar cells including an active layer comprising a blend of BODIPY-based backbone polymer and PCBM can have a V_oc of at least about 0.6 eV, at least about 0.65 eV, at least about 0.7 eV, at least about 0.75 eV, at least about 0.8 eV , at least about 0.85 eV, or at least about 0.9 eV. In some embodiments, BHJ solar cells including a blend of BODIPY-based backbone polymer and PCBM can have a power conversion efficiency ("PCE") of at least about 2% with V₀₀ of at least about 0.8 eV and J_sc of at least about 4.8 mA/cm².

[0067] Suitable BODIPY-based polymers for use in the present invention include a polymer according to formula (I):

(I) wherein each -A- is independently selected from -AR- -AR- AR- or

-AR- wherein each -AR- is independently selected from arylene or heteroarylene; wherein each R₃ is independently selected from R, alkyl, aryl or heteroaryl wherein each R₂ and R₄ are independently selected from alkyl or H; wherein each R₁ and R₅ are independently selected from hydrogen, alkyl, or = AR ^• wherein each R₀ is -F, -OR, -R, aryl, heteroaryl, — ≡≡≡- I Aryl , or ^^EΞ Heteroaryl . wherein each R is independently selected from -H, -(CH₂)_mRio, -(CH₂)_mCOO(CH₂)_pCH₃, -(CH₂)_mSO₃Na, -(CH₂)J³O₃Na₁ -(CH₂)_mN(CH₃)₃ ⁺Br, -(CH₂)_mCOH(CH₂)_pCH₃, - (CH₂)_mOR_10, -(CH₂)_mOR_8, -CH₂CH₂(OCH₂CH₂)_H1OR₁O, -CH₂CH₂(OCH₂CH₂)_mOR_B, -

CH₂CH₂(OCH₂CH₂)_mSR₈, or

; and wherein each R₈ is independently selected from a carbohydrate residue; and wherein each R₁₀ is independently selected from hydrogen, alkyl, heteroalkyl, hydroxy, amino, ammonic acid, thiol, carboxylic acid, nitrile, azide, ethynylene, halo, and tosylate; wherein m is from O to 100; wherein n is from 2 to 300 and wherein p is from 0 to 20.

[0068] In another embodiment, the polymer may be according to formula (II):

(H) wherein each -A- is independently selected from -AR- -AR- -AR- or

-AR- wherein each -AR- is independently selected from arylene or heteroarylene; wherein each R₃ is independently selected from R, alkyl, aryl or heteroaryl wherein each R₂ and R₄ are independently selected from alkyl or H; wherein each R₆ is independently selected from H or alkyl; wherein each R₀ is -F, -OR, -R, aryl, heteroaryl, — ≡≡- -Aryl , or ΞΞΞ Heteroaryl . wherein each R is independently selected from -H, -(CH₂)_mR₁₀, -(CH₂)_mCOO(CH₂)_pCH₃, -(CH₂)_mSO₃Na, -(CH₂)J³O₃Na, -(CH₂)_mN(CH₃)₃ ⁺Br, -(CH₂)_mCOH(CH₂)_pCH₃, - (CH_z)_mOR_10, -(CH₂)_mOR_8, -CH₂CH₂(OCH₂CH₂)_mORi₀, -CH₂CH₂(OCH₂CH₂)_mOR₈, -

CH₂CH₂(OCH₂CH₂)mSR8, or

\ — Λ — A — / ; and wherein each R₈ is independently selected from a carbohydrate residue; and wherein each R₁₀ is independently selected from hydrogen, alkyl, heteroalkyl, hydroxy, amino, ammonic acid, thiol, carboxylic acid, nitrile, azide, ethynylene, halo, and tosylate; wherein m is from O to 100; wherein n is from 2 to 300 and wherein p is from 0 to 20.

[0069] In yet another embodiment, the polymer may be according to formula (III):

(III) wherein each -A- is independently selected from -AR- -AR- -AR- ^', or

-AR- wherein each -AR- is independently selected from arylene or heteroarylene; wherein each R₃ is independently selected from R, alkyl, aryl or heteroaryl wherein each R₂ and R₄ are independently selected from alkyl or H; wherein each R₆ is independently selected from H or alkyl; wherein each R₀ is -F₁ -OR, -R₁ aryl, heteroaryl, — ≡≡- -Aryl , or ΞΞΞEΞ Heteroaryl . wherein each R is independently selected from -H₁ -(CH₂)_mRi₀, -(CH₂)_mCOO(CH₂)pCH3, -(CH₂)_mSO₃Na, -(CH₂)_mPO₃Na, -(CH₂)_mN(CH₃)₃ ⁺Br, -(CH₂)_mCOH(CH₂)_pCH₃, - (CH₂)_mOR₁₀. -(CH₂)_mOR₈. -CH₂CH₂(OCH₂CH₂)_mOR₁₀. -CH₂CH₂(OCH₂CH₂)_mOR₈, -

CH₂CH₂(OCH₂CH₂)_mSR₈, or

\ — Λ — /\ — / ; and wherein each R₈ is independently selected from a carbohydrate residue; and wherein each Ri₀ is independently selected from hydrogen, alkyl, heteroalkyl, hydroxy, amino, ammonic acid, thiol, carboxylic acid, nitrile, azide, ethynylene, halo, and tosylate; wherein m is from O to 100; wherein n is from 2 to 300 and wherein p is from 0 to 20.

[0070] In a further embodiment, the polymer may be according to formula (IV):

(IV) wherein each -A- is independently selected from -AR-

-AR- ^", or

-AR- wherein each -AR- is independently selected from arylene or heteroarylene; wherein each R₃ is independently selected from R₁ alkyl, aryl or heteroaryl wherein each R₂ and R₄ are independently selected from alkyl or H; wherein each R₆ is independently selected from H or alkyl; wherein each R₀ is -F, -OR, -R, aryl, heteroaryl, — ≡≡ — R , ^■ Aryl , or ΞΞΞ= Heteroaryl . wherein each R is independently selected from -H, -(CH^R^, -(CH₂)mCOO(CH₂)_pCH₃, -(CH₂)_mSO₃Na, -(CH₂)_mPO₃Na, -(CH₂)_mN(CH₃)₃ ⁺Br, -(CH₂)_mCOH(CH₂)_pCH₃, - (CH₂)_mOR₁₀, -(CH₂)_mOR_β -CH₂CH₂(OCH₂CH₂)_mOR₁₀, -CH₂CH₂(OCH₂CH₂)_mOR₈, -

CH₂CH₂(OCH₂CHa)_1nSRe₁ Or

wherein each R₈ is independently selected from a carbohydrate residue; and wherein each R₁₀ is independently selected from hydrogen, alkyl, heteroalkyl, hydroxy, amino, ammonic acid, thiol, carboxylic acid, nitrile, azide, ethynylene, halo, and tosylate; wherein m is from O to 100, wherein n is from 2 to 300 and wherein p is from 0 to 20.

[0071] In certain embodiments, -AR- is selected from the following:

wherein each R_A, R₈, Rc and Rp is independently selected from R, OR, hydrogen, alkyl, heteroalkyl, hydroxy, amino, thiol, carboxylic acid, nitrile, azide, halo or R_A and R₈ may together form an aromatic ring, or R_c and R₀ may together form an aromatic ring or both R_A and R_B and R_c and R_D may together form an aromatic ring; wherein each R_E, RF and R_G is independently selected from R, OR, hydrogen, alkyl, heteroalkyl, aryl, heteroaryl, hydroxy, amino, thiol, carboxylic acid, nitrile, azide, halo, or

RE and R_F may together form a ring; wherein each R_H, Ri, Rj, RK, RL, RM, R_N, and R₀ is independently selected from R, OR₁ hydrogen, alkyl, heteroalkyl, hydroxy, amino, thiol, carboxylic acid, nitrile, azide, halo, or

Ri and Rj may together form a ring, or R_M and R_N may together form a ring; wherein each R_P and R_Q is independently selected from hydrogen or together form an aromatic ring; wherein each R_s is independently selected from hydrogen or OR; wherein each X is independently a carbon atom or a heteroatom; wherein q is an integer from 1 to 3; wherein M is selected from Zn, Cu, Fe, and Pt; wherein M2 is selected from Ru or Ir; and

wherein bpy is wherein each R is independently selected from -H, -(CH₂)_mRio, -(CH₂)_mCOO(CH₂)pCH₃, -(CH₂)_mSO₃Na, -(CH₂)_mPO₃Na, -(CH₂)_mN(CH₃)₃ ⁺Br, -(CH₂)_mCOH(CH₂)_pCH₃, - (CH₂)_mOR₁₀. -(CH₂)_mOR₈,

-CH₂CH₂(OCH₂CH₂)_mOR₈, -

wherein each R₈ is independently selected from a carbohydrate residue; and wherein each R₁₀ is independently selected from hydrogen, alkyl, heteroalkyl, hydroxy, amino, ammonic acid, thiol, carboxylic acid, nitrile, azide, ethynylene, halo, and tosylate.

[0072] Alternatively, -AR- may be

(bpy)₂

wherein each R_A, RB, RC and R_D is independently selected from R, OR, hydrogen, alkyl, heteroalkyl, hydroxy, amino, thiol, carboxylic acid, nitrile, azide, halo or R_A and R_B may together form an aromatic ring, or Rc and Rp may together form an aromatic ring or both

R_A and R₈ and R_c and R_D may together form an aromatic ring; wherein each R_ε, R_F and R_G is independently selected from R, OR, hydrogen, alkyl, heteroalkyl, aryl, heteroaryl, hydroxy, amino, thiol, carboxylic acid, nitrile, azide, halo, or

RE and R_F may together form a ring; wherein each R_H, Ri, Rj, RK, RL, RM, RN, and R₀ is independently selected from R, OR, hydrogen, alkyl, heteroalkyl, hydroxy, amino, thiol, carboxylic acid, nitrile, azide, halo, or

Ri and Rj may together form a ring, or R_M and R_N may together form a ring; wherein each Rp and R_Q is independently selected from hydrogen or together form an aromatic ring; wherein each R_s is independently selected from hydrogen or OR; wherein each X is independently a carbon atom or a heteroatom; wherein q is an integer from 1 to 3; wherein M is selected from Zn, Cu, Fe, or Pt; wherein M2 is selected from Ru or Ir; and

wherein bpy is

wherein each R is independently selected from -H, -{CH₂)_mRio, -(CH₂)_mCOO(CH₂)pCH₃, -(CH₂)_mSO₃Na, -{CH₂)_mPO₃Na. -{CH₂)_mN(CH₃)₃ ⁺Br, -(CH₂)_mCOH(CH₂)_pCH₃, - (CH₂)_mOR_10, -(CH₂)_mOR₈. -CH₂CH₂(OCH₂CH₂)mORio, -CH₂CH₂(OCH₂CH₂)_mOR₈, -

CH₂CH₂(OCH₂CH₂)_mSR₈, or

; and wherein each R₈ is independently selected from a carbohydrate residue; and wherein each R₁₀ is independently selected from hydrogen, alkyl, heteroalkyl, hydroxy, amino, ammonic acid, thiol, carboxylic acid, nitrile, azide, ethynylene, halo, and tosylate.

[0073] For example, -AR- may be those moieties shown in FIG. 2.

[0074] In certain embodiments, R₃ may be

where R is as defined above.

[0075] In other embodiments, R₃ may be

wherein each R_F is independently selected from R, OR, hydrogen, alkyl, heteroalkyl, aryl, heteroaryl, hydroxy, amino, thiol, carboxylic acid, nitrile, azide or halo; and wherein each R is independently selected from -H, -<CH₂)_mR₁₀, -(CH₂)_mCOO(CH₂)_pCH₃, -(CH₂)_mSO₃Na, -(CH₂)_mPO₃Na, -(CH₂)_mN(CH₃)₃ ⁺Br, -(CH₂)_mCOH(CH₂)_pCH₃, - (CH₂)_mOR₁₀. -(CH₂)_mOR₈. -CH₂CH₂(OCH₂CH₂)_mOR₁₀, -CH₂CH₂(OCH₂CH₂)_mOR_β, -

CH₂CH₂(OCH₂CH₂)_mSR_8> or

[0076] In certain embodiments, R₁ or R₅ may be \ /

where R is as defined above.

[0077] In some embodiments, R₀ may be

wherein each R is as defined above.

[0078] In some embodiments, m is from 0 to 50 or from 0 to 30 or from 0 to 20. In some embodiments, n is from 2 to 200 or 2 to 150. In some embodiments, p is from 1 to 10 or 3 to 15.

[0079] As used herein, "alkyl" refers to a saturated or unsaturated hydrocarbon chain having 1 to 12 carbon atoms (e.g. methyl, ethyl, propyl, butyl). Alkyl groups may be straight or branched. In some embodiments, branched alkyl groups have one or two branches. Unsaturated alkyl groups have one or more double bonds and/or one or more triple bonds. Suitably, unsaturated alkyl groups have one or two double bonds or one triple bond. Alkyl chains may be unsubstituted or substituted with from 1 to about 4 substituents unless otherwise specified. Suitably, alkyl groups are mono-, di-, or tri- substituted. Suitable alkyl substituents include, but are not limited to, cyano, oxo, halo, hydroxy, aryl (e.g., phenyl, tolyl, alkyloxphenyl, alkyloxycarbonylphenyl, halophenyl), heterocyclyl, and heteroaryl. "Lower alkyl" refers to alkyl chains having from 1 to 4 carbon atoms. [0080] "Aryl" refers to an aromatic carbocyclic group. "Aryl" may be exemplified by phenyl. The aryl group may be substituted or unsubstituted. More than one substituent may be present. Substituents may also be themselves substituted. When substituted, the substituent group is preferably but not limited to heteroaryl; acyl, carboxyl, carbonylamino, nitro, amino, cyano, halogen, or hydroxyl. "Arylene" refers to a divalent aryl group.

[0081] "Aromatic ring" refers to a mono, bicyclic, or polycyclic ring structure which is conjugated and has a much greater stability due to electron derealization than the hypothetical localized structure. The aromatic ring optionally contains one or more heteroatoms independently selected from nitrogen, oxygen, selenium, or sulfur. Suitable aromatic rings include, for example: anthracenyl, bipyridyl, fluorenonyl, furanyl, naphthyl, phenanthryl, phenyl, pyrazinyl, pyrenyl, pyridinyl, pyrrolyl, selenopheyl, thiazolyl, thienyl. Aromatic rings may be unsubstituted or substituted with from 1 to about 4 substituents. Suitable aromatic ring substitutents may include, for example: aryl, alkyl, alkenyl, alkynyl, halo, heteroalkyl, heterocyclyl, and heteroaryl.

[0082] "Halo" refers to fluoro, chloro, bromo or iodo.

[0083] "Heteroalkyl" refers to a saturated or unsaturated chain containing carbon and at least one heteroatom, wherein no two heteroatoms are adjacent. Heteroalkyl groups contain from 1 to 12 member atoms (carbon and heteroatoms) in the chain. Heteroalkyl groups may be straight or branched. Suitably, the branched heteroalkyl may have one or two branches. Unsaturated heteroalkyl have one or more double bonds and/or one or more triple bonds. Heteroalkyl groups may be unsubstituted or substituted with from 1 to about 4 substituents unless otherwise specified. Suitable heteroalkyl substituents include halo, aryl (e.g., phenyl, tolyl, alky loxy phenyl, alkyloxycarbonylphenyl, halophenyl), heterocyclyl, heteroaryl. For example, alkyl chains substituted with the following substituents are heteroalkyl: alkoxy (e.g., methoxy, ethoxy, propoxy, butoxy, peπtoxy), aryloxy (e.g., phenoxy, chlorophenoxy, tolyloxy, methoxy phenoxy, benzyloxy, alkyloxycarbonylphenoxy, acy loxy phenoxy), acyloxy (e.g., propionyloxy, benzoyloxy, acetoxy), carbamoyloxy, carboxy, mercapto, alkylthio, acylthio, arylthio (e.g., phenylthio, chlorophenylthio, alkylphenylthio, alkoxyphenylthio, benzylthio, alkyloxycarbonylphenylthio), amino (e.g., amino, mono- and di- C1-C3 alkanylamino, methylphenylamino, methylbenzylamino, C1-C3 alkanylamido, carbamamido, ureido, guanidino). "Lower heteroalkyl" refers to heteroalkyl chains having 1 to 4 member atoms. [0084] "Heteroaryl" refers to a monocyclic or tricyclic aromatic carbocyclic radical having one or more heteroatoms in the carbocyclic ring. Heteroaryl may be substituted or unsubstituted. More than one substituent may be present. When substituted, the substituents may themselves be substituted. Preferred but non limiting substituents are aryl, C₁-C₄ alkylaryl, amino, halogen, hydroxy, cyano, nitro, carboxyl, carbonylamino, or Ci-C₄ alkyl. Preferred heteroaromatic groups include tetrazoyl, triazolyl, thienyl, thiazolyl, purinyl, pyrimidyl, pyridyl, and furanyl. More preferred heteroaromatic groups include benzothiofuranyl; thienyl, furanyl, tetrazoyl, triazolyl, and pyridyl. "Heteroarylene" refers to a divalent heteroaryl group.

[0085] "Heteroatom" refers to a nitrogen, sulfur, selenium or oxygen atom. Groups containing more than one heteroatom may contain different heteroatoms. As used herein, halogens are not heteroatoms.

[0086] "Member atom" refers to a polyvalent atom (e.g., C, O, N, or S atom) in a chain or ring system that continues the chain or ring system. For example, in benzene the six carbon atoms are member atoms and the six hydrogen atoms are not member atoms.

[0087] "Ring" refers to a cycloalkyl, heterocycloalkyl, or an aromatic ring. The ring has from 5 to 7 members. A ring may be unsubstituted or substituted with from 1 to about 4 substituents. Suitable ring substitutents may include, for example: aryl, alkyl, alkenyl, alkynyl, halo, heteroalkyl, heterocyclyl, or heteroaryl.

[0088] As used herein,

refers to any of the following:

[

As used herein, refers to any of the following: [009

As used herein, refers to any of the following:

[0091] The polymers of the present invention may display significant red shifts of both UV -absorption and emission maxima compared with their BODIPY counterparts due to significantly extended π-conjugation. Commonly, polyfluorene homopolymers possess a large band gap and emit blue light. A variety of narrow-band-gap monomer units such as 2,1 ,3-benzoselenadiazole, 2,1 ,3-naphthoselenadiazole and 4,7-dithiophen-2'-yl-2,1 ,3- benzothiazole can be incorporated into the polyfluorene backbone to tune the polymer emission wavelengths from orange to red or even to the near-infrared region. In one embodiment, the BODIPY-based polymers are soluble in aqueous solution or organic solvents such as chloroform, methylene chloride, acetone, dimethylformamide, dimethyl sulfoxide and tetrahydrofuran. Suitably, aromatic groups can be introduced at the meso- position to enhance solubility. meso

[0092] The use of poly(ethylene glycol) linkers between carbohydrates and polymer backbone makes fluorene-based conjugated glycopolymers highly soluble in aqueous solution and enables sensitive detection of a few cells of E. coli bacteria.

[0093] In one embodiment, the present invention provides fluorescent conjugated polymers with BODIPY backbone bearing ethyl phenoxybutanoate groups at the meso- position (polymers I and II).

POLYMER I POLYMER Il

Synthesis of BODIPY-based polymers

[0094] The BODIPY-based polymers may be synthesized using a palladium catalyzed Suzuki polymerization of boronic acid substituted monomers and diiodo-substituted BODIPY-monomers, by employing a palladium catalyzed Sonogashira polymerization of diiodo-substituted BODIPY monomers with diethynyl-substituted BODIPY monomers or aryl monomers, by polymerizing diethynyl-substituted BODIPY monomers with CuCI, or by utilizing a palladium catalyzed Heck polymerization of diiodo-substituted BODIPY- monomers with divinyl-functionalized BODIPY monomers or aryl monomers. Various polymers and their syntheses are described in Color Tuning of Polyfluorene Emission with BODIPY Monomers. Ge Meng, Singaravelu Velayudham, Adrian Smith, Rudy Luck, and Haiying Liu, Macromolecules, 42 (2009) 1995-2001 , which is incorporated by reference herein; Synthesis and Optical Properties of Red and Deep-Red Emissive Polymeric and Copolymeric BODIPY Dyes, Venkat R. Donuru, Giri K. Vegesna, Singaravelu Velayudham, Sarah Green, and Haiying Liu, Chemistry of Materials, 21(10) (2009) 2130-2138, which is incorporated by reference herein; and Deep-Red Emissive Conjugated Poly(2,6-BODIPY-Ethynylene)s Bearing Alkyl Side Chains, Venkat R. Donuru, Giri K. Vegesna, Singaravelu Velayudham, Ge Meng, Haiying Liu, Journal of Polymer Science, Part A: Polymer Chemistry, 47(20) (2009) 5354-5366, which is incorporated by reference herein.

[0095] For example, 9,9-dihexylfluorene-2,7-diboronic acid may be coupled with each one of three different 2,6-diiodo-substituted BODIPY monomers, affording polymers III, IV and V.

POLYMER III POLYMER IV POLYMER V

EXAMPLES

[0096] Characterization of BODIPY-based Monomers and Functional Conjugated Polymers. All intermediates, carbohydrates, BODIPY dyes and conjugated polymers and glycopolymers will be fully characterized by ¹H, ¹³C and ¹¹B NMR spectroscopy, mass spectrometry, FI-IR and elemental analysis. Spectrophotometer and spectrofluometer will be used to study optical absorption, bandgap, Stoke's shift, fluorescence quantum yield and vibrational structures of fluorescent conjugated glycopolymers. The molecular weights of the glycopolymers can be manipulated by controlling polymerization time for conjugated polymers. Gel permeation chromatography ("GPC") will be used to determine molecular weight of the conjugated polymers. Matrix- assisted laser desorption/ionization time of flight mass spectrometer will also be used to determine molecular weights, repeated units, and capping end groups of conjugated polymers.

Example 1 : Synthesis of Meso-aryl-substituted BODIPY-Based Polymers

[0097] Meso-aryl-substituted BODIPY derivatives (3a and 3b) were prepared through the reaction of the formyl benzene derivatives (1a and 1b) with a large excess of 2,4- dimethylpyrrole under acid catalysis, and followed by oxidization with 2,3- dichloro-5,6- dicyano-1 ,4-benzoquinone (DDQ) and treatment with BF₃ etherate in the presence of Λ/,Λ/-diisopropylethylamine (DIEA) (FIG. 3). Further iodination of BODIPY derivatives (3a and 3b) afforded 2,6-diiodo-tetramethyl BODIPY derivatives (4a and 4b). 2,6-Diethynyl BODIPY derivatives (6a and 6b) were prepared by palladium-catalyzed Sonogashira reaction of compounds 4a and 4b with ethynyltrimethylsilaπe, affording compounds 5a and 5b, respectively, and followed by hydrolysis of compounds 5a and 5b in the presence of tetrabutylammonium fluoride.

[0098] Diethynylation of compound 4a causes peaks at 1 ,4 ppm corresponding to methyl group of compound 4a at 2 position to shift to lower field at 1.5 ppm and result in an additional peak at 3.3 ppm corresponding to diethynyl groups of monomer 6a. BODIPY polymers (I and II) were synthesized by palladium-catayzed Sonogashira polymenzation of diiodo-functionalized BODIPY monomers (4a and 4b) with diethynyl- functionalized BODIPY monomers (6a and 6b) (FIG. 3). ¹H NMR peaks of polymer I became a little broader than those of its monomer counterparts. Polymers I and Il exhibit solubility similar to that of their BODIPY monomers and are soluble in common organic solvents such chloroform, methylene chloride and THF.

[0099] Arylation at the meso position has no significant effect on the absorption and emission maxima since the arylated moiety is not coplanar with the BODIPY core due to the steric hindrance although the substitution position is structurally unique. As a result, polymers I and Il and their monomer counterparts have only 1 nm difference in their absorption and emission maxima as conjugated polymers do not amplify the tiny difference. However, the quantum yields of the meso-phenyl compounds (3a, 4a, 5a and 6a) are a little less than the corresponding more substituted analogues (3b, 4b, 5b and 6b).

[00100] Compound 1b: ¹H NMR (400 MHz, CDCI₃) §9.80 (s, 1H), 7.42-7.37 (m, 2H), 6.94 (d, J= 8.0 Hz, 1H), 4.15-4.06 (m, 8H), 2.54-2.49 (m, 4H), 2.17-2.12 (m, 4H), 1.23 (t, J= 7.2 Hz, 6H); ¹³C NMR (100 MHz, CDCI₃) δi91.0, 173.2, 154.4, 149.3, 130.3, 126.9, 112.2, 11 1.5, 68.1 , 68.0, 60.6, 30.8, 30.6,24.6,24.5; 14.4.

[00101] Compound 3b: ¹H NMR (400 MHz, CDCI₃) Sβ.95 (d, J = 8.4 Hz, 1H), 6.78- 6.76 (m, 2H), 5.95 (s, 1 H), 4. 17-4.05(m, 6H), 3.98(t, J = 6.0 Hz, 2H) 2.56-2.48 (m, 10H),

2.18-2.08 (m, 4H), 1.44(s, 6H), 1.26-1.20 (m, 6H); ¹³C NMR (100 MHz, CDC₁₃) 6i73.3,

173.2, 155.5, 149.7, 143.3, 141.7, 131.8, 127.7, 121.3, 121.1 , 114.3, 113.9, 68.5, 68.2, 60.6, 30.8, 24.8, 14.7, 14.6, 14.4. ESI-MS calculated for M+ 584.4, found 607.3 (M+Na)

[00102] Compound 4b: ¹H NMR (400 MHz, CDCI₃) δδ.97 (d, J = 8.4 Hz, 1 H), 6.75- 6.71 (m, 2H), 4.17-4.09 (m, 6H), 3.97(t, J = 6.0 Hz, 2H), 2.61(s, 6H) 2.57-2.48 (m, 4H),

2.18-2.08 (m, 4H), 1.45 (s, 6H), 1.27-1.20 (m, 6H); ¹³C NMR (100 MHz, CDCI₃) δi73.3,

173.1 , 156.8, 150.0, 149.9, 145.5, 141.4, 131.8, 127.2, 120.9,114.3, 113.6, 85.7, 68.6, 68.2, 60.6, 30.8, 24.8, 17.3, 16.2, 14.4. ESI-MS calculated for M+ 836.2, found 859.4 (M+Na).

[00103] Compound 5b: ¹H NMR (400 MHz, CDCI₃) δβ.96 (d, J = 8.4 Hz, 1H), 6.74- 6.71 (m, 2H), 4.15-4.07 (m, 6H), 3.97 (t, J = 6.0 Hz, 2H), 2.60(s, 6H) 2.57-2.48 (m, 4H), 2.18-2.09 (m, 4H), 1.52 (5, 6H), 1.27-1.20 (m, 6H), 0.19 (5, 18H); ¹³C NMR (100 MHz,

CDCI₃) δ 173.3, 173.1 , 158.8, 149.9, 149.8, 145.0, 142.7, 131.4, 127.0, 120.9, 116.4,

114.3, 113.6, 101.9, 97.3, 68.6, 68.2, 60.6, 30.8, 24.8, 14.4, 13.7, 13.6, 0.28; ESI-MS calculated for M+ 776.8, found 776.9

[00104] Compound 6b: ¹H NMR (400 MHz, CDCI₃) δ 6.97 (d, J = 8.4 Hz, 1 H), 6.76- 6.71 (m, 2H), 4.15-4.07 (m, 6H), 3.96(t, J = 6.0 Hz, 2H), 3.30(s, 2H)₁ 2.60(s, 6H) 2.57- 2.48 (m, 4H), 2.18-2.09 (m, 4H), 1.54 (s, 6H), 1.27-1.20 (m, 6H); ¹³C NMR (100 MHz,

CDC13) δ 173.3, 173.1 , 158.9, 150.0, 149.9, 143.2, 131.4, 126.8, 120.9, 115.2, 114.3, 113.6, 84.6, 76.1, 68.6, 68.2, 60.6, 30.8, 24.8, 14.4, 13.7, 13.6; ESI-MS calculated for M+ 632.5, found 656.9 (M+Na).

[00105] Polymer II: ¹H NMR (400 MHz, CDCI₃) δδ.97 (d, J = 8.4 Hz, 1H), 6.76-6.71 (m, 2H), 4.15-4.07 (m, 6H), 3.97(t, J = 6.0 Hz₁ 2H), 2.60(5, 6H) 2.57-2.48 (m, 4H), 2.18- 2.09 (m, 4H), 1.54 (s, 6H), 1.27-1.20 (m, 6H); ¹³C NMR (I OO MHZ, CDCb) 0173.3, 173.1 ,

158.2, 150.0, 149.8, 143.3, 142.3, 131.7, 126.9, 120.9, 116.5, 114.2, 113.6, 89.0, 76.1 , 68.6, 68.2, 60.6, 30.8, 24.8,14.4,13.8,13.7. Example 2: Preparation and Characterization of BODIPY -Based Polvfluorene Derivatives

[00106] Instrumentation. ¹H NMR and ¹³C NMR spectra were taken on a 400 MHz Varian Unity Inova spectrophotometer instrument. ¹H and ¹³C NMR spectra were recorded in CDCI₃, chemical shifts (δ) are given in ppm relative to solvent peaks (1H: δ 7.26; 13C δ 77.3) as internal standard. UV spectra were taken on a Hewlett Packard 8452A Diode Array UV-visible spectrophotometer. Fluorescence spectra were recorded on a Spex Fluorolog 1681 0.22m steady-state fluorometer. Fluorescence quantum yields of BODIPY dyes and polymers were measured in methylene chloride and DMF, and calculated by using fluorescein excited at 490 nm in 0.1 N NaOH as the reference absolute quantum efficiency (φn = 85%). Molecular weights of the polymers were determined by gel permeation chromatography ("GPC") by using a Waters Associates Model 6000A liquid chromatograph Three American Polymer Standards Corp. Ultrastyragel columns in series with porosity indices of 10³, 10⁴, and 10^s A were used and housed in an oven thermostated at 30 ⁰C. Mobile phase was HPLC grade THF which was filtered and degassed by vacuum filtration through a 0.5 μm fluoropore filter prior to use. The polymers were detected by a Waters Model 440 ultraviolet absorbance detector at a wavelength of 254 nm and a Waters Model 2410 refractive index detector. Molecular weights were measured relative to polystyrene standards. An Enraf Nonius CAD-4 X-Ray diffractometer was used in the crystal structure determination. The windows program WmGX was used as the interface for the solution and refinement of the model. The data were first reduced and corrected for absorption using the psi-scans, and then solved using the program SIR2004. The model was refined using SHELXL97.

[00107] Materials. Unless otherwise indicated, all reagents and solvents were obtained from commercial suppliers (Aldrich, Sigma, Fluka, Acros Organics, Fisher Scientific, Lancaster), and were used without further purification. Air- and moisture- sensitive reactions were conducted in oven-dried glassware using standard Schlenk line or dry box techniques under an inert atmosphere of dry nitrogen.

[00108] The synthetic scheme for polymers III, IV and V is shown in FIG. 5 and detailed below.

[00109] 4,4-Dif luoro-β-fSAS-trimethoxyphenyO-i ,3,5,7-tetramethy l-4-bora-3a,4a- diaza-s-indacene (9): 3,4,5-Trimethoxylbenzaldehyde 7 (1.65 g, 8.4 mmol) and 2,4- dimethylpyrrole (1 6 g, 16.8 mmol) were dissolved in dry CH₂CI₂ (800 mL) under a nitrogen atmosphere. Nine drops of trifluoroacetic acid (TFA") (about 0.5 mL) were added, and the mixture was stirred at room temperature overnight. After TLC monitoring showed complete disappearance of the aldehyde, a solution of 2,3-dichloro-5,6-dicyano- 1 ,4-benzoquinone ("DDQ") (1.9 g, 8.4 mmol) in anhydrous CH₂CI₂ (200 mL) was added. This mixture was further stirred for 3 hours, washed with water three times, dried over anhydrous NaSO₄, filtered, and concentrated to dryness. The resulting compound was roughly purified by using aluminum oxide column chromatography to give a brown powder as the crude compound 8 (about 1.0 g, 2.7 mmol, yield of the first step is 32%). This product 8 was used without further purification in the next step. The brown powder (1.0 g, 2.7 mmol) and Λ/,Λ/-diisopropylethylamine ("DIEA") (16 mL, 168 mmol) were dissolved in anhydrous CH₂CI₂ (500 mL) under a nitrogen atmosphere. The solution was stirred at room temperature for 30 minutes and BF₃-OEt₂ (164 mL, 100 mmol) was subsequently added. This mixture was stirred for 3 hours whereupon the complexation was found to be completed by TLC monitoring. The mixture was washed thoroughly with water and brine, dried over anhydrous Na₂SO₄, filtered, and evaporated under vaccum. The crude compound was purified by silica gel column chromatography (eluent: petroleum ether/ethyl acetate: from first 10:1 to final 5:1 , increasing the polarity of the solvent) to give a shiny green powder as the pure compound 9 (600 mg, 1.45 mmol, yield of the second step is 53%, yield overall 17%). ¹H NMR (400 MHz, CDCI₃): δ 1.50 (s, 6H, 2 x CAV₃); 2.51 (s, 6H, 2 * CH₃), 3.79 (s, 6H, 2 * OCAV₃-3,5), 3.88 (s, 3H, OCAV₃-4), 5.97 (S₁ 2H₁ Pyr-AV), 6.49 (d, 2H, Ph-CAV) ppm; ¹³C NMR (100 MHz, CDCI₃): δ 14.40 (Py- CH₃), 14.73 (Py-CH₃), 56.57 (OCH₃), 61.50 (OCH₃), 105.40, 121.40, 130.28, 131.52, 138.90, 141.54, 143.24, 154.41 , 155.81 ppm; IR (KBr) 3117, 3007, 2954, 2837, 1739, 1578, 1462, 1408, 1384, 1248, 1186 cm^"1. MS (El⁺): C₂₂H₂₅BF₂N₂O₃. mlz. calcd. 414.2 (M), found. 414 (M⁺).

[00110] 4,4-Difluoro-8-(3,4,5-trimethoxyphenyl)-2,6-diiodo-1,3,5,7-tetramethyl-4- bora-3a,4a-diaza-5-indacehe (10): Iodic acid (176 mg, 1 mmol) dissolved in a minimal amount of water was added drop-wise over 20 min to a solution of compound 9 (207 mg, 0.5 mmol) and iodine (158 mg, 1.25 mmol) in EtOH (40 ml). This mixture was stirred at 6O⁰C for 30 min. After cooling, the mixture was evaporated under vacuum. The crude product was purified by silica gel column chromatography from ethyl acetate and n- hexane to afford a golden compound as pure 10 (287 mg, 430 mmol, yield 86%). ¹H NMR (400 MHz₁ CDCI₃): δ 1.55 (s, 6H, 2 * CAV₃), 2.64 (s, 6H, 2 x CAV₃), 3.83 (s, 6H, 2 x OCAV₃-3,5), 3.93(S₁ 3H₁ OCAV₃-4), 6.48 (s, 2H) ppm. ¹³C NMR (100 MHz, CDCI₃): δ 16.22, 17.09, 56.63, 61.61, 85.40, 105.15, 129.91 , 131.43, 139.32, 141.17, 145.47, 154.68, 157.11 ppm. IR (KBr) 2927, 2845, 2279, 1742, 1575, 1525, 1505, 1489, 1464, 1450, 1405, 1384, 1369, 1342, 1324, 1306, 1230, 1165, 1117, 1093, 1075, 1043 cm^'1. MS (El⁺): C₂₂H₂₃BF₂I₂N₂O₃. mlz. calcd. 666.0 (M), found. 666 (M⁺).

[00111] Polymer III: To a mixture of compound 10 (50 mg, 0.075 mmol, 1 equiv), Pd(PPh₃)₄ (tetrakis(triphenylphosphine)palladium) (2.6 mg, 0.005 mmol, 0.6%), and 9,9- dihexylfluorene-2,7-diboronic acid 11 (35 mg, 0.083 mmol, 1.1 equiv) was added a degassed mixture of toluene (10 ml_), EtOH (4 mL) and H₂O (4 mL) containing Na₂CO₃ (80 mg, 10 equiv) under a nitrogen atmosphere. The mixture was vigorously stirred at 85 ⁰C for 72 hours and then the solvent was evaporated under vacuum. The residue was dissolved in 100 mL of ethyl acetate and washed with water three times. The organic layer was collected, dried over anhydrous Na₂SO₄ and filtered. The filtrate was concentrated and added to ethanol to precipitate the polymer. A red powder was obtained by filtration, further washed with ethanol and then dried under vacuum for 24 hours to afford polymer III in a yield of 69%. ¹H NMR (400MHz, CDCI₃): δ 0.72 (t, 6H, 2 x CH₃), 1 04 (m, 16H, 8 x CH₂), 1.52 (s, 6H, 2 * CH₃), 1.95 (br, 2H, 2 * CH₂), 2.58 (br, 6H, 2 x CH₃), 3.86 (br, 6H, 2 x OCH₃ ), 3.88 (br, 3H, OCH₃ ), 6.63 (2H, Bodipy-Ph-H), 7.15 (4H, Ph-H), 7.72(d, 2H, Ph-H,) ppm; ¹³C NMR (100MHz, CDCI₃): δ 12.87 (1C, Pyr-CH₃), 13.69, 14.13, 22.61 , 24.01 , 29.75, 31.66, 36.68, 40.58, 55.34, 56.66, 61.53, 105.53, 119.76, 124.91 , 129.05, 131.50, 132.46, 134.53, 139.06, 140.02, 141.77, 151.16, 154.59, 154.73, 162.76 ppm; IR (KBr) 2928, 2855, 2051 , 1677, 1578, 1456, 1387, 1228, 1176cm-¹.

[00112] 4,4-Difluoro-8-(4-methoxyphenyl)-1, 3, 5, 7-tetramethyl-4-bora-3a, 4a- diaza-s-indacene (14): Compound 14 was prepared from 4-methoxybenzaldehyde 12 in 28% yield according to the method for compound 9. ¹H NMR (400 MHz, CDCI₃): δ 1.43 (s, 6H, 2 x CH₃); 2.55 (s, 6H, 2 x CH₃), 3.87 (s, 3H, 2 * OCH₃-4), 5.97 (s, 2H, Pyr- H), 7.01 (d, 2H, Ph-CH, J = 8.4), 7.17 (d, 2H, Ph-CH, J = 8.4) ppm; ¹³C NMR (100 MHz, CDCI₃): δ 14.75, 55.50, 94.62, 114.73, 121.29, 127.26, 129.41 , 132.07, 142.07, 143.36, 155.47, 160.35 ppm. IR (KBr) 3038, 2967, 2932, 2841 , 1609, 1573, 1538, 1505, 1463, 1441, 1407,1368, 1303, 1289, 1246, 1184, 1155, 1109, 1075, 1050, 1022 cm^"1. MS (EI⁺): C₂₀H₂₁BF₂N₂O₃. mlz. calcd. 354.2(M), found. 354 (M⁺).¹⁹

[00113] 4,4-Difluoro-8-(4-methoxyphenyl)-2,6-diiodo-1, 3, 5, 7-tetramethyl-4-bora- 3a, 4a-diaza-s-indacene (15): Compound 15 was prepared from 4,4-difluoro-8-(4- methoxylphenyl)-1,3,5,7-tetramethyl-4-bora-3a,4a-diaza-s-indacene 14 in 88% yield according to the method for compound 10. ¹H NMR (400 MHz, CDCI₃): δ 1.43 (s, 6H, 2 x CH₃), 2.62 (s, 6H, 2 x CH₃), 3.87 (s, 3H, OCH₃-4), 7.02 (d, 2H, Ph-H, J = 8.4), 7.12 (d, 2H, Ph-H, J = 8.4) ppm. ¹³C NMR (100 MHz. CDCI₃): δ 16.21 , 17.38, 55.61 , 85.74, 115.08, 126.89, 129.30, 131.95, 141.80, 145.58, 156.78, 160.77 ppm. IR (KBr) 2953, 2925, 2837, 2041 , 1723, 1609, 1572, 1458, 1397, 1345, 1290, 1 174, 1117 cm^"1. MS (El⁺): C₂₀Hi₉BF₂I₂N₂O₃. m/z. calcd. 605.9 (M), found. 606 (M⁺).

[00114] Polymer IV: Polymer IV was prepared from compound 15 with 9,9- dihexylfluoreπe-2,7-diboronic acid in 54% yield according to the method for polymer III. ¹H NMR (400MHz, CDq₃): δ 0.67 (d, 6H, 2 * CH₃), 0.95 (m, 16H, 8 x CH₂), 1.67 (s, 6H, 2 x CH₃), 1.88 (4H, 2 x CH₂), 2.16-2.60 (m, 6H, 2 * CH₃), 3.80 (s, 3H, OCH₃), 6.99 (2H, Ph-H), 7.07(4H₁ Ph-H), 7.66 (3H, Bodipy-Ph-H) ppm. IR (KBr) 2927, 2856, 1724, 1610, 1529, 1458, 1388, 1292, 1176 cm^"1.

[00115] 4,4-Dif luoro-8-(2,6-dimethy IphenylH ,3,5,7-tetramethy l-4-bora-3a,4a- diaza-s-indacene (18): Compound 18 was prepared from 2,6-dimethylbenzaldehyde 16 in 67% yield according to the method for compound 9. ¹H NMR (400 MHz, CDCI₃): δ 1.36 (s, 6H, 2 x CH₃); 2.15 (s, 6H, 2 x CH₃), 2.56 (s, 6H, 2 x CH₃-2,6), 5.97 (s, 2H, Pyr-H), 7.13-7.27(m, 3H, Ph-H) ppm; ¹³C NMR (100 MHz, CDCI₃): δ 13.49 (Py-CH₃), 14.86(Py- CH₃), 19.77(Ph-CH₃), 121.08 (Py-C), 128.39, 129.09, 130.55, 134.30, 135.45, 141.40, 142.40, 155.49 ppm; MS (El⁺): C₂₁H₂₃BF₂N₂. m/z. calcd. 352.2(M), found. 352 (M⁺).²⁰ IR (KBr) 2962, 2923, 2856, 1541 , 1466, 1369, 1258, 1189 cm^"1. Single crystals of compound 18 (0.40 x 0.40 x 0.40 mm) were grown by vapor diffusion of hexane into a solution of the compound in ethyl acetate. A suitable crystal was cut to size, rolled in epoxy resin and mounted on a glass fiber. Crystal data for compound 18: C₂₁H₂₃BF₂N₂, monoclinic, space group C2/c, a = 20.442 (5) A, b = 7.847(2) A, c = 25.831(8) A, β = 112.49 (2)°, V = 3828.4(18) A³, Z = 8, D_c = 1.223 g cm^"1, μ(Mo-Kσ ) = 0.09 mm^"1, T = 293(2) K. Independent reflections measured = 2496, R₁ = 0.059, wR₂ = 0.190 for 2496 independent observed reflections [F > 4σ (F)], S = 1.04.

[00116] 4,4-Difluoro-8-(2,6-dimethylphenyl)-2,6-diiodo-1,3,5,7-tetramethyl-4-bora- 3a,4a-diaza-s-indacene (19). Compound 19 was prepared from 4,4-difluoro-8-(2,6- dimethylphenyl)-1 ,3,5,7-tetramethyl-4-bora-3a,4a-diaza-s-indacene 18 in 90% yield according to the method for compound 10. ¹H NMR (400 MHz₁ CDCI₃): δ 1.23 (s, 6H, 2 x CH₃), 2.12 (S, 6H, 2 x CH₃), 2.65 (s, 6H₁ 2 x CH₃-2,6), 7.15-7.32 (m, 3H, Ph-H) ppm. ¹³C NMR (100 MHz, CDCI₃): δ 15.93, 16.28, 19.83, 85.63 (Py-C-I), 128.71, 129.70, 130.44, 133.99, 135.32, 141.37, 144.68, 156.82 ppm. IR (KBr) 3063, 3018, 2957, 2916, 2856, 1736, 1596, 1459, 1343, 1241 , 1173, 1085 cm^'1. MS (El⁺): C₂₁H₂₁BF₂I₂N₂O₃. mlz. calcd. 603.99(M), found. 604 (M⁺). [00117] Polymer V: Polymer V was prepared from compound 19 with 9, 9- dihexylfluorene-2,7-diboronic acid in 52% yield, according to the method for polymer III. ¹H NMR (400MHz, CDCI₃): δ 0.66 (m, 6H, 2 x CH₃), 0.98 (m, 12H, 6 * CH₂), 1 -30 (t, 6H, 2 * CH₃), 1.58 (broad, 4H, 2 x CAV₂). 1 -90 (s, broad, 4H, 2 * CH₂), 2.19 (t, 6H, 2 x CH₃), 2.52 (d, 6H, 2 * CH₃), 7.09 (broad, 6H, Ph-H), 7.65 (2H, Bodipy-Ph-H) ppm; ¹³C NMR (100MHz, CDCI₃): δ 10.06 (1 C, Pyr-CH3), 11.82, 13.75, 14.15, 19.94, 20.11 , 22.64, 24.01 , 29.76, 31.67, 40.49, 55.35, 119.67, 124.92, 128.47, 129.09, 130.52, 132.51 , 134.18, 135.51 , 138.21 , 139.93, 151.10, 154.36, 215.64 ppm. IR (KBr) 2925, 2855, 1598, 1535, 1457, 1392, 1225, 1176, 1073 cm^"1.

[00118] Photophysical Properties. The photophysical characteristics of BODIPY dyes, monomers and polymers were investigated in methylene chloride and DMF solutions. The absorption properties of the BODIPY dye 9 are characterized by a strong S₀-^S₁ (π-π*) transition at 502 nm and a weaker broad band at a shorter wavelength around 356 nm ascribed to the S₀->S₂ (π-π*) transition (FIG. 6). BODIPY dyes 14 and 18 display similar absorption features as BODIPY dye 9. The introduction of diiodo substituent to the dipyrromethene core (9, 14 or 18) results in a significant red shift (up to 33 nm and 38 nm) of both the UV-absorption and fluorescent maxima, respectively, and significantly quenches the fluorescence quantum yield because of the heavy atom effect (FIGS. 6-8 and Table 2). Absorption and fluorescence spectra of 2,6-diiodo-substituted BODIPY monomers (10, 15 and 19) exhibit good mirror symmetry with similar band shapes for the absorption and emission spectra which was also verified by measuring their full width at half-maximum (FIG. 6). When low-band-gap BODIPY units are incorporated into the polyfluorene backbone, the fluorescence corresponding to the fluorene segment completely disappears while the emission consists exclusively of one peak at longer wavelength responsible for the BODIPY units. The complete disappearance of the fluorene segment arises from an efficient photoinduced energy transfer from the fluorene segment to the BODIPY unit which functions as a powerful trap in the copolymer backbone. Extended π-conjugation of the polymer III results in significant red shifts (55 nm and 76 nm) of both the UV-absorption and fluorescent maxima, respectively, compared to its starting BODIPY dye 9. As shown in Table 2, the similar red shifts were also observed in polymers IV and V. In addition, fluorescent conjugated copolymers display slightly broader absorption and emission peaks due to extension of π-conjugation compared to their BODIPY monomers, as shown in FIG. 6. Table 2. The UV-visible absorption and emission maxima, and fluorescent quantum yields of BODIPY derivatives and copolymers in CH₂CI₂ solution.

BODIPY Absorption Emission maxima Quantum yield maxima (nm) (nm)

9 502 511 71.5%

10 535 549 7 52%

Polymer III 557 587 63.8%

14 500 510 80.1%

15 533 548 5.72%

Polymer IV 547 585 55.6%

18 501 510 86.7%

19 535 549 8.64%

Polymer V 549 588 84.8%

[00119] BODIPY dyes with different arylated moieties at the meso position (9, 14 and 18) only display a 1 nm to 2 nm difference between their UV-visible absorption maxima or emission maxima although the substitution position is structurally unique (Table 2). lodization of BODIPY dyes (9, 14 and 18) at the 2 and 6 positions does not increase this minor difference (Table 1). This minor difference arises from the fact that the arylated moiety is not coplanar with the BODIPY core due to steric hindrance (FIG. 7). As a result, arylation at the meso position does not significantly affect the absorption and emission spectral maxima of BODIPY dyes. The extended π-conjugation of polymers III, IV and V also fails to amplify the minor difference of emission maxima of their monomers. However, as shown in Table 2, BODIPY dyes (9, 14 and 18) possess different fluorescent quantum yields. BODIPY dye 18 is highly fluorescent with fluorescent quantum yield of 86.7% which is the highest among three BODIPY dyes (9, 14 and 18). Without wishing to be bound by a particular theory, this may be because the ortho-methyl groups on the meso-phenyl ring introduce steric constraints on the phenyl ring, and suppress non-radiative deactivation to increase quantum yield by restricting internal free rotation of the phenyl ring at the meso position relative to the BODIPY core in the excited state (FIG. 7). As a result, polymer V is highly fluorescent with a fluorescent quantum yield of 84.8% in methylene chloride solution, which is higher than those of polymers III and IV.

[00120] The UV-visible absorption and emission maxima of BODIPY dyes (9, 10, 14, 15, 18 and 19) are relatively insensitive to the solvent polarity with similar shapes of the UV-visible absorption and emission spectra in methylene chloride and DMF (Tables 2 and 3; FIGS. 6 and 8). The emission maxima of 2,6-diiodo-subsititued BODIPY derivatives (10, 15 and 19) undergo bathochromically red shifts by 1-2 nm in more polar solvent, (such as DMF) (Tables 2 and 3). However, the fluorescent quantum yields of all BODIPY dyes (9, 10, 14, 15, 18 and 19) decrease in more polar solvent (DMF) (Tables 2 and 3). The UV-visible absorption and emission maxima of conjugated copolymers III, IV and V are also slightly red-shifted and their fluorescent quantum yields decrease significantly in a more polar solvent (DMF) (Tables 2 and 3; FIGS. 6 and 8). This might arise from increased π-π stacking interactions between the polymer backbones promoted in DMF solution.

Table 3. The UV-visible absorption and emission maxima, and fluorescent quantum yields of BODIPY derivatives and copolymers in DMF solution.

BODIPY Absorption Emission maxima Quantum yield maxima (nm) (nm)

9 501 511 55.3%

10 534 551 3.4%

Polymer III 564 590 15.5%

14 500 510 71.6%

15 533 551 4.9%

Polymer IV 554 589 15.6%

18 502 510 73.8%

19 536 552 4.4%

Polymer V 558 590 16.4% Example 3: Synthesis of Highly Water-soluble BODIPY-based Conjugated Glvcopolvmers

[00121] The present Example discloses preparation of a new kind of fluorescent conjugated polymer, poly(2,6-BODIPY-ethynylene)s with deep-red emission at around 680 nm, by palladium-catalyzed Sonogashira polymerization of 2,6-diiodo BCDIPY monomers with 2,6-diethynyl BODIPY monomers. Near-infrared emissive poly(2,6- BODIPY-ethyny1ene)s (XIII-XV) are prepared by 3,5-functionalization of BODIPY dyes with vinylphenyl groups.

[00122] BODIPY-based conjugated glycopolymers are prepared by introducing a variety of carbohydrates (R groups) to the meso-phenyl groups relative to BODIPY cores through well-defined oligo(ethylene glycol) tethered spacers (its repeat unit (m) from 2, 6, 10, 19, 27, 35 to 43) via thioether bridges (FIG. 13).

[00123] Carbohydrate density and orientations of BODIPY-based glycopolymers is controlled by controlling functionalization of the meso-phenyl groups (a - m) relative to BODIPY cores with oligo(ethylene glycol) tethered spacers to address the fundamental issues of the multivalent effects in a given system (FIG. 13). In addition, the density, spacing and orientation of carbohydrate units of BODIPY-based conjugated glycopolymers (polymers VII-XV) is controlled by using diluting BODIPY monomers with meso-phenyl groups (n-v) bearing branched groups of oligo(ethylene glycol) monomethyl ether to optimize multivalent cooperative interactions between carbohydrates and pathogenic bacteria or influenza virus, investigate the influence of carbohydrate clustering and orientation on their multivalent interactions with specific receptors since the effectiveness of the chelate effect depends on the spatial match between the receptors and the carbohydrate residues and on the flexibility of the spacer arms (FIG. 13).

[00124] Although functionalization of the meso-phenyl groups will not significantly change absorption and emission spectral maxima of BODIPY-based conjugated glycopolymers since the meso-phenyl groups are not coplanar with BODIPY cores, it will affect fluorescence quantum yields of the glycopolymers. In order to enhance fluorescence quantum yields of the glycopolymers in aqueous solution, ortho-substituent groups on the meso-phenyl rings (e-v) are used to introduce steric constraints on the meso-phenyl rings, and suppress non-radiative deactivation by restricting internal free rotation of the phenyl ring at the meso position relative to the BODIPY core in the excited state (FIG. 13). In addition, the bulky ortho-substituent groups on the meso-phenyl ring preclude potential formation of aggregates of the conjugated glycopolymers by prevent π-π stacking interactions between polymer backbones through the enhanced steric hindrances.

[00125] In order to further increase stability and fluorescent quantum yields of BODIPY-based conjugated glycopolymers, C-BODIPY- (C for "carbocycle") and E- BODIPY-based (E for "ethynyl") conjugated glycopolymers are prepared by replacing the usual fluorine atoms of F-BODPY dyes with aryl , ethynyl and ethynylaryl subunits (FIG. 13). Although replacement of the usual fluorine atoms with aryl or ethynylaryl subunits will not considerably change absorption and emission spectral maxima of BODIPY- based conjugated glycopolymers, it will not only enhance stability of the glycopolymers in a strong acid or base because of stabilization of the tetrahedral boron center by the ethynyl donors, but also increase water-solubility of the glycopolymers in aqueous solution, and fluorescent quantum yields of the glycopolymers because the bulky aryl, ethynyl or ethynylaryl substituents bearing highly-branched groups of oligo(ethylene glycol) monomethyl ether will increase hydrophilicity of BODIPY dyes, and further prevent ττ-π stacking interactions between the polymer backbones due to their steric hindrances.

Example 4: Synthesis of BODIPY-based Near-infrared Emissive Conjugated Glvco- copolvmers

[00126] Different amounts from 5% to 50% of narrow-band-gap monomer units such as 2,1 ,3-benzoselenadiazole, 6,7-dimethyl[1 ,2,5]thiadiazolo[3,4-g]quinoxaline and benzo[1 ,2-c:4,5-c']bis([1 ,2,5]thiadiazole) are incorporated into backbones of BODIPY- based conjugated glycopolymers to tune polymer fluorescence with near-infrared emissions ranging from 700 nm to 900 nm (FIG. 14).

Example 5: Synthesis of Highly Water-soluble Conjugated Glycopolymers

[00127] Facile, versatile pre-polymerization and post-polymerization functionalization approaches to prepare well-defined fluorene-based fluorescent conjugated polymers bearing β-glucose pendants (polymers XIX and XX), and regioregular head-to-tail conjugated glycopolythiophenes (polymers XXI and XXII) through thioether bridges (FIGS. 15 and 16) have been developed. The post-polymerization functionalization approach offers a very effective and fast way to synthesize well-defined fluorescent conjugated glycopolymers bearing a variety of carbohydrate pendants since the post- polymerization reaction of polymeric bromide groups with thiol-carbohydrates is 100% completed in a mild basic condition. Conjugated glycopolythiophenes with tetra(ethylene glycol) tethered spacers (polymers XXI and XXII) are highly soluble in water while the glycopolymers with hydrophobic hexyl tethered spacers (polymers XIX and XX) are insoluble in water. However, fluorene-based conjugated glycopolymers with poly(ethylene glycol) tethered spacers (polymers XXIII and XXIV) are highly soluble in water with high fluorescent quantum yield of 45% due to highly hydrophilic feature of poly(ethylene glycol) tethered spacers (FIG. 17). The repeated unit number (m) of poly( ethylene glycol) tethered spacer is 9.0 (FIG. 17).

Example 6. Synthesis of Deep-red Emissive Conjugated POIV(BODIPY- ethynyleneϊs.

[00128] Bromide-bearing poly(BODIPY-ethynylene) has been prepared for further functionalization with carbohydrates or peptides through thioether bridges (FIG. 18). The synthetic strategy to prepare bromide-bearing poly(BODIPY-ethynylene)s is detailed in Example 7. Bromide-bearing poly(BODIPY-ethynylene) (polymer XXV) was prepared by palladium-catalyzed Sonogashira polymerization of 2,6-diiodo BODIPY monomer (a) with 2,6-diethynyl BODIPY monomer (c) in DMF solution in presence of Pd(OAc)2 and tetrabutylammonium acetate (FIG. 18).35

[00129] Deep-red emissive poly(BODIPY-ethynylene)s bearing ethyl phenoxybutanoate groups at the meso-positions (polymers XXVI and XXVII) have also been prepared (FIG. 18). Poly(BODIPY-ethynylene)s emit in deep-red region with fluorescent spectral maxima at around 680 nm and display significant red shifts (up to 163 nm and 172 nm) of both absorption and emission maxima compared with their starting BODIPY dyes (d1 , d2) (Table 4). In addition, BODIPY-based copolymers have been prepared. (FIG. 19). Polymer XXVIII emits in orange region at 588 nm and shows significant red shifts to 48 nm and 78 nm) of both absorption and emission maxima compared with their starting BODIPY dye (h). Polymer XXIX emits at 616 nm (corresponding to fluorene moiety) and 680 nm (corresponding to BODIPY moiety), and show no shift in both absorption and emission maxima compared with BODIPY dye (K) in CH₂CI₂. All BODIPY-based polymers are highly florescent with 84.8% of fluorescent quantum yield for polymer XXVIII.

Table 4. Absorption and emission maxima of BODIPY dyes and polymers in methylene chloride. BODJPY <U ei ft Polymer sxvi da ea f2 Polymer xxvπ

Absorption 501 533 553 53» 659 502 534 554 539 t>&5 maxima (nm) hπussioπ 510 54» 569 552 67« 5U 549 570 553 683 maxima (nm)

Example 7: Synthesis of Highly Water-soluble BODlPY-based Conjugated Glvcopolvmers

[00130] Highly water-soluble BODIPY-based deep-red and near-infrared emissive fluorescent conjugated glycopolymers with controlled carbohydrate density and orientation, and apply these glycopolymers in detection of pathogenic bacteria and virus is described.

[00131] Synthesis of Deep-red Emissive Conjugated Glycopoly(F-BODIPY- ethynylene)s. FIG. 20 outlines synthetic route to conjugated poly(F-BODIPY- ethynylene) through a well-developed postpolymerization functionalization approach. Monotosylate oligo(ethylene glycol) (2a) will be prepared by reacting oligo(ethylene glycol) with a stoichiometric amount of p-toluenesulfonyl chloride in the presence of silver(l) oxide and a catalytic amount of potassium iodide. Various well-defined oligo(ethylene glycol)s will be used and their repeated units (m) will be varied from 2, 6, 10, 19, 27, 35 to 43. Bromide-bearing formal benzene derivative (5a) will be prepared by reacting mono-tosylated oligo(ethylene glycol) (2a) with 4-hydroXY-2,6- dimethylbenzaldehyde (1a), and followed tosylation of an alcohol (3a), and replacement of tosylate group with bromide ion. Bromide-bearing BODIPY dye (7a) will be prepared through the reaction of the formyl benzene derivative (5a) with an excess of 2,4- dimethylpyrrole under acid catalysis, and followed by oxidization with 2,3-dichloro-5,6- dicyano-1 ,4-benzoquinone (DDQ) and treatment with BF₃-etherate in the presence of N,N-diisopropylethylamine (DIEA) (FIG. 20). Further iodination of BODIPY dye (7a) will afford 2,6-diiodo-tetramethyl BODIPY monomer (8a). 2,6-Diethynyl BODIPY monomer (10a) will be prepared by palladium-catalyzed Sonogashira reaction of monomer 8a with ethynyltrimethylsilane in DMF solution in the presence of Pd(OAc)2 and tetrabutylammonium acetate, affording BODIPY dye (9a), and followed by hydrolysis of compound 9a in the presence of tetrabutylammonium fluoride. Bromide-bearing conjugated Poly(BODIPY-ethynylene) (polymer 1a) will be synthesized by palladium- catalyzed Sonogashira polymerization of 2,6-diiodo BODIPY monomers (8a) with 2,6- diethynyl BODIPY monomer (1Oa) in DMF solution in presence of Pd(OAc)₂ and tetrabutylammonium. [00132] A series of well-defined glycopoly(BODIPY-ethynylene)s (polymer 2a) bearing different carbohydrate residues will be prepared by postpolymeπzation functionalization of polymer 1a with a little excess of thiol-functionalized carbohydrate (11) in DMF in a mild basic condition (K₂CO₃) through 100% thioether formation (Table 5) The glycopolymer will be put in a cellulose dialysis tube, dialysized against a large amount of water and lyophilized Different olιgo(ethylene glycol)s (m = 2, 6, 10, 19, 27, 35 and 43) will be used as a tethered spacers between polymer backbone and carbohydrate residues Long olιgo(ethylene glycol) (m > 10) will be needed to make polymer 2a soluble in water since polymer 2a will have only one tethered spacer and BODIPY unit is hydrophobic Polymer 2a is expected to have high fluorescent quantum yield with emission maximum at 680 nm according to our preliminary results above because the ortho-methyl groups on the meso-phenyl ring introduce steric constraints on the phenyl ring, and suppress non-radiative deactivation to increase quantum yield by restricting internal free rotation of the phenyl ring at the meso position relative to the BODIPY core in the excited state

[00133] A library of highly water-soluble deep-red emissive conjugated glycopoly(F- BODIPY-ethynylene)s with well-controlled carbohydrate density and orientation will be prepared by using different starting aldehyde derivatives (Ib - 1 m) and tosylated compound (2a - 2C) according to the synthetic approach outlined in FIG 20 Table 5 outlines a library of BODIPY-based conjugated glycopolymers with different lengths of tethered spacers, carbohydrate densities and orientations, and carbohydrate residues Different numbers and positions of olιgo(ethylene glycol) tethered spacers on the meso- phenyl ring relative to each BODIPY unit will be used to control carbohydrate density and orientation, and water-solubility and fluorescent quantum yields of the glycopolymers The library of the glycopolymers will be prepared by Sonogashira polymerization of one or two (1 0 equivalent) of 2,6-dιodιo monomers (10a -10m) with one, or two (1 0 equivalent) of 2,5-dιethynyl monomers (8a - 8m, 8n-8v), and followed by postpolymeπzation functionalization of bromide-bearing polymers with different thiol- functionalized carbohydrates (11) (Tables 5 and 6) Monomers 8n-8v, and 10n-10v will be used as diluting co-monomers to control carbohydrate density of the glycopolymers, and facilitate water-solubility of the glycopolymers Table 5. Thiol-functionalized carbohydrates (R-SH) (H)^40"55 in FIGS. 20-24

Table 6. Starting materials (1b-1m, and 2b-2c), bromide-bearing BODIPY monomers (8a-8m and 1Oa-IOm), diluting monomers (8n-8v and 1On-IOv), bromide-bearing poly(2,6-BODIPY-ethynylene)s (polymers) 1a-1m, 1n-1v, 3a-3z, and 4a-4z), and glycopoly(2,6-BODIPY-ethynylene)s (polymers Vl, VII₁ VIII and IX).

R,θJLβR«

[00134] Anticipated results: Multi-substituent groups of oligo(ethylene glycol) on each of meso-phenyl ring relative to BODIPY core will make BODIPY-based conjugated glycopolymers highly soluble in aqueous solution. Ortho-substituent groups on the meso-phenyl rings (e-v) will introduce steric constraints on the meso-phenyl rings, and suppress non-radiative deactivation by restricting internal free rotation of the phenyl ring at the meso position relative to the BODIPY core in the excited state to increase fluorescence quantum yields of the glycopolymers in aqueous solution. In addition, the bulky ortho-substituent groups on the meso-phenyl ring with preclude potential formation of aggregates of the conjugated glycopolymers by preventing π- π stacking interactions between polymer backbones through the enhanced steric hindrances. The polymerization time will be prolonged due to the bulky ortho-substituent groups on meso- phenyl ring relative to BODIPY core.

Example 8: Synthesis of Cascade-type Deep-red Emissive Glvcopolv(C-BODIPY- ethynylene)s and GIvcopoME-BODIPY-ethynylenels

[00135] In order to further increase stability and fluorescent quantum yields of BODIPY-based conjugated glycopolymers, a library of cascade-type C-BODIPY (C for carbocycle) and E-BODIPY (E for ethynyl) dyads are prepared by replacing the fluorine atoms with aryl, ethynyl and ethynylaryl subunits to incorporate conjugated polymer backbones. Grignard reagents have been used to efficiently substitute the fluorine atoms and E-BODIPY dyes are reported to be very stable and insensitive to strong base or acid, as well as polar solvents and reagents, which is due to stabilization of the tetrahedral boron center by the ethynyl donors. A series of C- or E-BODIPY monomers (13a-13m, 13n-13v) are prepared by reacting 2,5-diiodo BODIPY monomers (8a-8m, 8n-8v) in Table 6 with Grignard reagents (12a, 12b, 12C or 12d) in dry THF at 60 ⁰C. The bromide groups of BODIPY dyes (8a-8m) will be intact under Grignards reaction condition. 2,6-Diethynyl C- or E-BODIPY monomers (15a-15m, 15n-15v) are prepared by palladium-catalyzed Sonogashira reaction of monomers (13a-13m, 13n-13v) with ethynyltrimethylsilane in DMF solution in the presence of Pd(OAc)₂ and tetrabutylammonium acetate, affording BODIPY dyes (14a-14m, 14n-14v), and followed by hydrolysis of intermediates (14a-14m, 14n-14v) in the presence of tetrabutylammonium fluoride. Bromide-bearing conjugated Poly(BODIPY-ethynylene)s (polymers 5a-5m) are synthesized by palladium-catalyzed Sonogashira polymerization of one of 2,6-diiodo C- or E-BODIPY monomers (13a-13m) with one of 2,6-diethynyl C- or E-BODIPY monomers (15a-15m) in DMF solution in the presence of Pd(OAc)₂ and tetrabutylammonium acetate (FIG. 21). Well-defined glycopoly(C- or E-BODIPY- ethynylene)s (polymers XXV) bearing different carbohydrate residues are prepared by post-polymerization functionalization of bromide-bearing polymers 5a-5m with a little excess of thiol-functionalized carbohydrate (11) in DMF in a mild basic condition (K₂CO₃) through 100% thioether formation (Table 5). Polymers VII, VIII, XIX with controlled density of carbohydrate residues will be prepared by polymerizing one or two (1.0 equivalent) of monomers 15a-15m with one or two (1.0 equivalent) of monomers 13n- 13v according to the approach for polymer XXV (FIG. 21).

[00136] Anticipated results: Replacement of the fluoride atoms with aryl, ethynyl and ethynylaryl subunits will not only significantly enhance stability of glycopoly(C- or E- BODIPY-ethynylene)s in a strong acid or base because of stabilization of the tetrahedral boron centers by the ethynyl donors, but also further increase water-solubility of the glycopolymers in aqueous solution, and fluorescent quantum yields of the glycopolymers because the bulky aryl, ethynyl, ethynylaryl substituents bearing highly-branched groups of oligo(ethylene glycol) monomethyl ether will significantly increase hydrophilicity of BODIPY dyes, and further prevent π-ττ stacking interactions between the polymer backbones. Polymerization time may need to be prolonged due to introduction of bulky groups to the monomers.

Example 9: Synthesis of Near-infrared Emissive Glycopoly(F-. C- and E-BODIPV- vinylerte)s

[00137] According to our preliminary results, poly(BODIPY-ethynylene)s emit deep-red emission with emission spectral maximum at 680 nm. In order to tune the fluorescence of conjugated glycopolymers with near-infrared emission, highly water-soluble glycopoly(BODIPY-vinylene)s are prepared which emit near-infrared emission due to more extended π-conjugation of their polymer backbones than those of poly(BODIPY- ethynylene)s (FIG. 22). 2,6-bis(4.4,5,5-tetramethyl-1 ,3,2-dioxoborolan-2-yl-ethenyl) BODIPY monomers (16a - 16h) are obtained by reaction of one of 2,6-diethynyl F-, C- or E-BODIPY monomers (1On - 1Ov, 15n-15v) in Table 6 and FIG. 21 with 4,4,5,5- tetramethyl-1 ,3,2-dioxaborolane (pinacolborane) in mixed solution of THF and toluene at 80 "C. Glycopoly(BODIPY-vinylene)s (polymers X) are prepared by palladium-catalyzed Suzuki polymerization of one (1.0 equivalent) of BODIPY monomers (16a -16h) with one of bromide-bearing 2,6-diiodo BODIPY monomers (8a - 8m, 13a-13m) in 1-methyl-2- pyrrolidinone (NMP) solution at 90 °C, affording bromide-bearing poly(BODIPY- vinylene)s (polymers 6a-6m), and followed by postpolymerization functionalization of bromide-bearing poly(BODIPY-vinylene)s (polymers 6a-6m) with thiol-functionalized carbohydrates (11) in Table 4. A library of glycopoly (BODI PY-vinylene)s with various carbohydrate density and orientation (Polymers Xl and XII) are prepared by polymerizing one or two (1.0 equivalent) of BODIPY monomers (16a-16h) with one or two (1.0 equivalent) of BODIPY monomers (8a -8m, 13a-13m) in Table 6 and FIG. 21 for a series of bromide-bearing poly(F-, C- and E-BODIPY-vinylene)s, and followed by functionalization of the bromide-bearing polymers with thiol-functionalized carbohydratesd 1) in Table 5 (FIG. 22).

[00138] Anticipated results: Bromide groups of monomers (8a-8m, 13a-13m) will be intact in palladium-catalyzed Suzuki polycoπdensation. Glycopoly(F-, C- and E-BODIPY- vinylene)s (polymer X-XII) will emit in near-infrared region with emission maxima larger than 700 nm due to their more extended π-conjugation than deep-red emissive poly(F-, C-, E-BODIDPY-ethynylene)s (polymers X-XIV).

Example 10: Synthesis of Near-infrared Emissive GlvcopolvfF-BODIPY- ethynylene)s.

[00139] In order to further tune fluorescence of glycopoly(BODIPY-ethynylene)s with near-infrared emission, π-conjugation of BODIPY monomers is extended by condensation reactions of BODIPY monomers (8n-8v) with aldehyde derivative (3w), affording highly water-soluble BODIPY monomers (15a-15h) due to several highly branched oligo(ethylene glycol) monomethyl ether groups (FIG. 23). Highly water- soluble near-infrared emissive conjugated glycopoly(BODIPY-ethynylene)s (polymers XIII) are prepared by palladium-catalyzed Sonogashira polymerization of one of BODIPY monomers (17a-17h) with one of BODIPY monomers (1Oa-IOm) in Table 6 in DMF in the presence of Pd(OAc)₂ and tetrabutylammonium acetate, resulting in bromide-bearing polymer 7a-7m, and followed by postpolymerization functionalization of polymer 7a-7m with thiol-functionalized carbohydrate (11) in Table 4 (FIG. 23). A library of the glycopolymers with various carbohydrate density and orientation (Polymers XIV and XV) are prepared by polymerizing one or two (1.0 equivalent) of BODIPY monomers (16a- 16h) with one or two (1.0 equivalent) of BODIPY monomers (10a-10m) in Table 5 for a series of bromide-bearing poly(BODIPY-ethynylene)s, and followed by functionalization of the bromide-bearing polymers with thiol-functionalized carbohydrates (11) in Table (FIG. 23).

[00140] Anticipated results: The chemical transformation of the 3,5-methyl groups of 2,5-diodo-BODIPY dyes (8n- 8v) to two vinylphenyl groups will cause a dramatic bathochromic shift to 680 nm in emission of BODIPY dyes (17a-17h) relative to 2,5- diodo-BODIPY dyes which emit around 548 nm. The enhanced derealization imparted by a more conjugated and planar vinyl system will reduce the energy required to reach the excited state. As a result, the conjugated glycopoly(BODIPY-ethynylene)s (Polymer XIII-XV) will have significant bathochromic shift and emit in near-infrared region. The polymerization time may need to be prolonged due to the bulky monomers 16a-16h. In addition, water-solubility of glycopoly(BODIPY-ethynylene)s will be further enhanced by strong hydrophilic feature of monomers 17a-17h which will have more than six (up to twenty) hydrophilic groups of oligo(ethylene glycol) monomethyl ether (FIG. 23 and Table 6).

Example 11. Synthesis of BODIPY-based Near-infrared Emissive Glyco- copolymers

[00141] Glycopoly(BODIPY-ethynylene)s (polymers V-IX) will emit in deep-red region with emission spectra maxima at 680 nm according to our preliminary results. Narrowband-gap monomer units are incorporated such as benzo[c] [1 ,2,5]thiadiazole, 2,1 ,3- benzoselenadiazole, 6,7-dimethyl[1 ,2,s]thiadiazolo[3,4-g]quinoxaline and benzo[1 ,2- C:4,5-c']bis([1 ,2,5]thiadiazole) to backbones of poly(BODIPY-ethynylene)s to tune the polymer fluorescence with near-infrared emission ranging from 700 nm to 900 nm (FIG. 24). Bromide-bearing conjugated. BODIPY-based copolymers (polymers 8a-8m) are synthesized by palladium-catalyzed Sonogashira polymerization of one of 2,6-diiodo F-, C- or E-BODIPY monomers (8a-8m, 13a-13m) with one of narrow-band-gap monomers (18a-18e) in DMF solution in the presence of Pd(OAc)₂ and tetrabutylammonium acetate (FIG. 21). Well-defined F-, C- or E-BODIPY-based near-infrared emissive copolymers (polymers XVII) bearing different carbohydrate residues are prepared by post- polymerization functionalization of bromide-bearing polymers 8a-8m with a little excess of thiol-functionalized carbohydrate (11) in DMF in a mild basic condition (K₂CO₃) through 100% thioether formation (Table 5). BODIPY-based glyco-copolymers with different amount of narrow-band-gap monomer units (polymer XVII) are prepared by polymerizing one (1.0 equivalent) of monomers (8a-8m, 13a-13m) with 1.0 equivalent of one of narrow-band-gap monomers (18a-18e) and one of monomer (10a-10, 15a-15m) according to the approach for polymer XVI (FIG. 24). BODIPY-based glyco-copolymers with less density of carbohydrate residues (polymer XVIII) are prepared by polymerizing one (1.0 equivalent) of monomers (8v-8v, 13n-13v) with 1.0 equivalent of one of narrowband-gap monomers (18a-18e) and one of monomer (10a-10m, 15a-15m) according to the approach for polymer XVI (FIG. 24).

[00142] Anticipated results: Incorporation of small amount of narrow-band-gap monomers (from 5% to 50%) will efficiently tune fluorescence of poly(BODIPY- ethynylene)s to near-infrared emission at more than 700 nm due to very effective photoinduced energy transfer along π-conjugated polymer backbones. The amount of narrow-band-gap monomers will need to be optimized to have highly water-soluble BODIPY-based conjugated glycopolymers with near-infrared emission.

Example 12. Synthesis of Fluorescent conjugated qlvcopolvmers A-E

[00143] Polymers A-E are shown in FIG. 25.

[00144] Instrumentation. ¹H NMR and ¹³C NMR spectra were taken on a 400 MHz Varian Unity Inova spectrophotometer instrument. ¹H and ¹³C NMR spectra were recorded in CDCI₃, and chemical shifts (<5) are given in ppm relative to solvent peaks (at 7.24 ppm for ¹H spectra and at 77.3 for ¹³C spectra) as internal standard. UV spectra were taken on a Hewlett-Packard 8452A Diode Array UV-visible spectrophotometer. Fluorescence spectra were recorded on a Spex Fluorolog 1681 0.22m steady-state fluorometer. Fluorescence quantum yields of BODIPY dyes and polymers were measured in methylene chloride and calculated by using fluorescein excited at 490 nm in 0.1 N NaOH as the reference (its quantum efficiency of 85%). Fluorescence lifetimes were measured on a GL-3300 Nitrogen Laser laserstrobe PTI instrument and analyzed using FeliX32 software.

[00145] Materials. Unless otherwise indicated, all reagents and solvents were obtained from commercial suppliers (Aldrich, Sigma, Fluka, Acros Organics, Fisher Scientific, Lancaster) and were used without further purification. Air- and moisture- sensitive reactions were conducted in oven-dried glassware using a standard Schlenk line or drybox techniques under an inert atmosphere of dry nitrogen. 4,4-Difluoro-8-(4- methoxyphenyl)-1 ,3,5,7-tetrarnethyl-4-bora-3a, 4a-diaza-s-indacene (2) and 1 ,4- diethynyl-2,5-didecyloxybenzene (7) were prepared according to the reported procedure.

BODIPY dyes 4 and 5

[00146] The synthetic scheme to the BODIPY dyes 4 and 5 is shown in FIG. 26 and detailed below.

[00147] 4,4-Difluoro-8-(4-methoxyphenyl)-2,6-diiodo-1, 3, 5, 7-tetramethyl-4-bora- 3a, 4a-diaza-s-indacene (3). When iodic acid (11.26 mmol, 1.98 g) in 4 mL of water was added dropwise to the ethanol solution (50 mL) containing BODIPY dye (2) (5.63 mmol 2.0 g) and iodine (6.19 mmol 1.57 g) over 30 min, the mixture was stirred for 3 h. The mixture was concentrated under reduced pressure, dissolved in CH₂CI₂, and washed twice with water and saturated sodium chloride solution. The organic layer was collected, dried over anhydrous Na₂SO₄, and concentrated under reduced pressure. The crude product was purified according to a reported procedure to yield compound 3 as red crystals (3.2 g, 94%).

[00148] 2,6-diiodo-BODIPY Dye bearing monostyryl and distyryl groups (4, 5):

Piperidine (2.88 mL) and acetic acid (2.44 mL) were added to the solution of benzene (120 mL) containing 2,6-diiodo BODIPY dye (3) (1.326 mmol, 0.80 g) and compound 3 (5.18 mmol, 1.93 g) in a 250-mL flask. After the mixture was stirred and refluxed by using a Dean Stark trap for 4 hours, it was cooled to room temperature and concentrated under reduced pressure. The crude product was dissolved in ethyl acetate and washed twice with water. The organic phase was collected, dried over Na₂SO₄, and filtered. After the filtrate was concentrated, the residue was purified by silica gel column chromatography using hexane/EtOAc (5/1 to 3/1 , v/v) to afford dark blue solid compound 4 (540 mg, 43%), dark green solid compound 5 (410 mg, 24%). BODIPY Dye bearing monostyryl group (4): ¹H NMR (400 MHz, CDCI₃): δ 8.05 (d, J=16.8 Hz, 1 H), 7.49 (d, .7=16.8 Hz, 1H), 7.26 (d, J= 8.4 Hz, 1H), 7.14 (m, 2H), 7.02 (d, J=8.0 Hz, 2H), 6.88 (d, J=8.0 Hz, 1H), 4.18-4.06 (m, 8H), 3.87 (s, 3H), 2.68 (S, 3H), 2.59-2.53 (m, 4H), 2.18-2.13 (m, 4H), 1.48 (s, 3H), 1.44 (s, 3H), 1.26 (t, J= 7.0 Hz, 6H). ¹³C NMR (100 MHz, CDCI₃): δ 173.4, 173.3, 160.7, 156.8, 150.5, 149.2, 146.3, 145.2, 140.5, 139.2, 132.8, 132.5, 130.4, 129.9, 129.5, 127.1 , 121.9, 117.2, 115.1 , 113.9, 113.2, 86.3, 82.6, 68.5, 68.2, 60.6, 55.6, 30.9, 24 9, 24.8, 17.9, 17.4, 16.4, 14.5. IR (cm^"1): 2924, 1728, 1511 , 1468, 1346, 1246, 1164, 1109, 995, 706. ESI-MS: M⁺ (C₄, H₄₈BF₂I₂N₂O₇) Calcd: m/z = 983.0, Found: m/z = 980.3. The compound shows absorption maximum at 597 nm and emission maximum at 631 nm in CH₂CI₂ solution; BODIPY Dye bearing distyryl group (5): ¹H NMR (400 MHz, CDCI₃): δ 8.04 (d, J=16.8 Hz, 2H)₁ 7.51 (d, J=16.4 Hz, 2H), 7.23 (d, J= 9.2 Hz, 2H), 7.17 (d, J=8.4 Hz₁ 2H)₁ 7.10 (s, 2H), 7.01 (d, J=8A Hz, 2H), 6.89 (d, J=8A Hz, 2H)₁ 4.15-4.05 (m, 16H), 3.85 (s, 3H), 2.55-2.51 (m, 8H), 2.16-2.09 (m, 8H), 1.46 (S, 6H), 1.27-1.20 (m, 12H) ppm. ¹³C NMR (100 MHz, CDCI₃): δ 173.4, 173.3, 160.7, 150.5, 149.1 , 145.9, 139.4, 138.9, 133.6, 130.5, 129.8, 127.4, 121.7, 117.3, 115.0, 114.0, 113.7, 83.3, 68.5, 68.2, 60.6, 60.5, 55.6, 30.9, 24.9, 24.8, 17.9, 14.4 ppm. IR (cm ¹): 2978, 2933, 1726, 1595, 1509, 1431 , 1354, 1244, 1170, 1094, 1010, 770, 708. ESI-MS: M⁺ (C₆₂H₇₆BF₂I₂N₂OI ₃+Na) Calcd: m/z = 1382.0, Found: m/z = 1381.8. The compound shows absorption maximum at 665 nm and emission maximum at 701 nm in CH₂CI₂ solution. Polymers A and B

[00149] The synthetic scheme to Polymers A and B is shown in FIG. 27 and detailed below.

[00150] Polymer A: BODIPY dye bearing monostyryl group (4) (0.15 mmol, 150 mg), 2,6-diethynyl BODIPY dye (6) (0.18 mmol, 169 mg), and CuI (3 mg) were added to a 100-mL three-neck flask under a nitrogen atmosphere. Pd(PPh₃)₄ (6 mg) was added to the flask in a glove box under a nitrogen atmosphere. When degassed anhydrous THF (40 mL) and diisopropylamine (40 mL) were added to the flask under a nitrogen atmosphere, the resulting mixture was stirred under reflux for 24 h. After removal of the solvent, the residue was dissolved in 250 mL of methylene chloride and washed with water three times. After the organic layer was collected, dried over anhydrous MgSO₄, and filtered, the filtrate was concentrated under reduced pressure and added to 250 mL of ethanol to precipitate the polymer. The precipitated solid was collected, washed with ethanol and hexane, and dried under vacuum for 24 h at room temperature to obtain dark-violet solid (0.202 g). ¹H NMR (400 MHz, CDCI₃): δ 8.19 (br.d, 1 H), 7.56 (br.d, 1H), 7.16-7.10 (br.m, 4H), 7.02-7.00 (br. m, 2H), 6.84 (br. d, 1 H), 6.42 (br. s, 2H), 4.14-4.06 (br. m, 8H), 3.98 (br.m, 2H), 3.86 (br. m, 7H), 2.68-2.64 (br. m, 9H), 2.57-2.52 (br. m, 4H)₁ 2.18-2.13 (br. m, 4H), 1.76 (br. m, 6H), 1.66 (br. s, 6H), 1.54-1.23 (br. m, 66H), 0.86-0.85(br. m, 9H). IR (cm^'1): 2922, 2852, 1734, 1509, 1313, 1228, 1164, 1086, 1000, 759; The compound shows absorption maximum at 697 nm and emission maximum at 715 nm in CH₂CI₂ solution.

[00151] Polymer B: 2,6-diiodo BODIPY dye bearing distyryl groups (5) (0.11 mmol, 150 mg), 2,6-diethynyl BODIPY dye (6) (0.13 mmol, 122 mg), and CuI (3 mg) were added to a 100-mL three-neck flask under a nitrogen atmosphere. Pd(PPh₃J₄ (6 mg) was added to the flask in the glove box under a nitrogen atmosphere. After degassed anhydrous THF (40 mL) and diisopropylamine (40 mL) were added to the flask under a nitrogen atmosphere, the mixture was stirred under reflux for 24 h. Polymer B was purified by using the procedure for polymer A to obtain dark-violet solid (0.182 g). ¹H NMR (400 MHz, CDCI₃): 58.20 (br.d, 2H), 7.63 (br.d, 2H), 7.16-7.10 (br. m, 4H), 7.03 (br. s, 2H), 7.02 (br. d, 2H), 6.88 (br. d, 2H)₁ 6.43 (br. s, 2H), 4.15-4.08 (br.m, 16H), 3.99 (br. m, 2H), 3.87 (br. m, 7H), 2.66 (br. s, 6H), 2.57-2.52 (br.m, 8H), 2.18-2.14 (m, 8H), 1.76 (br. m, 6H), 1.66 (br. s, 12H), 1.56-1.23 (br. m, 66H), 0.86-0.85 (br.m, 9H) ppm. ¹³C NMR (100 MHz, CDCI₃): δ 173.4, 173.3, 160.7, 154.5, 152.3, 150.7, 149.2, 144.6, 143.4, 139.1 , 133.5, 131.5, 130.4, 125.2, 122.1 , 117.4, 114.9, 113.9, 113.2, 106.3, 94.6, 91.5, 74.0, 69.8, 68.6, 68.2, 60.6, 60.5, 55.5, 32.1 , 31.8, 30.9, 30.5, 29.9, 29.8, 29.5, 26.4, 26.2, 24.9, 24.8, 23.6, 22.9, 14.4, 14.3 ppm. IR (cm ¹). 2921 , 2852, 1733, 1506, 1313, 1238, 1179, 1082, 1004, 758, 709; The compound shows absorption maximum at 738 nm and emission maximum at 760 nm in CH₂CI₂ solution.

Polymers C and D

[00152] The synthetic route to Polymers C and D is shown in FIG. 28 and detailed below.

[00153] Compound 8. 2,5-diiodo-3-decylthiophene (7) (4.20 mmol, 2 g), CuI (4 mg), and Pd(PPh₃)₂CI₂ (10 mg) were added to a 100-mL three-neck flask under a nitrogen atmosphere. After degassed anhydrous THF (20 mL), diisopropylamine (20 mL), and trimethylsilylacetylene (12.6 mmol, 1.2 g) were added to the flask under a nitrogen atmosphere, the mixture was stirred at room temperature for 12 h. The mixture was concentrated, dissolved in 50 mL of CH₂CI₂ and washed twice with water and saturated saline solution. When the organic layer was collected, dried over anhydrous MgSO₄, and filtered, the filtrate was concentrated under reduced pressure. The product was purified by silica gel column chromatography using hexane/EtOAc (98/2 v/v) to yield thick liquid (1 46 g, 84%). ¹H NMR (400 MHz, CDCI₃): (56.94 (s, 1 H)₁ 2.59 (t, J = 7.6 Hz, 2H), 1.56 (t, J = 6.8 Hz, 2H), 1.31-1.26 (m, 14H), 0.87 (t, J = 6.8 Hz, 3H), 0.19 (s, 18H) ppm. ¹³C NMR (100 MHz, CDCI₃): 6 148.6, 133.6, 122.9, 120.1 , 101.9, 99.6, 97.6, 97.1 , 32.1 , 30.1 , 29.8, 29.7, 29.5, 29.3, 22.9, 14.3, 0.09 ppm.

[00154] 2,5-diethynyl-3-decylthiophene (9). When tetrabutylamine fluoride (5.63 mmol 2.0 g) was added to the degassed solution of compound 8 (12.1 mmol, 0.50 g) in dry THF (50 mL) at -70 ⁰C through syringe, the resulting mixture was stirred at room temperature for two hours. After the reaction was quenched with dilute acetic acid and 50 mL of dichloromethane was added to the flask, the mixture was washed twice with water and saturated saline solution. When the organic layer was collected, died over anhydrous MgSO₄, and filtered, the filtrate was concentrated. The residue was purified by column chromatography using hexane/EtOAc (95/5 v/v) to yield yellow liquid (0.28 g, 87%). The compound was immediately stored at 4 ⁰C. ¹H NMR (400 MHz, CDCI₃): δ 7.00 (s, 1 H), 3.42 (d, J = 1.2 Hz, 1 H), 3.30(d, J = 0.8 Hz, 1 H), 2.63 (t, J = 7.0 Hz, 2H), 1.58(t, J = 7.0 Hz, 2H)₁ 1.31-1.27 (m, 14H), 0.89(t, J = 6.4 Hz, 3H) ppm. ¹³C NMR (100 MHz, CDCI₃): δ 148.8, 133.9, 122.3, 119.1, 84.2, 81.9, 76.9, 76.2, 32.2, 30.2, 29.9, 29.8, 29.6, 29.5, 29.4, 22.9, 14.4 ppm. [00155] Polymer C. 2,5-Diiodo BODIPY dye bearing distyryl groups (5) (0.11 mmol, 150 mg), 2,5-diethynyl-3-decylthiophene (9) (0.14 mmol, 36 mg), and CuI (3 mg) were added to a 100-mL three-neck flask under a nitrogen atmosphere. Pd(PPh₃)₄ (6 mg) was added to the flask in the glove box under a nitrogen atmosphere. When degassed anhydrous THF (40 ml_) and diisopropylamine (40 mL) were added to the flask under a nitrogen atmosphere, the mixture was stirred under reflux for 24 h. The mixture was concentrated and added dropwise to 250 mL of ethanol under stirring to precipitate the polymer. The precipitated polymer was collected, washed with water, ethanol, acetone and hexane and dried under vacuum for 24 h at room temperature to afford dark-violet solid (0.113 g). ¹H NMR (400 MHz, CDCI₃): 58.22 (br. d, 2H), 7.65 (br. d, 2H), 7.16-7.10 (br. m, 4H), 7.05 (br. s, 2H), 7.02 (br. m, 3H), 6.89 (br. d, 2H), 4.15-4.08 (br. m, 16H), 3.87 (br. s, 3H), 2.67-2.63 (br. m, 10H), 2.16-2.09 (br.m, 8H), 1.58 (br.t, 2H), 1.46 (br.s, 6H), 1.30-1.20 (br. m, 26H), 0.87 (br. t, 3H) ppm. IR (cm^'1): 2921 , 2852, 1732, 1509, 1457, 1262, 1249, 1175, 1135, 1044, 958, 750, 723; The compound shows absorption maximum at 713 nm and emission maximum at 758 nm in CH₂CI₂ solution.

[00156] Polymer D. 2,5-Diiodo BODIPY dye bearing monostyryl group (4) (0.10 mmol, 100 mg), diethynyl-3-decylthiophene (9) (0.12 mmol, 34 mg), and CuI (3 mg) were added to a 100-mL three-neck flask under a nitrogen atmosphere. Pd(PPh₃)₄ (6 mg) was added to the flask in the glove box under a nitrogen atmosphere. When degassed anhydrous THF (40 mL) and anhydrous diisopropylamine (40 mL) were added to the flask under a nitrogen atmosphere, the mixture was stirred under reflux for 24 h. The polymer D was purified by using the same procedure for polymer C to afford dark-violet solid (0.082 g). ¹H NMR (400 MHz, CDCI₃): 58.17 (br.d, 1 H), 7.54 (br.d, 1H), 7.15-7.08 (br.m, 4H), 7.02-6.98 (br.m, 3H), 6.82 (br.d, 1H), 4.12-4.03 (br.m, 8H), 3.87 (br.s, 3H), 2.67-2.63 (br.m, 5H), 2.58-2.51 (br.m, 4H)₁ 2.16-2.13 (br.m, 4H), 1.58 (br.t, 2H), 1.48- 1.24 (br.m, 26H), 0.88 (br.t, 3H) ppm. IR (cm^"1): 2921 , 2851 , 1732, 1509, 1403, 1247, 1178, 1022, 1007, 835; The compound shows absorption maximum at 649 nm and emission maximum at 694 nm in CH₂CI₂ solution.

Polymer E

[00157] The synthetic route to Polymer E is shown in FIG. 29 and detailed below.

[00158] Polymer E. 2,6-diethynyl-BODIPY dye (6) (0.14 mmol, 150 mg), 2,5-diiodo-3- decylthiophene (8) (0.12 mmol, 60 mg), and CuI (3 mg) were added to a 100-mL three- neck flask under a nitrogen atmosphere. Pd(PPh₃J₄ (6 mg) was added to the flask in the glovebox under a nitrogen atmosphere. Anhydrous THF (40 mL) and diisopropylamine (40 mL) were added to the flask in a nitrogen atmosphere. When the mixture was stirred under reflux for 24 h, the mixture was added dropwise to 500 mL of ethanol to precipitate the polymer. The precipitated polymer was collected, washed with water, ethanol, acetone and hexane and dried under vacuum for 24 h at room temperature to obtain dark-violet solid (0.132 g). ¹H NMR (400 MHz, CDCI₃): <56.95 (br.s, 1H), 6.45 (br. s, 2H), 4.02 (br. s, 2H), 3.91 (br. s, 4H), 2.67 (br. s, 6H), 1.77(br. t, 4H), 1.64 (br.s, 6H), 1.49- 1.44 (br. m, 6H), 1.24 (br. m, 72H), 0.85 (br. t, 12H) ppm. ¹³C NMR (100 MHz, CDCI₃): δ 158.7, 154.6, 147.5, 143.2, 142.5, 139.2, 132.4, 131.5, 115.8, 106.3, 90.2, 88.8, 73.9, 69.7, 32.2, 32.1 , 30.5, 30.3, 29.9, 29.8, 29.6, 29.5, 26.3, 26.2, 22,9, 14!3, 13.9, 13.5 ppm. IR (Cm^"1): 2921, 2852, 1525, 1315, 1229, 1111 , 1004, 759, 720. The compound shows absorption maximum at 634 nm and emission maximum at 669 nm in CH₂CI₂ solution.

[00159] Optical Properties of BODIPY Polymeric and Copolymeric Dyes. The photophysical characteristics of BODIPY intermediate, monomeric and polymeric dyes were investigated in methylene chloride. The absorption properties of the BODIPY dye 2 in methylene chloride solution are characterized by a strong S₀^S₁ (π-π*) transition at 502 nm and a weaker broad band at a shorter wavelength around 356 nm due to the S₀->S₂ (π-π^*) transition (FIG. 30). The introduction of diiodo substituent to the dipyrromethene core (2) results in a significant red shift (up to 33 nm and 38 nm) of both the UV-absorption and fluorescent maxima, respectively (FIGS. 30 and 31), and significantly quenches the fluorescence quantum yield because of the heavy atom effect (Table 7). Absorption and fluorescence spectra of 2,6-diiodo-substituted BODIPY dye 2 exhibit good mirror symmetry with similar band shapes for the absorption and emission spectra which was also verified by measuring their full width at half-maximum (FIGS. 30 and 31). Further condensation of 2,6-diiodo BODIPY dye bearing methyl sbustituents at 3 and 5 positions (3) with aldehyde derivative gave longer wavelength absorbing BODIPY dyes bearing alkoxymonostyryl and alkoxydistyryl (4,5). The extended π- conjugation in these dyes results in significant red shifts in both absorption and emission spectra compared with their precursor BODIPY dye (3). Alkoxymonostyryl-bearing BODIPY dye (4) shows absorption and emission maxima at 579 nm and 631 nm with red shifts of 79 nm and 121 nm in absorption and emission spectra, respectively, compared with its starting BODIPY dye (2). Alkoxydistyryl-bearing BODIPY dye (5) displays red shifts of 165 nm and 170 nm in absorption and emission spectra with absorption and emission maxima of 665 nm and 701 nm, respectively, compared with its starting BODIPY dye (2) (Table 7). Both alkoxymonostyryl- and alkoxydistyryl-substituted BODIPY dyes (4,5) exhibit low fluorescence quantum yields because of heavy atom effect Palladium-catalyzed Sonogashira polymerization of alkoxymonostyryl- and alkoxydistyryl-substituted BODIPY dyes (4,5) with 2,6-dιethynyl-substιtuted BODIPY (6) resulted in near-infrared emissive BODIPY polymeric dyes (polymers A and B) with the further extended ττ-conjugatιon, respectively Polymer A shows significant red shifts of 100 nm and 84 nm in absorption and emission with absorption and emission maxima of 679 nm and 715 nm, respectively, compared with its alkoxymonostyryl-substituted BODIPY monomeric dye (4) Polymer B display absorption and emission maxima at 738 nm and 760 nm with significant red shifts of 73 nm and 59 nm in absorption and emission with, respectively, compared with its alkoxydistyryl-substituted BODIPY monomeric dye (5) (FIGS 30 and 31)

[00160] Palladium-catalyzed Sonogashira polymerization of alkoxydistyryl- and alkoxymonostyryl-substituted BODIPY dyes (5,4) with 2,5-dιethynyl-3-decylthιophene (10) resulted in near-infrared and deep-red emissive BODIPY copolymers dyes with emission maxima of 758 nm and 694 nm (polymers C and D), respectively (FIG 32) Palladium-catalyzed Sonogashira polymerization of 2,6-dιethynyl-substιtuted BODIPY dyes (6) with 2,5-dιιodo-3-decylthιophene (8) resulted in red emissive BODIPY copolymers dye with emission maxima of 634 nm and 669 nm (polymers E), respectively All BODIPY copolymers dyes display low fluorescence quantum yields because of heavy sulfur atom effect (Table 7)

[00161] Solid-state absorption and emission spectra were collected to evaluate effect of the polymer aggregation on their optical properties as the absorption and emission spectra of the film reflect polymer π-π stacking effects The solid state film was prepared by spin-casting methylene chloride solutions of the polymers onto quartz discs The absorption spectra of the polymers in thin films became a little broader, and maximum peaks were obviously red-shifted compared with those in methylene chloride solutions The fluorescence spectra of the polymers in solid state thin films retain most of the spectra features in solution and exhibit further red shifts with their absorption and emission maxima in near-infrared region compared with those in methylene chloride solution, indicating the presence of intermolecular electronic interaction and/or increase in coplanarity of the polymer in the solid state (Table 8) Table 7. Absorption and emission maxima, fluorescence quantum yields and lifetimes of BODIPY dyes and polymeric dyes in methylene chloride solution

Table 8. Absorption and Emission Maxima of thin films on quartz surface

Thermal stabilities of the polymers.

[00162] Thermal stabilities of BODIPY polymeric and copolymeric dyes were evaluated by thermogravimetrc analysis (TGA) at the heating rate of 20 ⁰C /min under nitrogen atmosphere. The thermograms show that polymers A, B and C lost 5% of their weight at 250 ⁰C (the decomposition temperature (T_d) that corresponds to weight loss of 5%), respectively, which suggests their good thermal stability (FIG. 33). Differential scanning calorimetry (DSC) of polymers did not give a clear phase, may be because of rigid backbone of the BODIPY. Example 13. Synthesis of Fluorescent Conjugated Glycopolymers A-C

[00163] The structures of Polymers A-C are shown in FIG. 34.

EXPERIMENTAL SECTION

[00164] Instrumentation. ¹H NMR and ¹³C NMR spectra were taken on a 400 MHz Varian Unity Inova spectrophotometer instrument. ¹H and ¹³C NMR spectra were recorded in CDCI₃, chemical shifts (δ) are given in ppm relative to solvent peaks (¹H: δ 7.26; ¹³C: δ 77.3) as internal standard. UV spectra were taken on a Hewlett Packard 8452A Diode Array UV-visible spectrophotometer. Fluorescence spectra were recorded on a Spex Fluorolog 1681 0.22m steady-state fluorometer. Fluorescence quantum yields of BODIPY dyes and polymers were measured in methylene chloride and DMF, and calculated by using fluorescein excited at 490 nm in 0.1 N NaOH as the reference quantum efficiency (φ_n = 85%).^{3()| 31} Molecular weights of the polymers were determined by gel permeation chromatography (GPC) by using a Waters Associates Model 6000A liquid chromatograph. Three American Polymer Standards Corp. Ultrastyragel columns in series with porosity indices of 10³, 10⁴, and 10⁵ A were used and housed in an oven thermostated at 30 ⁰C. Mobile phase was HPLC grade THF which was filtered and degassed by vacuum filtration through a 0.5 μm fluoropore filter prior to use. The polymers were detected by a Waters Model 440 ultraviolet absorbance detector at a wavelength of 254 nm and a Waters Model 2410 refractive index detector. Molecular weights were measured relative to polystyrene standards.

[00165] Materials. Unless otherwise indicated, all reagents and solvents were obtained from commercial suppliers (Aldrich, Sigma, Fluka, Acros Organics, Fisher Scientific, Lancaster), and were used without further purification. Air- and moisture- sensitive reactions were conducted in oven-dried glassware using standard Schlenk line or dry box techniques under an inert atmosphere of dry nitrogen.

Polymer A

[00166] The synthetic route to Polymer A is shown in FIG. 35 and detailed below.

[00167] Compound 1a: When 150 mL of degassed DMF was added to in a 500 mL three-neck round-bottom flask containing 4-hydroxybezaldehyde (40.9 mmol, 5 g), 1- bromododecane (49.2 mmol, 12.2 g) and K₂CO₃ (122 mmol, 16.8 g) under a nitrogen atmosphere, the mixture was stirred for 4 hours at 80⁰C under a nitrogen atmosphere. After completion of the reaction (which was monitored by TLC)₁ the reaction mixture was concentrated under reduced pressure, added to water and extracted with EtOAc. The organic layer was washed twice with water and saturated NaCI solution, dried over anhydrous MgSO₄ and concentrated under reduced pressure. The resulting crude product was purified by silica gel column chromatography using hexane/EtOAc (80/20, v/v) to obtain brown liquid (11.6 g, 98%). ¹H NMR (400 MHz, CDCI₃) δ 9.86 (s, 1 H), 7.81 (d, J = 8.8 Hz, 2H), 6.97 (d, J = 8.8 Hz, 2H), 4.01 (t, J = 6.6 Hz, 2H), 1.81-1.77 (m, 2H), 1.46-1.44 (m, 2H), 1.42-1.25 (m, 16H), 0.86(t, J = 6.8 Hz, 3H); ¹³C NMR (100 MHz, CDCI₃) δ 191.0, 164.9, 132.2, 130.0, 115.0, , 68.6, 32.1 , 29.8, 29.7, 29.5, 29.2, 26.1 , 22.9, 14.3.

[00168] Compound 3a: 1a (17.4 mmol, 5.06 g) and 2,4-dimethylpyrrole (34.9 mmol, 3.32 g) were dissolved in 1200 mL of dry CH₂CI₂ in a 2000-mL three-neck flask. Eight drops of TFA were added to the reaction mixture, and resulting mixture was stirred in dark for 12 hours under nitrogen atmosphere at room temperature. After the complete consumption of aldehyde (1a) (which was conformed by TLC), DDQ (2,3-dichloro-5,6- dicyano-1 ,4-benzoquinone) (17.4 mmol 3.95 g) in 100 mL of CH₂CI₂ was added to the reaction mixture. When the mixture was stirred for 30 minutes, 35 mL of diisopropylethylamine (DIEA) and 35 mL of BF₃OEt₂ were added to the mixture. After the mixture was further stirred for 30 minutes, it was concentrated to 200 mL and filtered. The filtrate was washed once with sodium bicarbonate solution and twice with water, dried over anhydrous MgSO₄ and concentrated under reduced pressure. The crude product was purified by column chromatography using hexane/ EtOAc (90/10 to 70/30, v/v) to obtain dark brown crystalline solid (3.15 g, 36 %). ¹H NMR (400 MHz, CDCI₃) δ 7.13 (d, J = 8.4 Hz, 2H), 6.97 (d, J = 8.4 Hz, 2H), 5.95 (s, 2H), 3.99 (t, J = 6.6 Hz, 2H), 2.53(s, 6H), 1.82-1.78 (m, 2H), 1.49-1.42 (m, 8H), 1.36-1.26 (m, 16H), 0.87 (t, J = 6.6 Hz, 3H); ¹³C NMR (100 MHz, CDCI₃) δ 159.9, 155.4, 143.4, 142.2, 132.1 , 129.3, 127.0, 121.3, 115.3, 68.4, 32.1, 29.9, 29.8, 29.6, 29.5, 29.4, 26.3, 22.9, 14.8, 14.3. IR(cm^"1): 2922, 2850,1540, 1508,1465,1408, 1306, 1247, 1182, 1155, 1084, 971 , 832, 811 , 704. ESI-MS. M⁺ (C₃₁H₄₃BF₂N₂O) Calcd: m/z =508.5, Found: m/z =509.2.

[00169] Compound 4a: When iodic acid (12.3 mmol, 2.18 g) in 5 mL of water was added dropwise to the ethanol solution (50 mL) containing compound 3a (5.9 mmol 3.0 g) and iodine (12.9 mmol 1.65 g) over 30 minutes, the mixture was stirred for 2 hours. After the completion of the reaction, the unreacted iodine was quenched with sodium thiosulphate and the mixture was concentrated under reduced pressure and dissolved in CH₂CI_2, and washed twice with water and saturated saline solution. The organic layer was collected, dried over anhydrous MgSO₄ and concentrated under reduced pressure. The crude product was purified by column chromatography to yield 4a as red crystals (4.4 g, 98%). ¹H NMR (400 MHz, CDCI₃) δ 7.10 (d, J = 8.8 Hz, 2H), 7.00 (d, J = 8.8 Hz, 2H), 4.00 (t, J = 6.6 Hz, 2H), 2.62 (s, 6H), 1.84-1.80 (m, 2H), 1.48-1.43 (m, 8H), 1.38- 1.26 (m, 16H), 0.87 (t, J = 6.6 Hz, 3H); ¹³C NMR (100 MHz, CDCI₃) δ 160.4, 156.7, 145.6, 142.0, 132.0, 129.2, 126.6, 115.6, 85.8, 68.5, 32.2, 29.9, 29.8, 29.7, 29.6, 29.5, 26.3, 22.9, 17.4, 16.2, 14.4; IR (cπV¹): 2923, 2853,1528, 1465, 1398, 1344, 1307, 1248, 1178, 998. M⁺ (C₃iH₄₁BF₂1₂N₂O) Calcd: m/z = 760.3, Found: m/z = 760.0.

[00170] Compound 5a: Compound 4a (3.28 mmol, 2.5 g), CuI (0.02 mmol, 0.004 g) and Pd(PPh₃)₂CI₂ (0.02 mmol, 0.015 g) were added to a 250-mL three-neck round- bottom flask under a nitrogen atmosphere. When 20 mL of anhydrous degassed THF, 30 mL of anhydrous diisopropylamine, and trimethylsilylacetylene (8.2 mmol, 0.8 g) were added to the flask, the mixture was stirred under reflux for 12 hours. After the completion of the reaction (which was monitored by TLC), the reaction mixture was concentrated and dissolved in 50 mL of CH₂CI₂, washed twice with water and saturated saline solution. The organic layer was collected, dried over anhydrous MgSO₄, and concentrated under reduced pressure. The product was purified by neutralized silica gel column chromatography using hexane/EtOAc (95/5 to 80/20, v/v) to yield orange-red solid (1.86 g, 81%). ¹H NMR (400 MHz, CDCI₃) δ 7.08 (d, J = 8.8 Hz, 2H), 6.98 (d, J = 8.8 Hz, 2H), 4.00 (t, J = 6.6 Hz, 2H)₁ 2.61 (s, 6H), 1.83-1.79 (m, 2H), 1.47-1.46 (m, 8H), 1.36-1.25 (m, 16H), 0.87 (t, J = 6.6 Hz, 3H), 0.19 (s, 18H); ¹³C NMR (100 MHz, CDCI₃) δ 160.3, 158.7, 145.2, 143.3, 131.7, 129.2, 126.3, 1 16.2, 115.4, 101.8, 97.4, 68.5, 32.1 , 29.9, 29.8, 29.6, 29.5, 29.4, 29.2, 26.3, 22.9, 14.4, 13.8, 0.28. ¹¹B NMR (400 MHz, CDCI₃): 3.82 (t, J = 97.6 MHz). IR(cm^"1) :2922, 2853, 2150, 1608, 1526, 1469, 1393, 1365, 1316, 1247, 1195, 1093, 833, 703. ESI-MS. M⁺ (C₄₁H₅₉BF₂N₂OSi₂) Calcd: m/z = 700.9, Found: m/z =700.9.

[00171] Compound 6a: When compound 5a (2.1 mmol, 1.5Og) was dissolved in degassed THF (8 mL) in a 100-mL flask at -70 ^CC, tetrabutylammonium fluoride (TBAF) (5.2 mmol, 1.3 g, 5.2 mL of 1 M solution) was added dropwise to the mixture via syringe. The reaction temperature was brought to the room temperature and the mixture was further stirred for 2 hours. After completion of the reaction, the mixture was acidified with acetic acid and extracted with CH₂CI₂. The extracted organic layer washed twice with water and saturated saline solution, dried over anhydrous MgSO₄, and concentrated under reduced pressure. The crude product was purified by column chromatography using hexane/EtOAc (20/80, v/v) to give the desired product as orange-pink crystalline solid (0.84 g, 72%). ¹H NMR (400 MHz, CDCI₃) δ 7.11 (d, J = 8.8 Hz, 2H), 7.00 (d, J = 8.8 Hz, 2H), 4.00 (t, J = 6.6 Hz₁ 2H), 3.3 (s, 2H), 2.63 (s, 6H), 1.83-1.79 (m, 2H), 1.51- 1.46 (m, 8H), 1.44-1.26 (m, 16H), 0.87 (t, J = 6.6 Hz, 3H); ¹³C NMR (100 MHz, CDCI₃) δ 160.3, 158.8, 145.8, 143.3, 131.6, 129.2, 126.2, 115.5, 115.2, 84.2, 76.2, 68.5, 32.1 , 29.9, 29.8, 29.6, 29.5, 29.4, 26.2, 22.9, 14.3, 13.7; ¹¹B NMR (400 MHz, CDCI₃): 3.82 (t, J = 97.6 MHz). IR(Cm^"1): 3299, 2921 , 2852, 2105, 1726, 1602, 1532, 1468, 1392, 1313, 1288, 1248, 1161, 1125, 1070, 1007, 833,800, 708. ESI-MS. M⁺ (C₃₅H₄₃BF₂N₂O) Calcd: m/z =556.5, Found: m/z = 557.2.

[00172] Polymer A: Compound 4a (0.133 mmol, 0.100 g), compound 6a (0.144 mmol, 0.080 g ), CuI (0.01 mmol, 0.002 g) were added to 100-mL flask under a nitrogen atmosphere. In the glove box, Pd(PPh₃J₄ (0.01 mmol, 0.012 g) was added to the flask. When a degassed mixed solution of anhydrous THF (20 mL) and anhydrous diisopropylamine (20 mL) were added to the flask, the mixture was stirred under reflux for 24 hours. After removal of the solvent, the residue was dissolved in methylene chloride (5mL) added to 400 mL of ethanol and stirred for 2 hrs to precipitate the polymer. The precipitated solid was filtered and washed with excess ethanol and hexane. The obtained solid dried under vacuum for 24 h at room temperature to obtain dark-violet solid (0.150 g). ¹H NMR (400 MHz, CDCI₃) δ 7.09 (br, 2H), 6.99 (br, 2H), 3.99 (br, 2H)₁ 2.62(s, 6H), 1.82 (br, 2H), 1.66 (br, 6H), 1.51 (br, 4H), 1.26 (br,14H), 0.87 (br, 3H); ¹³C NMR (100 MHz, CDCI₃) δ 160.3, 158.8, 145.7, 142.3, 131.7, 129.1 , 126.2, 115.5, 113.6, 88 9. 68.5, 32.1 , 29.9, 29.8, 29.6, 29.5, 29.4, 26.2, 22.9, 14.3, 13.7; IR(Cm^"1): 3675, 2988, 2972, 2902, 1406, 1394, 1383, 1249, 1242, 1230, 1075, 1066, 1057, 892, 880.

Polymer B

[00173] The synthetic route to Polymer B is shown in FIG. 36 and detailed below.

[00174] Compound 1b: When 150 mL of degassed DMF was added to in a 500 mL three-neck round-bottom flask containing 3,4-dihydroxybezaldehyde (22.3 mmol, 3 g), 1- bromododecane (49.2 mmol, 12.2 g) and K₂CO₃ (122 mmol, 16.8 g) under a nitrogen atmosphere, the mixture was stirred for 4 hours at 80 ⁰C under a nitrogen atmosphere. After completion of the reaction (which was monitored by TLC)₁ the reaction mixture was concentrated under reduced pressure, added to water and extracted with EtOAc. The organic layer was washed twice with water and saturated NaCI solution, dried over anhydrous MgSO₄ and concentrated under reduced pressure. The resulting crude product was purified by silica gel column chromatography using hexane/EtOAc (80/20, v/v) to obtain white solid (10.3 g, 98%). ¹H NMR (400 MHz, CDCI₃) δ 9.81 (s, 1 H), 7.41- 7.37 (m, 2H), 6.93 (d, J = 8.4 Hz, 1 H), 4.08-4.02 (m, 4H), 1.86-1.80 (m, 4H), 1.47-1.44 (m, 4H), 1.34-1.24(m, 32 H), 0.86 (t, J = 6.8 Hz, 6H); ¹³C NMR (100 MHz, CDCI₃) δ 191.2, 154.9, 149.7, 130.1 , 126.8, 112.0, 11 1.2, 69.3, 32.1 , 29.9, 29.8, 29.7, 29.6, 29.5, 29.3, 29.2, 26.2, 26.1, 22.9, 14.3.

[00175] Compound 3b. 1b (17.4 mmol, 8.25 g) and 2,4-dimethylpyrrole (34.88 mmol, 3.32 g) were dissolved in 1200 mL of dry CH₂CI₂ in a 2000-mL three-neck flask. Eight drops of TFA were added to the reaction mixture, and resulting mixture was stirred in dark for 12 hours under nitrogen atmosphere at room temperature. After the complete consumption of aldehyde (1b) (which was conformed by TLC), DDQ (2,3-dichloro-5,6- dicyano-1 ,4-benzoquinone) (17.4 mmol 3.95 g) in 100 mL of CH₂CI₂ was added to the reaction mixture. Wl\en the mixture was stirred for 30 minutes, 35 mL of diisopropylethylamine (DIEA) and 35 mL of BF₃OEt₂ were added to the mixture. After the mixture was further stirred for 30 minutes, it was concentrated to 200 mL and filtered. The filtrate was washed once with sodium bicarbonate solution and twice with water, dried over anhydrous MgSO₄ and concentrated under reduced pressure. The crude product was purified by column chromatography using hexane/ EtOAc (90/10 to 80/20, v/v) to obtain dark brown crystalline solid (4.2 g, 35 %). ¹H NMR (400 MHz, CDCI₃) δ 6.94 (d, J = 8.8 Hz, 1 H), 6.77-6.75 (m, 2H), 5.96 (s, 2H), 4.02 (t, J = 6.8 Hz, 2H), 3.93(t, J = 6.8 Hz, 2H), 2.53 (s, 6H), 1.86-1.77 (m, 4H), 1.46(s, 6H), 1.43-1.24 (m, 32H), 0.88-0.85 (m, 6H); ¹³C NMR (100 MHz, CDCI₃) δ 155.5, 150.0, 149.8, 143.4, 142.1 , 132.2, 127.3, 121.2, 120.6, 115.0, 113.6, 69.7, 69.4, 32.1 , 29.9, 29.8, 29.7, 29.6, 29.5, 29.4, 29.1, 26.3, 26.1 , 22.9, 14.8, 14.6, 14.3; IR(CnV¹): 2921 , 2852, 1543, 1509, 1467, 1412, 1372, 1306, 1263, 1156, 1136, 1121 , 1084, 979, 817, 760, 723. ESI-MS. M⁺ (C₄₃H₆₇BF₂N₂O₂) Calcd: m/z = 692.8, Found: m/z = 693.1.

[00176] Compound 4b. When iodic acid (12.1 mmol, 2.13 g) in 5 mL of water was added dropwise to the ethanol solution (50 mL) containing compound 3b (5.7 mmol 4.0 g) and iodine (12.9 mmol 1.62 g) over 30 minutes, the mixture was stirred for 2 hours. After the completion of the reaction, the unreacted iodine was quenched with sodium thiosulphate solution and the mixture was concentrated under reduced pressure and dissolved in CH₂CI₂, and washed twice with water and saturated saline solution. The organic layer was collected, dried over anhydrous MgSO₄ and concentrated under reduced pressure. The crude product was purified by column chromatography to yield 4b as red crystals (5.2 g, 98%). ¹H NMR (400 MHz, CDCI₃) δ 6.96 (d, J = 8.4 Hz, 1H), 6.73-6.71 (m, 2H), 4.04 (t, J = 6.8 Hz, 2H), 3.92 (t, J = 6.8 Hz, 2H), 2.62 (s, 6H), 1.87- 1.77 (m, 4H), 1.48 (s, 6H), 1.45-1.24 (m, 32H), 0.88-0.84 (m, 6H); ¹³C NMR (100 MHz, CDCI₃) δ 156.8, 150.3, 150.2, 145.6, 141.8, 131.9, 127.0, 120.5, 114.1 , 113.2, 85.7, 69.7, 69.5, 32.1 , 29.9, 29.8, 29.7, 29.6, 29.5, 29.4, 26.2, 26.1 , 22.9, 17.2, 16.2, 14.3; IR(cm^"1): 2917, 2849, 1542, 5122, 1508, 1463, 1397, 1345, 1311 , 1263, 1243, 1213, 1184, 1140, 1 119, 1082, 992, 915, 759, 724. ESI-MS. M⁺ (C₄₃H₆₅BF₂1₂N₂O₂) Calcd: m/z = 944.6, Found: m/z = 944.7.

[00177] Compound 5b. Compound 4b (3.2 mmol, 3.0 g), CuI (0.02 mmol, 0.004 g) and Pd(PPh₃)₂CI₂ (0.02 mmol, 0.015 g) were added to a 250-mL three-neck round- bottom flask under a nitrogen atmosphere. When 20 mL of anhydrous degassed THF, 30 mL of anhydrous diisopropylamine, and trimethylsilylacetylene (8.0 mmol, 0.78 g) were added to the flask, the mixture was stirred under reflux for 12 hours. After the completion of the reaction (which was monitored by TLC), the reaction mixture was concentrated and dissolved in 50 mL of CH₂CI₂, washed twice with water and saturated saline solution. The organic layer was collected, dried over anhydrous MgSO₄, and concentrated under reduced pressure. The product was purified by neutralized silica gel column chromatography using hexane/EtOAc (95/5 to 80/20, v/v) to yield orange-red solid (2.2 g, 80%). ¹H NMR (400 MHz, CDCI₃) δ 6.95 (d, J = 8.4 Hz, 1 H), 6.73-6.70 (m, 2H), 4.02 (t, J = 6.8 Hz, 2H), 3.92 (t, J = 6.8 Hz, 2H), 2.62 (s, 6H), 1.87-1.78 (m, 4H), 1.55 (s, 6H), 1.52-1.24 (m, 32H), 0.88-0.84 (m, 6H), 0.19(s, 18H); ¹³C NMR (100 MHz, CDCI₃) 5 158.8, 150.2, 145.1 , 143.1 , 131.5, 126.6, 120.4, 116.3, 114.1 , 113.2, 101.8, 97.4, 69.7, 69.5, 32.1 , 29.9, 29.8, 29.8, 29.7, 29.6, 29.5, 29.4, 26.3, 26.2, 22.9, 14.3, 13.7, 0.28; ¹¹B NMR (400 MHz, CDCI₃): 3.82 (t, J = 97.6 MHz). IR(cnY¹): 2919, 2850, 246, 1531 , 1517, 1470, 1391 , 1316, 1268, 1249, 1197, 1139, 1092, 1072, 1013, 1003, 840, 761, 725, 700. ESI-MS. M⁺ (C₅₃H₈₃BF₂N₂O₂Si₂) Calcd: m/z = 885.2, Found: m/z = 885.3.

[00178] Compound 6b. When compound 5b (2.2 mmol, 2.Og) was dissolved in degassed THF (50 mL) in a 250-mL flask at -70 ⁰C₁ tetrabutylammonium fluoride (TBAF) (5.6 mmol, 1.47 g, 5.6 mL of 1M solution) was added dropwise to the mixture via syringe. The reaction temperature was brought to the room temperature and the mixture was further stirred for 2 hours. After completion of the reaction, the mixture was acidified with acetic acid and extracted with CH₂CI₂. The extracted organic layer washed twice with water and saturated saline solution, dried over anhydrous MgSO₄, and concentrated under reduced pressure. The crude product was purified by column chromatography using hexane/EtOAc (20/80, v/v) to give the desired product as orange-pink crystalline solid (1.1 g, 70%). ¹H NMR (400 MHz, CDCI₃) δ 6.96 (d, J = 8.4 Hz, 1H), 6.73-6.72 (m, 2H), 4.04 (t, J = 6.8 Hz, 2H), 3.92 (t, J = 6.8 Hz, 2H), 3.3(s, 2H), 2.63 (s, 6H), 1.87-1.61 (m, 4H), 1.51 (s, 6H), 1.49-1.24 (m, 32H), 0.88-0.84 (m, 6H); ¹³C NMR (100 MHz, CDCI₃) δ 158.8, 150.2, 145.8, 143.6, 131.5, 126.4, 120.4, 115.2, 114.0, 113.1 , 84.3, 76.2, 69.7, 69.4, 32.1 , 29.9, 29.8, 29.7, 29.6, 29.4, 26.3, 26.1 , 22.9, 14.3, 13.7, 13.6; ¹¹B NMR (400 MHz, CDCI₃): 3.82 (t, J = 97.6 MHz). IR(cm^"1): 3309, 2921, 2852, 2107, 1526, 1468, 1403, 1390, 1366, 1312, 1263, 1180, 1137, 1080, 1003, 761 , 725. ESI-MS. M⁺ (C₄₇H₆₇BF₂N₂O₂) Calcd: m/z = 740.8, Found: m/z = 739.1.

[00179] Polymer B. Compound 4b (0.105 mmol, 0.100 g), compound 6b (0.1 15 mmol, 0.085 g ), CuI (0.01 mmol, 0.002 g) were added to 100-mL flask under a nitrogen atmosphere. In the glove box, Pd(PPh₃J₄ (0.01 mmol, 0.012 g) was added to the flask. When a degassed mixed solution of anhydrous THF (20 mL) and anhydrous diisopropylamine (20 mL) were added to the flask, the mixture was stirred under reflux for 24 hours. After removal of the solvent, the residue was dissolved in methylene chloride (5mL) added to 400 mL of ethanol and strried for 2 hrs to precipitate the polymer. The precipitated solid was filtered and washed with excess ethanol and hexane. The obtained solid dried under vacuum for 24 h at room temperature to obtain dark-violet solid (0.155 g). ¹H NMR (400 MHz, CDCI₃) δ 6.94 (br, 1 H), 6.73 (br, 2H), 4,02 (br, 2H), 3.92 (br, 2H), 2.62 (s, 6H), 1.84(br, 2H), 1.79 (br, 2H), 1.56 (s, 6H), 1.49-1.24 (m. 32H), 0.88-0.86 (m, 6H); ¹³C NMR (100 MHz, CDCI₃) δ 157.9, 150.0, 143.2, 142.5, 134.8, 131.6, 120.3, 116.3, 113.8, 113.1 , 88.8, 69.5, 69.3, 31.9, 29.7, 29.6, 29.5, 29.4, 29.2, 26.0, 22.7, 16.9, 14.1 , 13.5; IR(crτϊ¹): 2921 , 2852, 1514, 1467, 1435, 1389, 1310, 1262, 1227, 1162, 1083, 995, 813, 760, 724.

Polymer C

[00180] The synthetic route to Polymer C is shown in FIG. 37 and detailed below.

[00181] Compound 02. When 200 mL of degassed DMF was added to in a 500 mL three-neck round-bottom flask containing methyl-3,4,5-trihydroxybenzoate (13.6mmol, 2.5 g), 1-bromododecane (47.6 mmol, 11.8 g) and K₂CO₃ (54 mmol, 7.5 g) under a nitrogen atmosphere, the mixture was stirred for 4 hours at 80 ⁰C under a nitrogen atmosphere. After completion of the reaction (which was monitored by TLC), the reaction mixture was concentrated under reduced pressure, added to water and extracted with hexane. The organic layer was washed twice with water and saturated NaCI solution, dried over anhydrous MgSO₄ and concentrated under reduced pressure. The resulting crude product was purified by silica gel column chromatography using hexane/EtOAc (98/2, v/v) to obtain white solid (9.2 g, 98%). ¹H NMR (400 MHz, CDCI₃) δ 7.23 (s, 2H), 4.02-4.00 (m, 6H), 3.86 (s, 3H), 1.80 (q, J = 6.8 Hz, 6H), 1.49-1.44 (m, 6H), 1.33-1.25 (m, 48H), 0.88-0.84 (m, 9H); ¹³C NMR (100 MHz₁ CDCI₃) δ 167.1 , 153.0, 142.6, 124.9, 108.2, 73.7, 69.4, 52.3, 32.1 , 30.5, 29.9, 29.8, 29.7, 29.6, 29.5, 26.3, 26.1, 22.9, 14.3.

[00182] Compound 03. Compound 02 (13.1 mmol, 9g) in 50 ml of dry diethylether was added to LiAIH4 (26.2 mmol, 1g) suspended in 100 ml diethylether in a dry 250 mL three-neck round-bottom flask. After strring for 24hrs, the reaction was quenched with ethanol and water at 0 ⁰C. the resulting solution was filtered and washed twice with water, dried over anhydrous MgSO₄ and concentrated under reduced pressure. The resulting crude product was purified by silica gel column chromatography to obtain white solid (5.6 g, 65%). ¹H NMR (400 MHz, CDCI₃) δ 6.52 (s, 2H), 4.55(s, 2H), 3 96-3.91 (m, 6H), 3.60 (t, J = 6.4 Hz, 1H), 1.79-1.68 (m, 6H), 1.50-1.41 (m, 6H), 1.40-1.25 (m, 48H), 0.90-0.85 (m, 9H); ¹³C NMR (100 MHz, CDCI₃) δ 153.4, 137.7, 136.3, 105.5, 73.6, 69.3, 65.8, 63.2, 33.0, 32.1 , 30.5, 29.9, 29.6, 26.3, 26.0, 22.9, 14.3.

[00183] Compound 1c. Compound 03 (8.3 mmol, 5.5 g) and pyridiniumchlorocromate (PCC) (12.4 mmol, 2.6 g) were taken in a 250 ml round bottom flask and 100 ml of dry CH₂CI₂ was added in nitrogen atmosphere. After refluxing for 4 hrs the mixture was filtered and the organic layer was washed with brine, dried over anhydrous MgSO₄ and concentrated under reduced pressure. The resulting crude product was purified by silica gel column chromatography to obtain white solid (5.1 g, 95%). ¹H NMR (400 MHz, CDCI₃) δ 9.81 (s, 1H), 7.06 (s, 2H), 4.06-4.00 (m, 6H), 1.84-1.77 (m, 6H), 1.46-1.42 (m, 6H), 1.33-1.25 (m, 48H), 0.88-0.85 (m, 9H); ¹³C NMR (100 MHz, CDC₁₃) δ 191.4, 153.7, 144.1 , 131.7, 108.1 , 73.8, 69.4, 32.1, 30.6, 29.9, 29.8, 29.6, 29.5, 26.3, 26.2, 22.9, 14.3.

[00184] Compound 3c. 1c (17.4 mmol, 11.4 g) and 2,4-dimethylpyrrole (34.88 mmol, 3.32 g) were dissolved in 1200 mL of dry CH₂CI₂ in a 2000-mL three-neck flask. Eight drops of TFA were added to the reaction mixture, and resulting mixture was stirred in dark for 12 hours under nitrogen atmosphere at room temperature. After the complete consumption of aldehyde (1c) (which was conformed by TLC), DDQ (2,3-dichloro-5,6- dicyano-1,4-benzoquinone) (17.4 mmol 3.95 g) in 100 mL of CH₂CI₂ was added to the reaction mixture. When the mixture was stirred for 30 minutes, 35 mL of diisopropylethylamine (DIEA) and 35 mL of BF₃OEt₂ were added to the mixture. After the mixture was further stirred for 30 minutes, it was concentrated to 200 mL and filtered. The filtrate was washed once with sodium bicarbonate solution and twice with water, dried over anhydrous MgSO₄ and concentrated under reduced pressure. The crude product was purified by column chromatography using hexane/ EtOAc (95/5 v/v) to obtain dark brown crystalline solid (4.5 g, 30 %). ¹H NMR (400 MHz, CDCI₃) δ 6.45 (s, 2H), 5.97 (S, 2H), 3.99 (t, J = 6.4 Hz, 2H), 3.90 (t, J = 6.4 Hz, 4H), 2.53 (s, 6H), 1.75 (q, J = 6.8 Hz, 6H), 1.52 (s, 6H), 1.48-1.42 (m, 6H), 1.40-1.24 (m, 48H), 0.88-0.85 (m, 9H); ¹³C NMR (100 MHz, CDCI₃) δ 155.6, 154.3, 143.3, 142.0, 138.9, 131.6, 129.8, 121.2, 106.6, 73.9, 69.6, 32.1 , 30.5, 29.9, 29.8, 29.6, 29.5, 26.3, 26.2, 22.9, 14.7, 14.4, 14.3; IR (cm^"1): 2922, 2853, 1544, 1509, 1467, 1417, 1373, 1327, 1307, 1156, 1113, 1086, 1026, 977, 834, 804, 758, 721. ESI-MS. M⁺ (C₅₅H₉₁BF₂N₂O₃) Calcd: m/z = 877.1 , Found: m/z = 877.5.

[00185] Compound 4c. When iodic acid (9.5 mmol, 1.6 g) in 5 ml_ of water was added dropwise to the ethanol solution (50 ml.) containing compound 3c (4.5 mmol 4.0 g) and iodine (9.9 mmol 1.3 g) over 30 minutes, the mixture was stirred for 2 hours. After the completion of the reaction, the unreacted iodine was quenched with sodium thiosulphate solution and the mixture was concentrated under reduced pressure and dissolved in CH₂CI₂, and washed twice with water and saturated saline solution. The organic layer was collected, dried over anhydrous MgSO₄ and concentrated under reduced pressure. The crude product was purified by column chromatography to yield 4c as red crystals (4.8 g, 96%). ¹H NMR (400 MHz, CDCI₃) δ 6.41 (s, 2H), 4.01 (t, J = 6.4 Hz, 2H), 3.89 (t, J = 6.4 Hz, 4H), 2.62 (s, 6H), 1.75 (q, J = 6.8 Hz, 6H), 1.53 (s, 6H), 1.49-1.43 (m, 6H), 1.40-1.24 (m, 48H), 0.88-0.84 (m, 9H); ¹³C NMR (100 MHz, CDCI₃) δ 156.9, 154.6, 145.6, 141.7, 139.2, 131.5, 129.4, 106.3, 85.7, 74.0, 70.0, 32.1 , 30.5, 29.9, 29.8, 29.6, 29.5, 26.3, 26.2, 22.9, 17.1 , 16.2, 14.3; IR(cnrϊ¹): 2920, 2851 , 1523, 1466, 1419, 1378, 1368, 1343, 1330, 1305, 1166, 1 115, 993, 918, 831. ESI-MS. M⁺ (C₅₅H₈₉BF₂I₂N₂O₃) Calcd: m/z = 1128.9, Found: m/z =1129.1.

[00186] Compound 5c. Compound 4c (3.5 mmol, 4.0 g), CuI (0.02 mmol, 0.004 g) and Pd(PPh₃)₂CI₂ (0.02 mmol, 0.015 g) were added to a 250-mL three-neck round- bottom flask under a nitrogen atmosphere. When 20 mL of anhydrous degassed THF, 30 mL of anhydrous diisopropylamine, and trimethylsilylacetylene (8.8 mmol, 0.86 g) were added to the flask, the mixture was stirred under reflux for 12 hours. After the completion of the reaction (which was monitored by TLC), the reaction mixture was concentrated and dissolved in 50 mL of CH₂CI₂, washed twice with water and saturated saline solution. The organic layer was collected, dried over anhydrous MgSO₄, and concentrated under reduced pressure. The product was purified by neutralized silica gel column chromatography using hexane/EtOAc (95/5 to 90/10, v/v) to yield orange-red solid (2.9 g, 78%). ¹H NMR (400 MHz, CDCI₃) δ 6.40 (s, 2H), 4.00 (t, J = 6.4 Hz, 2H), 3.88 (t, J = 6.4 Hz, 4H), 2.61 (s, 6H), 1.76 (q, J = 6.8 Hz, 6H), 1.59 (s, 6H), 1.49-1.43 (m, 6H), 1.40-1.24 (m, 48H), 0.88-0.84 (m, 9H), 0.19 (S₁ 18H); ¹³C NMR (100 MHz₁ CDCI₃) δ 158.9, 154.5, 145.1 , 143.0, 139.1 , 131.2, 129.1 , 116.4, 106.2, 101.9, 97.3, 73.9, 69.7, 32.1 , 30.5, 29.9, 29.8, 29.6, 29.5, 26.3, 26.2, 22.9, 14.3, 13.7, 13.5, 0.28; IR(crτϊ¹): 2922, 2853, 2151, 1536, 1469, 1420, 1391, 1316, 1248, 1197, 1101 , 1004, 943, 853, 760, 721. ¹¹B NMR (400 MHz, CDCI₁): 3.82 (t, J = 97.6 MHz). ESI-MS. M⁺ (C₆₅H₁₀₇BF₂N₂O₃Si₂) Calcd: m/z = 1069.5, Found: m/z = 1069.5.

[00187] Compound 6c. When compound 5c (2.2 mmol, 2.4g) was dissolved in degassed THF (50 mL) in a 250-mL flask at -70 ⁰C, tetrabutylammonium fluoride (TBAF) (5.6 mmol, 1.47 g, 5.6 mL of 1 M solution) was added dropwise to the mixture via syringe. The reaction temperature was brought to the room temperature and the mixture was further stirred for 2 hours. After completion of the reaction, the mixture was acidified with acetic acid and extracted with CH₂CI₂. The extracted organic layer washed twice with water and saturated saline solution, dried over anhydrous MgSO₄, and concentrated under reduced pressure. The crude product was purified by column chromatography using hexane/EtOAc (20/80, v/v) to give the desired product as dark orange-pink crystalline solid (1.4 g, 72%). ¹H NMR (400 MHz, CDCI₃) δ 6.40 (s, 2H), 4.02 (t, J = 6.4 Hz, 2H), 3.90 (t, J = 6.4 Hz₁ 4H), 3.3(s, 2H), 2.62 (s, 6H), 1.75 (q, J = 6.8 Hz, 6H), 1.61 (S, 6H), 1.49-1.42 (m, 6H), 1.40-1.24 (m, 48H), 0.88-0.84 (m, 9H); ¹³C NMR (100 MHz, CDCI₃) δ 159.0, 154.5, 145.7, 143.4, 139.2, 131.1 , 129.0, 115.2, 106.3, 84.5, 76.1, 73.9, 69.7, 32.1 , 31.1 , 30.5, 29.9, 29.8, 29.6, 29.5, 26.3, 26.2, 25.8, 22.9, 14.3, 13.7, 13.5. ¹¹B NMR (400 MHz, CDCI₃): 3.82 (t, J = 97.6 MHz). IR(cιτϊ¹): 3300, 2922, 2853, 2108, 1526, 1469, 1420, 1387, 1334, 1310, 1183, 1112, 1066, 1003, 830, 720. ESI-MS. M⁺ (C₅₉H₉₁BF₂N₂O₃) Calcd: m/z = 925.2, Found: m/z = 925.1.

[00188] Polymer C. Compound 4c (0.13 mmol, 0.15 g), compound 6c (0.146 mmol, 0.135 g ), CuI (0.01 mmol, 0.002 g) were added to 100-mL flask under a nitrogen atmosphere. In the glove box, Pd(PPh₃)₄ (0.01 mmol, 0.012 g) was added to the flask. When a degassed mixed solution of anhydrous THF (20 mL) and anhydrous diisopropylamine (20 mL) were added to the flask, the mixture was stirred under reflux for 24 hours. After removal of the solvent, the residue was dissolved in methylene chloride (5mL), and added dropwise to 400 mL of ethanol to precipitate the polymer. The precipitated solid was collected by filtration and washed with excess ethanol and hexane. The obtained solid dried under vacuum for 24 h at room temperature to obtain dark-violet solid (0.196 g). ¹H NMR (400 MHz, CDCI₃) δ 6.42 (s, 2H), 3.99 (br, 2H), 3.89 (br, 4H), 2.63 (s, 6H), 1.75 (br, 6H), 1.61 (s, 6H)₁ 1.42 (br, 6H), 1.24 (br, 48H), 0.86-0.85 (br, 9H). ¹³C NMR (100 MHz, CDCI₃) δ 158.2, 154.5, 143.3, 141.1 , 139.3, 131.4, 129.0, 115.2, 106.3, 94.6, 74.0, 69.7, 32.1, 31 1 , 30.5, 29.9, 29.8, 29.6, 29.5, 26.3, 26.2, 25.8, 22.9, 14.3, 13.7, 13.5; IR(cm^'1): 2921 , 2852, 1521, 1466, 1421 , 1389, 1363, 1313, 1229, 1167, 1092, 1000, 758, 721.

[00189] Polymers A, B and C are soluble in common organic solvents such as chloroform, methylene chloride and THF. However, the solubility order is polymer C > polymer B > polymer A as the introduction of more side chains to each BODIPY core enhances solvation of conjugated polymers.

Photophysical Properties.

[00190] The absorption properties of green emissive BODIPY dye (3a) are characterized by a strong S₀->Si (π-π*) transition at 501 nm and a weaker broad band around 350 nm ascribed to the S₀-^S₂ (π-π*) transition (FIG. 38). Introduction of 2,6- diiodo substituents to the BODIPY core leads to a large red shifts (33 nm and 38 nm) of both the UV-absorption and fluorescence maxima, respectively, significantly depresses the fluorescence quantum yield because of efficient intersystem crossing induced by the heavy atom effect of iodine (FIG. 38, Table 9). 2,6-Diethynylation of 2,6-diiodo- tetramethyl BODIPY (4a) results in a little red shift due to the enhanced conjugation. However, polymer A emits in deep red region at 680 nm, and exhibits pronounced bathochromic shifts (149 nm and 211 nm) of both the absorption and fluorescence maxima relative to the initial BODIPY dye (3a) because of its significant extension of π- conjugation (FIG. 40 and Table 9). Polymer B displays an absorption maximum at 662 nm and fluorescence maximum at 684 nm, a slight red shifted relative to polymer A. Polymer C displays a slight red shift compared with polymer B as it shows absorption maximum at 669 nm and fluorescence maximum at 690 nm (FIG. 40). The absorption peaks of conjugated polymers become broader than BODIPY monomers due to the extended π-conjugation (FIG. 40). In addition, polymers A, B and C display a little more Stokes shifts than their corresponding BODIPY dyes (Table 9). BODIPY dyes (3a, 3b, 3c, 5a, 5b, 5c, 6a, 6b and 6c) show fluorescence lifetimes in several nanoseconds (Table 9). However, the diiodo-functionalized BODIPY dyes (4a, 4b and 4c) display much shorter fluorescence lifetimes (ranging from 0.15 ns to 0.21 ns), consistent with their decreased quantum yields because of efficient intersystem crossing induced by the heavy atom effect of iodine (Table 9).

[00191] Arylation at the meso position has no significant effect on the absorption and emission maxima of BODIPY dyes since the arylated moiety is not coplanar with the BODIPY core due to steric hindrance although the substitution position is structurally different (Table 9). As a result, three different BODIPY monomers (4a-4c and 6a-6c) each have only 1 or 2 nm difference among their respective absorption or emission spectral maxima. However, the absorption and emission maxima of polymer C are somewhat more red-shifted relative to those of polymers A and B, which might arise from amplification effect of conjugated polymers. Polymers A, B and C displays a little shorter fluorescence lifetimes than their starting BODIPY dyes (3a, 3b and 4c) (Table 9).

Table 9. Absorption and emission maxima, and quantum yields of BODIPY dyes and polymers in methylene chloride solution. Quantum yields of BODIPY dyes and polymeric dyes were determined by use of fluorescein (quantum yield of 0.85 in 0.1 N NaOH) as a standard.

BODIPY 3a 4a 5a 6a Polym Thin dyes or er A film of polymers polym er A

Absorption 501 533 554 539 650 680 maxima

(nm)

Emission 5 5 5 5 68 7 maxima 09 48 69 51 0 23

(nm)

Quantum 2.3 yield (%)

Fluorescen 3.9 0.21 4.4 3.6 1.4 ce lifetime -

(ns)

Stokes 8 15 15 12 30 43 shift (nm) BODIPY 3b 4b 5b 6b Polym Thin dyes or er B film of polymers polym er B

Absorption 502 534 555 540 662 728 maxima

(nm)

Emission 5 5 5 . 5 . 68 . 7 maxima 10 49 70 52 4 41

(nm)

Quantum 2.7 yield (%)

Fluorescen 4.1 0.15 4.6 3.9 1.1 ce lifetime

(ns)

Stokes 8 15 15 12 22 12 shift (nm)

BODIPY 3c 4c 5c 6c Polym Thin dyes or er C film of polymers polym er C

Absorption 503 535 - 556 541 669 726 maxima

(nm)

Emission 511 550 570 553 690 743 maxima

(nm)

Quantum 2.3 yield (%)

Fluorescen 3.2 0.19 4.4 3.0 1.6 ce lifetime

(ns)

Stokes 9 15 14 12 19 19 shift (nm) Thermal stabilities of the polymers.

[00192] Thermal stabilities of polymers A, B and C were determined by thermogravimetrc analysis (TGA) at the heating rate of 20 ⁰C /min under nitrogen atmosphere. From the graphs, the thermal decomposition temperatures (T_d) of the polymers ranged from 270 to 360 ⁰C, which suggests their good thermal stability. (FIG. 41) The small amount of weight loss of polymer C before its T_d is probably due to decomposition of the oliogmers. Differential scanning calorimetry (DSC) of polymers did not give a clear phase transition, which may arise from that polymer chain movements are limited by their rigid structures.

Example 14. Synthesis of Fluorescent Conjugated Glycopolymers A-E [00193] The structures of Polymers A-E are shown in FIG. 42

[00194] Instrumentation. ¹H NMR and ^13C NMR spectra were taken on a 400 MHz Varian Unity Inova spectrophotometer instrument. ¹H and ^13C NMR spectra were recorded in CDCI₃, and chemical shifts (δ) are given in ppm relative to solvent peaks (¹H, δ 7.26; ¹³C, δ 77.3) as internal standard. UV spectra were taken on a Hewlett-Packard 8452A Diode Array UV-visible spectrophotometer. Fluorescence spectra were recorded on a Spex Fluorolog 1681 0.22m steady-state .fluorometer. Fluorescence quantum yields of BODIPY dyes and polymers were measured in methylene chloride and calculated by using fluorescein exClted at 490 nm in 0.1 N NaOH as the reference (quantum efficiency, cPn = 85%). Fluorescence lifetimes were measured on a 010-3300 Nitrogen Laser laserstrobe PTI instrument and analyzed using FeliX32 software. Molecular weights of the polymers were determined by gel permeation chromatography (OPC) by using a Waters Associates model 6000A liquid chromatograph. Three American Polymer Standards Corp. ultrastyragel columns in series with porosity indices of 103, 104, and 105 A were used and housed in an oven thermostatted at 30⁰C. The mobile phase was HPLC grade THF which was filtered and degassed by vacuum filtration through a 0.5 ,um fluoropore filter prior to use. The polymers were detected by a Waters Model 440 ultraviolet absorbance detector at awavelength of 254 nm and a Waters Model 2410 refractive index detector. Molecular weights were determined relative to polystyrene standards.

[00195] Materials. Unless otherwise indicated, all reagents and solvents were obtained from commercial suppliers (Aldrich, Sigma, Fluka, Acros Organics, Fisher Scientific, Lancaster) and were used without further purification. Air- and moisture- sensitive reactions were conducted in oveπ-dried glassware using a standard Schlenk line or drybox techniques under an inert atmosphere of dry nitrogen. 9,9-Bis-(6'- bromohexyl)-2,7-diido-9H-fluorene, 1 ,4-diiodo-2,5didecyloxybenzene (7b), and 2,5- diiodo-3-decylthiophene (7C) were prepared according to the reported procedures.

Polymer A

[00196] The synthetic route to Polymer A is shown in FIG. 44 and is detailed below.

[00197] Ethyl 4-(4-Formylphenoxy)butanoate (1a). When 150 mL of degassed DMF was added to a 500 mL three-neck round-bottom flask containing 4- hydroxybezaldehyde (40.9 mmol, 5 g), ethyl 4-bromobuterate (49.1 mmol, 9.57 g), and K₂CO₃ (122 mmol, 16.8 g) under a nitrogen atmosphere, the mixture was stirred for 4 h at 80⁰C under a nitrogen atmosphere. After completion of the reaction (which was monitored by TLC), the reaction mixture was concentrated under reduced pressure. The residue was dissolved in 50 mL of EtOAc and washed twice with water and saturated NaCI solution. The organic layer was collected, dried over anhydrous MgSO4, and concentrated under reduced pressure. The resulting crude product was purified by silica gel column chromatography using hexane/EtOAc (70/30, v/v) to obtain white solid (9.36 g, 97%). ¹H NMR (400 MHz, CDCI₃): δ 9.85 (s, ¹H), 7.80 (d, J = 8.8 Hz, 2H), 6.99 (d, J = 8.8 Hz, 2H), 4.12 (q, J = 7.2 Hz, 2H), 4.07 (t, J = 6.0 Hz, 2H), 2.50 (t, J = 7.2 Hz, 2H), 2.12 (q, J = 6.4, 2H), 1.26 (t, J = 7.2 Hz, 3H). ¹³C NMR (100 MHz, CDCI₃): δ 190.9, 173.2, 164.1 , 132.2, 130.2, 114.9, 67.3, 60.7, 30.8, 24.6, 14.4.

[00198] BODIPY Dye 3a. Ethyl 4-(4-formylphenoxy)butanoate (1a) (8.72 mmol, 2.07 g) and 2,4-dimethylpyrrole (17.44 mmol, 1.66 g) were dissolved in 1000 mL of dry CH2CI2 in a 2000-mL threeneck flask. Eight drops of trifluoroacetic acid (TFA) were added to the reaction mixture, and the resulting mixture was stirred in the dark for 12 h under nitrogen atmosphere at room temperature. After the complete consumption of aldehyde (1a) (which was monitored by TLC), DDQ (2,3-dichjoro-5,6-dicyano-1,4- benzoquinone) (8.72 mmol 1.974 g) in 10 mL of CH₂CI₂ was added to the reaction mixture. When the mixture was stirred for 30 min, 17 mL of diisopropylethylamine (DIEA) and 17 mL of BF₃ ^«OEt₂ were added to the mixture. After the mixture was further stirred for 30 min, it was concentrated to 200 mL and filtered. The filtrate was washed twice with water and brine solution, dried over anhydrous MgSO₄, and concentrated under reduced pressure. The crude product was purified by column chromatography using hexanel EtOAc (90/10 to 70/30, v/v) to obtain a dark brown crystalline solid (1.51 g, 38%). ^1H NMR (400 MHz, CDCI₃): δ 7.13 (d, J= 8.4 Hz, 2H), 6.96 (d, J = 8.4 Hz, 2H), 5.95 (s, 2H), 4.14 (q, J= 7.2 Hz, 2H), 4.04 (t, J = 6.2 Hz, 2H)₁ 2.54-2.51 (m, 8H), 2.15-2.11 (m, 2H), 1.40 (s, 6H), 1.25 (I, J = 7.2 Hz, 3H).¹³C NMR (100 MHz₁ CDCI₃): δ 173.3, 159.6, 155.4, 143.3, 142.0, 132.0, 129.4, 127.3, 121.2, 115.2, 67.0, 60.67, 30.9, 24.8, 14.8, 14.4. IR: 2954, 2922, 2970, 1736, 1609, 1542, 1514, 1464, 1441 , 1408, 1375, 1365, 1309, 1281 , 1261, 1239, 1191 , 1179, 1153, 1090, 1043, 937, 828, 802, 763, 703 em^"1. ESI-MS: M⁺ (C₂₅H_29BF₂N₂O₃) calcd, mlz = 454.2; found, mlz = 454.9. It shows absorption maximum at 501 nm and emission maximum at 510 nm in CH₂CI₂ solution.

[00199] BODIPY Dye 4a. When iodic acid (6.13 mmol, 1.08 g) in 5 mL of water was added dropwise to the ethanol solution 50 mL) containing compound 3a (3.1 mmol 1.4 g) and iodine (6.7 mmol 0.85 g) over 30 min, the mixture was stirred for 2 h.¹⁴ After the completion of the reaction, the mixture was concentrated under reduced pressure, dissolved in CH₂CI₂ and washed twice with water and saturated saline solution. The organic layer was collected, dried over anhydrous MgSO₄, and concentrated under reduced pressure. The crude product was purified by column chromatography to yield 4a as red crystals (2.1 g, 98%). ¹H NMR (400 MHz, CDCI₃): δ 7.11 (d, J = 8.4 Hz, 2H), 6.99 (d, J = 8.4 Hz, 2H), 4.15 (q, J= 7.2 Hz, 2H), 4.06 (t, J = 6.0 Hz, 2H), 2.62 (s, 6H), 2.54 (t, J= 6.0, 2H), 2.17-2.13 (m, 2H), 1.42 (s, 6H), 1.26 (t, J = 6.8 Hz, 3H). ¹³C NMR (100 MHz, CDCI₃): δ 173.3, 160.0, 156.8, 145.5, 141.7, 131.9, 129.3, 126.9, 1 15.5, 85.7, 67.2, 60.7, 30.9, 24.8, 17.4, 16.2, 14.5. IR: 2961 , 2899,1720,1605,1538,1509,1464, 1431 , 1398, 1344, 1310, 1296, 1263, 1225, 1177, 1073, 1042, 1000, 916, 837, 763, 705 em^"1. ESI- MS: M⁺ (C₂₅H₂₇BF₂I₂N₂O₃) calcd, mlz = 706.0; found, mlz = 705.6. It shows an absorption maximum at 533 nm and emission maximum at 548 nm in CH₂CI₂ solution.

[00200] BODIPY Dye 5a. BODIPY dye 4a (1.69 mmol, 1.2 g), CuI (0.02 mmol, 0.004 g), and Pd(PPh₃)₂CI₂(0.02 mmol, 0.015 g) were added to a 100-mL three-neck round- bottom flask under a nitrogen atmosphere. When 20 mL of anhydrous degassed THF, 20 mL of anhydrous diisopropylamine, and trimethylsilylacetylene 5.0 mmol, 0.49 g) were added to the flask, the mixture was stirred under reflux for 4 h. After the completion of the reaction (which was monitored by TLC), the reaction mixture was concentrated and dissolved in 50 mL of CH₂CI₂and washed twice with water and saturated saline solution. The organic layer was collected, dried over anhydrous MgSO₄, and concentrated under reduced pressure. The product was purified by silica gel column chromatography using hexanelEtOAc (95/5 to 80120, v/v) to yield orange-red solid (0.91 g, 84%). ¹H NMR (400 MHz, CDCI₃): δ 7.17 (d, J = 8.4 Hz₁ 2H), 6.98 (d, J = 8.4 Hz, 2H), 4.15 (q, J = 7.2 Hz, 2H), 4 05 (t, J = 60 Hz, 2H), 2 60 (s, 6H), 2 54 (t, J = 6 0, 2H), 2 16-2 13 (m, 2H), 1 48 (s, 6H), 1 26 (t, J = 6 8 Hz, 3H) 0 19 (s, 18H) ¹³C NMR (I OO MHZ₁ CDCI₃) 5 173 3, 159 9, 158 7, 145 1 , 143 1 , 131 6, 129 3, 126 7, 116 3, 115 4, 101 8, 97 4, 67 1 , 60 7, 30 9, 24 8, 14 4, 13 8,0 28 IR 2955, 2923, 2152, 1737, 1609, 1530, 1472, 1393, 1366, 1318, 1290, 1247, 1198, 1174, 1086, 1048, 1001 , 946, 930, 765, 703 em ¹ ESI-MS [M]⁺ (C₃₅H₄₅BF₂N₂O₃Si₂) calcd, mlz = 646 3, found, mlz = 6474 It shows absorption maximum at 553 nm and emission maximum at 569 nm in CH₂CI₂ solution

[00201] BODIPY Dye 6a When BODIPY dye 5a (0 77 mmol, 0 50 g) was dissolved in degassed THF (8 mL) in a 50-mL flask at -70 DC, tetrabutylammonium fluoride (TBAF) (3 1 mmol, 3 mL of 1 M solution) was added dropwise to the mixture via syringe under a nitrogen atmosphere The reaction temperature was brought to the room temperature, and the mixture was further stirred for 4 h under nitrogen atmosphere After completion of the reaction, the reaction mixture was acidified with acetic acid, diluted with water, and then extracted with 50 mL of CH₂CI₂ When the reaction mixture was concentrated under reduced pressure, the residue was dissolved in 50 mL of CH₂CI₂ and washed twice with water and saturated saline solution The organic layer was collected, dried over anhydrous MgSO₄, and concentrated under reduced pressure The crude product was purified by column chromatography using hexane/EtOAc (20/80, v/v) to give the desired product as orange-pink crystalline solid (0 29 g, 76%) ¹H NMR (400 MHz₁ CDCI₃) δ 7 11 (d, J = 8 4 Hz, 2H), 6 99 (d, J = 8 4 Hz₁ 2H), 4 15 (q, J= 7 2 Hz, 2H), 4 06 (t J = 6 0 Hz, 2H), 3 29 (s, 2H), 2 62 (s, 6H), 2 54 (t, J = 6 0, 2H)₁ 2 17-2 13 (m, 2H)₁ 1 50 (s, 6H), 1 26 (t, J = 6 8 Hz, 3H) ¹³C NMR (100 MHz, CDCI₃) δ 173 3, 159 9, 158 9, 145 7, 143 5, 131 5, 129 2, 1264, 115 5, 115 2, 84 2, 76 2, 67 1 , 60 7, 30 9, 29 9, 24 8, 14 4, 13 7 IR 3293, 3257, 2936, 1719, 1529, 1474, 1394, 1368, 1316, 1288, 1272, 1244, 1196, 1178, 1004, 953, 806, 766, 707 erτϊ¹ ESI-MS [M]⁺ (C₂₉H₂₉BF₂N₂O₃) calcd, mlz = 502 2, found, mlz = 503 1 It shows absorption maximum at 538 nm and emission maximum at 552 nm in CH₂CI₂ solution

[00202] Polymer A BODIPY dye 4a (0 133 mmol, 94 mg), BODIPY dye 6a (0 139 mmol, 70 mg), and CuI (2 mg) were added to a 100-mL flask under a nitrogen atmosphere In the glovebox, Pd(PPh₃)* 5 mg) was added to the flask When a degassed mixed solution of anhydrous THF (20 mL) and anhydrous dnsopropylamine (20 mL) were added to the flask, the mixture was stirred under reflux for 24 h After removal of the solvent, the residue was dissolved in methylene chloride The organic layer was washed with water, dried over anhydrous MgSO₄, and filtered Then the filtrate was concentrated under reduced pressure and added to 200 mL of ethanol to precipitate the polymer The precipitated solid was collected, washed with ethanol, and dried under vacuum for 24 h at room temperature to obtain dark-violet solid (0.102 g). ¹H NMR (400 MHz, CDCh): δ 7.11 (d, 2H), 6.99 (d, 2H), 4.15 (broad q, 2H), 4.06 (broad t, 2H), 2.62 (s, 6H), 2.54 (broad t, 2H), 2.17-2.13 (broad m, 2H), 1.42 (s, 6H), 1.27 (broad t, 3H). ¹³C NMR (100 MHz, CDCI₃): δ 173.3, 159.9, 158.1 , 143.3, 142.3, 131.5, 129.2, 126.9, 116.5, 115.5, 89.0, 67.1 , 60.7, 30.9, 29.9, 24.8, 14.4, 13.7. IR: 2925, 1732, 1608, 1513, 1472, 1436, 1390, 1313, 1226, 1164, 1088, 836, 765, 703 em^"1. It shows absorption maximum at 659 nm and emission maximum at 678 nm in CH₂CI₂ solution. OPC (THF₁ polystyrene standard), M_n= 16500 g/mol; polydispersity = 1.8.

Polymer B

[00203] The synthetic route to Polymer B is shown in FIG. 43 and is detailed below.

[00204] Compound 1b. When 200 mL of DMF was added to a 500-mL three-neck round-bottom flask containing 3,4-dihydroxybezaldehyde 59.7 mmol, 8 g), ethyl A- bromobuterate (143.3 mmol, 27.9 g), and K₂CO₃ (238.8 mmol, 32.4 g) under a nitrogen atmosphere, the mixture was stirred for 4 h at 8O⁰C under a nitrogen atmosphere. After completion of the reaction (which was monitored by TLC), DMF was removed from the mixture under reduced pressure. The residue was dissolved in 150 mL of EtOAc and washed with water and saturated saline solution twice. The organic layer was collected, dried over MgSO₄, and concentrated under reduced pressure. The resulting crude product was purified by silica gel column chromatography using hexane/EtOAc (70/30, v/v) to obtain white solid (20.7 g, 95%). ¹H NMR (400 MHz, CDCI₃): δ 9.80 (s, LH), 7.42- 7.37 (m, 2H), 6.94 (d, J = 8.0 Hz, LH), 4.15-4.06 (m, 8H), 2.54-2.49 (m, 4H), 2.17-2.12 (m, 4H), 1.23 (t, J = 7.2 Hz, 6H). ¹³C NMR (100 MHz, CDC13): δ 191.0, 173.2, 154.4, 149.3, 130.3, 126.9, 112.2, 1 11.5, 68.1 , 68.0, 60.6, 30.8, 30.6, 24.6, 24.5, 14.4.

[00205] BODIPY Dye 3b. Compound 1b (8.72 mmol, 3.19 g) and 2,4-dimethylpyrrole (17.44 mmol, 1.66 g) were added to degassed anhydrous 1000 mL of CH₂CI₂ in a 2000- mL three-neck roundbottom flask. When eight drops of TFA were added to the reaction mixture, the mixture was stirred in the dark for 12 h at room temperature under nitrogen atmosphere. After the completion of aldehyde (1 b) (which was conformed by TLC), DDQ (2,3-dichloro-5,6-dicyano-1 ,4-benzoquinone) (8.72 mmol 1.974 g) in CH₂CI₂ was added. After the mixture was stirred for 30 min, DIEA (diisopropylethylamine) (17 mL) and BF₃OEt₂ (17 mL) were added. When the mixture was stirred for 1/2 h, it was concentrated to 200 mL and filtered. The filtrate was washed twice with water and brine solution, dried over MgSO₄ and concentrated under reduced pressure. The crude product was purified by column chromatography using hexane/EtOAc (90/10 to 70/30, v/v) to obtain a dark brown crystalline solid (1.8 g, 37%). ¹H NMR (400 MHz₁ CDCI₃): δ 6.95 (d, J = 8.4 Hz, LH), 6.78-6.76 (m, 2H), 5.95 (s, LH), 4.17-4.05 (m, 6H), 3.98 (t, J = 6.0 Hz, 2H), 2.56-2.48 (m, 10H), 2.18-2.08 (m, 4H), 1.44 (s, 6H), 1.26-1.20 (m, 6H). ¹³C NMR (100 MHz, CDC₁₃): δ 173.3, 173.2, 155.5, 149.7, 149.6, 143.3, 141.7, 131.8, 127.7, 121.3, 121.1, 114.3, 113.9, 68.5, 68.2, 60.6, 30.8, 24.8, 14.7, 14.6, 14.4. IR: 2926, 1739, 1720, 1543, 1509, 1470, 1413, 1371, 1306, 1265, 1160, 1134, 1060, 1037, 1007, 975, 954, 824, 802, 760, 744, 726 em^"1. ESI-MS [M + Na]⁺ (C₃IH₃₉BF₂N₂O₆Na) calcd, mlz = 607.3; found, mlz = 607.3. It shows absorption maximum at 502 nm and emission maximum at 511 nm in CH₂CI₂ solution.

[00206] BODIPY Dye 4b. When iodic acid (6.13 mmol, 1.08 g) in 5 mL of water was added dropwise to the ethanol solution 50 mL) containing BODIPY dye 3b (3.1 mmol 1.8 g) and iodine (6.7 mmol 0.85 g) over 30 min, the mixture was stirred for 2 h. After the completion of the reaction, the reaction mixture was concentrated under reduced pressure and dissolved in CH₂CI₂. The organic layer was washed twice with water and with saturated saline solution, dried over MgSO₄, and concentrated under reduced pressure. The crude product was purified by column chromatography using hexane/EtOAc (80/20, v/v) to yield 4b as red crystals (2.5 g, 98%). ¹H NMR (400 MHz, CDCI₃): δ 6.97 (d, J = 8.4 Hz, LH), 6.75-6.71 (m, 2H), 4.17-4.09 (m, 6H)₁ 3.97 (t, J = 6.0 Hz, 2H), 2.61 (S, 6H), 2.57-2.48 (m, 4H), 2.18-2.08 (m, 4H), 1.45 (s, 6H), 1.27-1.20 (m, 6H). ¹³C NMR (100 MHz, CDCI₃): δ 173.3, 173.1 , 156.8, 150.0, 149.9, 145.5, 141.4, 131.8, 127.2, 120.9, 114.3, 113.6, 85.7, 68.6, 68.2, 60.6, 30.8, 24.8, 17.3, 16.2, 14.4. IR: 2977, 2957, 2772, 2931 , 1730, 1539, 1508, 1463, 1396, 1345, 1309, 1265, 1245, 1178, 1138, 1119, 1085, 1048, 989, 956, 758, 724 em^"1. ESI-MS [M + Na]⁺ (C₃₁H₃₇BF₂I₂N₂O₆Na) calcd, mlz = 859.1 ; found, mlz = 859.4. It shows absorption maximum at 534 nm and emission maximum at 549 nm in CH₂CI₂ solution.

[00207] BODIPY Dye Sb. BODIPY dye 4b (1.7 mmol, 1.5 g), CuI (0.02 mmol, 4 mg) and Pd(PPh₃)₂CI₂ (0.02 mmol, 15 mg) were added to a 100-mL three-neck round-bottom flask under nitrogen atmosphere. When degassed anhydrous THF (20 mL), anhydrous diisopropylamine (20 mL), and trimethylsilylacetylene 5.3 mmol, 0.52 g) were added to the flask, the mixture was stirred under reflux for 4 h. After the completion of the reaction (which was monitored by TLC), the reaction mixture was concentrated under reduced pressure, dissolved in 50 mL of CH₂CI₂ and washed twice with water and saturated saline solution. The organic layer was collected, dried over MgSO₄, and concentrated under reduced pressure. The product was purified by silica gel column chromatography using hexane/EtOAc (95/5 to 70/30, v/v) to yield orange-red solid (1.07 g, 82%). ¹H NMR (400 MHz, CDCI₃): δ 6.96 (d, J = 8.4 Hz, LH), 6.74-6.71 (m, 2H), 4.15-4.07 (m, 6H)₁ 3.97 (t, J = 6.0 Hz, 2H), 2.60 (s, 6H), 2.57-2.48 (m, 4H), 2.18-2.09 (m, 4H), 1.52 (s, 6H), 1.27- 1.20 (m, 6H), 0.19 (s, 18H). ¹³C NMR (100 MHz, CDCI₃): δ 173.3, 173.1 , 158.8, 149.9,

149.8, 145.0, 142.7, 131.4, 127.0, 120.9, 116.4, 114.3, 113.6, 101.9, 97.3, 68.6, 68.2, 60.6, 30.8, 24.8, 14.4, 13.7, 13.6, 0.28. IR: 2921, 2852, 2201 , 1604, 1513, 1467, 1435, 1389, 1363, 1310, 1263, 1227, 1162, 1083, 994, 814, 760, 724 etτf¹. ESI-MS [M]+ (C₄₁H₅₅BF₂N₂O₆Si₂) calcd, mlz = 776.4; found, mlz = 776.9. It shows absorption maximum at 554 nm and emission maximum at 570 nm in CH₂CI₂ solution.

[00208] BODIPY Dye 6b. When BODIPY dye 5b (0.65 mmol, 0.50 g) was dissolved in degassed THF (8 mL) in a 50-mL flask at -70 DC, tetrabutylammonium fluoride (TRAF) (2.6 mmol, 2.6 mL of 1 M solution) was added dropwise to the mixture via syringe under nitrogen atmosphere. The reaction temperature was brought to room temperature, and the mixture was further stirred for 4 h under nitrogen atmosphere. After completion of the reaction, the reaction mixture was acidified with acetic acid, diluted with water, and then extracted with 50 mL of CH₂CI₂. The organic layer was washed twice with water and saturated saline solution. The organic layer was collected, dried over anhydrous MgSO₄, and concentrated under reduced pressure. The crude product was purified by column chromatography using hexane/EtOAc (20/80, v/v) to give the product as orange-pink crystalline solid (0.29 g, 75%). ¹H NMR (400 MHz, CDCI₃): δ 6.97 (d, J = 8.4 Hz, LH), 6.76-6.71 (m, 2H), 4.15-4.07 (m, 6H), 3.96 (t, J = 6.0 Hz, 2H), 3.30 (s, 2H), 2.60 (s, 6H), 2.57-2.48 (m, 4H), 2.18-2.09 (m, 4H), 1.54 (s, 6H), 1.27-1.20 (m, 6H). ¹³C NMR (100 MHz, CDCI₃): δ 173.3, 173.1 , 158.9, 150.0, 149.9, 145.7, 143.2, 131.4, 126.8, 120.9, 115.2, 114.3, 113.6, 84.3, 76.1, 68.6, 68.2, 60.6, 30.8, 24.8, 14.4, 13.7, 13.6. IR: 3296, 3255, 2958, 2933, 1728, 1532, 1467, 1392, 1316, 1265, 1247, 1184, 1084, 1013, 995, 761 em^"1. ESI-MS [M + Na]⁺ (C₃, H₃₇BF₂I₂N₂O₆Na) calcd, m/z = 655.3; found, m/z =

655.9. It shows absorption maximum at 539 nm and emission maximum at 553 nm in CH₂CI₂ solution.

[00209] Polymer B. BODIPY dye 4b (0.81 mmol, 0.677 g), BODIPY dye 6b (0.84 mmol, 0.531 g), and CuI (0.Q1 mmol, 4 mg) were added to a 100-mL round-bottom flask. Pd(PPh₃J₄ (10 mg) was added to the flask under a nitrogen atmosphere. When a degassed mixed solution of anhydrous THF (20 mL) and anhydrous diisopropylamine (20 mL) were added to the flask, the mixture was stirred under reflux for 24 h. After removal of the solvent, the residue was dissolved in methylene chloride and washed with water. The organic layer was collected, dried over anhydrous MgSO₄, and filtered. [00210] Then the filtrate was concentrated under reduced pressure and added to 200 mL of ethanol to precipitate the polymer The precipitated solid was collected washed with ethanol, and dried under vacuum for 24 h at room temperature to obtain dark-violet solid (0 912 g) ¹H NMR (400 MHz, CDCI₃) δ 6 96 (br, LH), 6 73 (br, 2H), 4 15-4 09 (br, 6H), 3 97 (br, 2H), 2 62 (s, 6H), 2 55-2 49 (br, 4H), 2 14-2 10 (br, 4H)₁ 1 54 (s, 6H), 1 25- 1 20 (br, 6H) ¹³C NMR (100 MHz, CDCI₃) δ 173 3, 173 1 158 2, 150 0, 149 8, 143 3, 142 3, 131 7, 126 9, 120 9, 116 5, 114 2, 113 6, 89 0, 68 6, 68 2, 60 6, 31 1 30 8, 24 8, 14 4, 13 8, 13 7 IR 2932, 1729, 1513, 1471, 1436, 1390, 1311 , 1264, 1228, 1161 , 1087, 992, 882, 816, 760, 725, 694, 681 em ¹ It displays absorption maximum at 665 nm and emission maximum at 683 nm in CH₂CI₂ solution OPC (THF, polystyrene standard), M_n= 23 800 g/mol, polydispersity = 1 9

Polymers C. D and E

[00211] The synthetic route to polymers C, D and E is shown in FIG 44 and detailed below

[00212] 9,9-Bis(6¹-(hexylthio)hexyl)-2,7-diiodo-9H-fluorene (7a) When 15O mL of degassed DMF was added to a 250-mL three-neck round-bottom flask containing 9,9- bιs-(6'-bromohexy1)-2,7-dιιdo9H-fluorene (2 69 mmol, 2 g), hexanethiol (8 07 mmol, 0 95 g), and K₂CO₃ (10 8 mmol, 1 48 g) under a nitrogen atmosphere, the mixture was stirred for 24 h at 40°C under a nitrogen atmosphere After completion of the reaction (which was monitored by TLC), the reaction mixture was concentrated under reduced pressure, added to water, and extracted with EtOAc The organic layer was washed twice with water and saturated NaCI solution, dried over anhydrous MgSO₄, and concentrated under reduced pressure The resulting cmde product was purified by silica gel column chromatography using hexane/EtOAc to obtain brown liquid (1 47 g, 67%) ¹H NMR (400 MHz, CDCI₃) δ 7 65-7 61 (m, 4H), 7 38 (d, J = 7 6, 2H), 2 44-2 35 (m, 8H), 1 89-1 85 (m, 4H) 1 53-1 47 (m, 4H), 1 4-1 22 (m, 20H)₁ 1 15-1 04 (m, 8H), 1 03-0 84 (m, 6H) ¹³C NMR (I OO MHZ₁ CDCI₃) 6 152 5, 140, 136 3, 132 1, 121 7, 934, 55 5, 40 2, 32 4, 32 3, 31 7, 31 6, 29 9, 29 8, 29 7, 28 8, 23 8, 22 8, 14 3, 14 2 IR 2924 9, 2853 4, 1593 4, 1567 8, 1448 0, 1409 4, 1393 4, 1377 0, 1279 1 , 1255 6, 1054 0, 1003 3, 879 2, 808 1 , 738 3 cm ¹ ESI-MS M⁺ (C₃₇H₅₆I₂S₂) calcd, m/z = 818 8, found, m/z = 818 7

[00213] Polymer C BODIPY dye 6b (0 126 mmol, 80 mg), 9,9- bιs(6¹(hexylthιo)hexyl)-2,7-dιιodo-9H-fluorene (7a) (0 115 mmol, 94 mg), and CuI (2 mg) were added to a 100-mL flask under a nitrogen atmosphere In the glovebox, Pd(PPh₃)₄ 5 mg was added to the flask When a degassed mixed solution of anhydrous THF (20 mL) and anhydrous diisopropylamine (20 mL) were added to the flask, the mixture was stirred under reflux for 24 h. After removal of the solvent, the residue was dissolved in methylene chloride 5 mL and added to 400 mL of ethanol to precipitate the polymer. The precipitated solid was filtered and washed with ethanol and hexane. The obtained solid was dried under vacuum for 24 h at room temperature to obtain dark-violet solid (0.147 g). ¹H NMR (400 MHz, CDCI₃): δ 7.65-7.60 (br, IH), 7.45-7.36 (m, 2H), 7.03-6.99 (br, IH), 6.84-6.77 (br, 2H), 4.19-4.12 (br, 6H), 4.12-4.00 (br, 2H), 2.76 (s, 6H), 2.59-2.13 (m, 16H), 1.94 (br, 4H), 1.66 (s, 6H), 1.56-1.47 (br, 4H), 1.36-1.09 (m, 34), 0.86-0.84 (br, 6H). ¹³C NMR (100 MHz, CDCI₃): δ 173.3, 173.2, 158.9, 151.1 , 149.9, 144.1 , 140.7, 132.3, 131.8, 130.8, 125.5, 121.1 , 120.2, 116.4, 114.4, 97.7, 68.7, 68.3, 60.7, 40.5, 32.4, 32.2, 31.6, 30.8, 29.8, 28.8, 24.8, 23.9, 22.7, 22.6, 14.5, 14.0, 13.9. IR: 2925.4, 1731.7, 1521.2, 1391.2, 1313.7, 1269.7, 1245.4, 1078.6, 1002.5, 820.6, 760.4 cm^"1 It shows absorption maximum at 606 nm and emission maximum at 641 nm in CH₂Cb solution. OPC (THF, polystyrene standard), M_n= 21 600 g/mol; polydisperstty = 2.1.

[00214] Polymer D. BODIPY dye 6b (0.08 mmol, 50 mg), 1 ,4-diiodo2,5- didecyloxybenzene (7b) (0.072 mmol, 46 mg), and CuI (2 mg) were added to a 100-mL flask under a nitrogen atmosphere. In the glovebox, Pd(PPh₃J₄ 5 mg was added to the flask. When a degassed mixed solution of anhydrous THF (20 mL) and anhydrous diisopropylamine (20 mL) were added to the flask, the mixture was stirred under reflux for 24 h. The polymer was purified in a way for polymer C to obtain dark-violet solid (0.073 g). ¹H NMR (400 MHz, CDCI₃): δ 6.99 (br, IH), 6.85-6.75 (br, 4H), 4.18-4.11 (br, 6H), 3.99-3.92 (br, 6H), 2.72 (s, 6H), 2.58-2.49 (m, 4H), 2.18-2.12 (br, 4H), 1.75 (br, 4H), 1.62 (S, 6H), 1.42 (br, 4H), 1.28-1.20 (br, 30H), 0.86-0.84 (br, 6H). ¹³C NMR (100 MHz₁ CDCI₃): δ 173.3, 173.1 , 158.8, 153.4, 152.0, 149.9, 143.8, 142.3, 131.8, 127.1 , 123.4, 121.0, 1(16.6, 116.0, 114.3, 1 13.8, 93.5, 87.4, 70.4, 69.5, 68.6, 68.3, 60.7, 33.9, 32.0, 30.9, 29.9, 29.8, 29.7, 29.54, 29.51, 29.4, 26.3, 26.2, 24.8, 22.9, 14.4, 14.4, 14.3, 13.8, 13.7. IR: 2924.6, 1726.2, 1526.4, 1314.8, 1009.7,762.0 em^"1. It exhibits absorption maximum at 635 nm and emission maximum at 657 nm in CH₂CI₂ solution. OPC (THF, polystyrene standard), M_n= 19200 g/mol; polydispersity = 1.9.

[00215] Polymer E. BODIPY dye 6b (0.126 mmol, 80 mg), 2,5-diiodo3- deeylthiophene (7c), (0.115 mmol, 54 mg), and CuI (2 mg) were added to a 100-mL flask under a nitrogen atmosphere. In the glovebox, Pd(PPh₃J₄ 5 mg was added to the flask. When a degassed mixed solution of anhydrous THF (20 mL) and anhydrous diisopropylamine (20 mL) were added to the flask, the mixture was stirred under reflux for 24 h. The polymer was purified in a way for polymer C to obtain dark-violet solid (0.106 g). ¹H NMR (400 MHz, CDCI₃): δ 7.00-6.98 (m, 2H), 6.76 (br, 2H), 4.18-4.10 (br, 6H), 3.98 (br, 2H)₁ 2.66 (s, 6H), 2.58-2.49 (m, 6H)₁ 2.18-2.12 (br, 4H), 1.57 (br, 8H), 1.27- 1.22 (br, 20H), 0.86-0.84 (br, 3H). ¹³C NMR (100 MHz, CDCI₃): δ 173.3, 173.1 , 158.7, 150.2, 149.9, 147.4, 144.3, 142.6, 132.7, 131.8, 126.8, 123.1 , 121 , 116.2, 115.9, 114.3, 113.7, 89.1 , 86.4, 76.9, 68.6, 68.2, 60.6, 32.1 , 30.8, 30.3, 29.9, 29.8, 29.7, 29.6, 29.5, 24.8, 22.9, 19.9, 14.44, 14.41, 14.3, 13.9, 13.8. IR: 2921.1 , 1731.0, 1516.5, 1391.3, 1312.0, 1246.0, 1170.0, 1000.0, 760.0, 724.7 em^"1. It shows absorption maximum at 628 nm and emission maximum at 664 nm in CH₂CI₂ solution. OPC (THF, polystyrene standard), M_n= 15 700 g/mol; polydispersity = 2.0.

[00216] Optical Properties of the Monomers and Polymers. The absorption properties of green emissive BODIPY dye (3a) are characterized by a strong S₀ → Si (π- TT^*) transition at 501 nm and a weaker broad band around 350 nm ascribed to the S₀ → S₂ (TT-TT^*) transition (FIG. 45). Introduction of 2,6-diiodo substituents to the BODIPY core leads to large red shifts (33 and 38 nm) of both the UV absorption and fluorescence maxima, respectively, significantly depressing the fluorescence quantum yield because of efficient intersystem crossing induced by the heavy atom effect of iodine (FIG. 45, Table 10). 2,6-Diethynylation of 2,6-diiodotetramethyl BODIPY (4a) results in a little red shift due to the enhanced conjugation. However, polymer A emits in the deep red region at 678 nm and exhibits pronounced bathochromic shifts (158 and 168 nm) of both the absorption and the fluorescence maxima relative to the initial BODIPY dye (3a) because of its significant extension of π-conjugation (FIG. 46 and Table 10). Polymer B displays an absorption maximum at 665 nm and fluorescence maximum at 683 nm, a slight red- shift relative to polymer A. The absorption peaks of conjugated polymers become broader than BODIPY monomers as a result of the extended π-conjugation (FIG. 46). BODIPY dyes (3a, 3b, 5a, 5b, 6a, and 6b) show fluorescence lifetimes of several nanoseconds (Table 10). However, the diiodo-functionalized BODIPY dyes (4a and 4b) display much shorter fluorescence lifetimes (ranging from 0.08 to 0.13 ns), consistent with their decreased quantum yields because of efficient intersystem crossing induced by the heavy atom effect of iodine (Table 10). Table 10. Absorption and Emission Maxima and Quantum Yields of BODIPY Dyes and Polymers in Methylene Chloride Solution

BODtPY d*e% Ot polvmers

*b 5b 6h polvmer R abTOrμuon ma* urn (urn) 5Ol S34 5ϊ4 66^s cmis-sinn nmifna (nm) 51 1 570 m quantum y ield l%t 81 ^■i S 79 67 03 fluoiesoence lifeline mO -I I 0OR 5 2 59 17

[00217] Arylation at the meso position has no significant effect on the absorption and emission maxima of BODIPY dyes since the arylated moiety is not coplanar with the BODIPY core because of steric hindrance, although the substitution position is structurally different (Table 10) As a result, two different BODIPY monomer pairs (4a-4b and 6a-6b) each have only 1 nm difference between their respective absorption or emission spectral maxima However, the absorption and emission maxima of polymer B are somewhat more redshifted relative to those of polymer A, which might arise from amplification effect of conjugated polymers. The quantum yields of the meso-phenyl BODIPY dyes (3b, 5b, and 6b) are a little higher than those of the corresponding less substituted analogues (3a, 5a, and 6a) (Table 10) The difference might result from reduced free rotation of the phenyl group in the more substituted compounds and a subsequent decrease in loss of energy from the excited states through nonirradiative molecular motions Polymers A and B displays similar fluorescence lifetimes to their starting BODIPY dyes (3a and 3b) (Table 10).

[00218] Incorporation of different band gap monomers such as fluorene, benzene, and thiophene units into the backbone of poly(2,6-BODIPY-ethynylene) results in the copolymers with different red emissions Fluorescence maxima of the copolymers with fluorene, benzene, and thiophene units are 641, 657, and 664 nm, respectively (Table 11), which is consistent with their band gap energy differences (fluorine > benzene > thiophene) Introduction of the thiophene unit to poly(2,6-BODIPY-ethynylene) significantly reduces the fluorescence quantum yield of the copolymer and shortens fluorescence lifetime of the copolymer due to efficient intersystem crossing induced by the heavy atom effect of sulfur. Table 11. Absorption and Emission Maxima and Quantum Yields of BODIPY-Based Copolymers in Methylene Chloride Solution

BODIPY-bαscd copolymers polymer C polymer D polymer K alwoipnαn ιua.ϋma fnm) 606 r.35 62S cmissiυii maxima (DIlO 641 657 664 quaimim weld (%) 25 6 fluorescence tifci tnτc fπO 2.8 36 023

" Quantum viclcis of BODIPV J>es and pokmerii. tkes were delermmeiϊ t>v u^e of fluorescein ('quantum yield of 0 R5 ia 0.1 N HaOH) as s standard "-'*

Example 15: Preparation of Bulk Heteroiunction ("BHJ"! Solar Cells

[00219] Materials. Patterned Indium tin oxide ("ITO") coated glass substrates were purchased from Thin Film Devices Inc. Poly(3,4-ethylenedioxythiophene) poly(styrenesulfonate) (PEDOT:PSS) (Baytron-PH) was purchased from H. C. Starck.

[00220] Devices Fabrication and Measurement. ITO glass substrates were cleaned using the following sequential steps: sonication in soap solution; rinsing with deionized water; sonication in warm (50 ⁰C) acetone, and isopropanol for 10 min each; and drying with nitrogen. Finally, the substrates were treated with UV ozone for 20 min. A filtered dispersion of PEDOTPSS in water (Baytron-PH) was spuncast at 4000 rpm for 40 s to produce a 40 nm thick layer, followed by baking at 140 ⁰C for 10 min in ambient. Solution processing of the films was performed in an inert-atmosphere (Argon) glove box. The Al cathode was evaporated through a shadow mask to produce an active area of 0.03 cm². After evaporation, a part of the organic layer was removed to allow contact with the ITO, and then conductive Silver paste was painted on the area in order to produce the electrical contact. All device properties were measured at room temperature in an argon atmosphere under AM 1.5 G solar illumination at 100 mWcm^'2 (1 sun) using a Thermal- Oriel 300W solar simulator with filter. External quantum efficiency ("EQE") values were obtained with a monochromator and calibrated with a silicon photodiode. The current density-voltage (J-V) characteristics were recorded in a Keithly 236 SMU. Absorption spectra were recorded in a Cary 50 UV-vis spectrometer. Film thickness measurements were performed using a Dektak 150 surface profiler. Tapping mode atomic force microscopy (AFM) measurements on the blend films were carried out on a Veeco Multimode V atomic force microscope. Cyclic voltammetry ("CV") measurements were carried out using a Solartron 1285 potentiostat under the control of CorrWare Il software. Polymer films were dipcoated on a R working electrode of 2 mm diameter from chloroform solutions. CV curves were obtained in CH₃CN solution containing 0.1 M Bu₄NPF₆ under a nitrogen atmosphere during all measurements. The counter electrode was a Pt wire and the reference electrode was a Ag wire. The potentials were calibrated with respect to the ferroceneVferrocene potential.

[00221] FIG. 47 shows the UV-Vis absorption spectra of the thin films prepared via spin coating polymers from chloroform solutions. Referring to FIG. 47, for the direct comparison of light absorption properties, the UV-Vis spectrum of poly(3-hexylthiophene) ("P3HT") film prepared from chlorobenzene soluton was also plotted. The absorption maximum peaks of the thin films of pBodipy and pBodipy-T were 721 nm and 692 nm respectively, which are red-shifted by ~60 nm from their absorption in dichloromethane solutions, probably due to the molecular stacking in solid state. The optical band gaps were estimated at -1.6 eV for both polymers (see Table 12). Noticeably, the light absorption of the BODIPY polymers was much broader and stronger than that of P3HT in the range of 300-800 nm, leading to much better overlap with the solar spectrum. Both of the low bandgap and strong absorption (extinction coefficient >10⁵/cm ) suggest that the BODIPY polymers could be attractive donor materials for PV application.

Table 12. Optical/Electrochemical Properties of pBodipy and pBodipy-T

p ec p opt

Polymer E_ox ^a/HOMO^b E_red ^a/LUMO^b g_V) g_y) pBodipy 0.47/5.58 -1.38/3.73 1.85 1.61 pBodipy- _{0 34/5 45} .L_{4073-71 1 J4 r65} a Potentials determined by cyclic voltammetry in 0.10 M Bu₄NPF₆- CH₃CN vs. ferrocene⁺/ferrocene. b Assuming the electrochemical potential of ferrocene⁺/ferroceπe = 5.10 eV vs. vacuum.

[00222] Cyclic voltammetry ("CV") measurements were carried out to determine the HOMO and LUMO levels of these polymers. The CV curves are provided in FIG. 50. From the oxidation potential and the reduction potential of the polymers, the HOMO and LUMO levels as well as the electrochemical band gap (E₉ ⁶⁰) were summarized in Table 1. Insertion of thiophene units into the backbone of the pBodipy polymer makes the HOMO level slightly changed from 5.58 eV to 5.45 eV with the LUMO levels nearly constant. This implies that the LUMOs (~3.7 eV) are primarily controlled by BODIPY moieties, while the HOMOs could be strongly affected by the donor units in the polymer backbone. Provided with the LUMO of PCBM at -4.1 eV, charge separation should be highly efficient at the polymer/PCBM interfaces for the energy level offset.

[00223] A series of BHJ polymer solar cells were fabricated with PCBM as electron acceptor in the device structure of ITO/PEDOT:PSS/active layer (polymer: PCBM)/AI. Table 13 summarizes the device characteristics of the polymer solar cells with different weight ratios of PCBM under 100 mVWcm² AM 1.5 G solar illumination.

Table 13. Device Characteristics of BODIPY-based backbone Polymer Solar Cells with Different Weight Ratios of PCBM

Active Layer _v - - J_{sc FF} PCE (wt/wt) ^{∞ κ ;} (πWcm²) ^rr (%) pBodipy. PCBM _{Q J3} ^_{21 Q 3Q Q Q}

PBodipy^PCBM 0.81 -3.39 0.45 1.2 pBodipy. PCBM _QJβ __{A QQ} ^₄₃ ^ pBodipy-T. PCBM _{Q π} ^ _{Q m 1 β}

^PBOdiP0^T3)^{PCBM 0 80} ^⁸² °-^{51 2 0} pBodipy-T. PCBM _Q ^ __{A 2Q Q 5A} ^

[00224] The optimal active polymer/PCBM layer thickness was found to be around 70 nm. The best solar cells were obtained under the ratio of polymer and PCBM at 1 :4 and 1 :3 for the pBodipy and pBodipy-T, respectively. FIG. 48(a) shows the current density-voltage (J-V) characteristics of the best solar cells. An open circuit voltage (V_oc) of -0.8 V was achieved for both polymer/PCBM composites, which is higher than that of typical P3HT/PCBM system by about 0.2 V. This result is consistent with the fact that the HOMO levels of these polymers are much deeper than that of P3HT by 0.2-0.4 eV. The pBodipy-T device showed higher current density (J_sc) and fill factor (FF) over the pBodipy, resulting in efficiencies of 2.0% vs. 1.3%. However, the current density is still much lowerthan that of the state-of-the-art polymer/fullerene derivative systems.

[00225] In order to understand the difference in the solar cell performance between the pBodipy/PCBM and pBodipy- T/PCBM devices, and to reveal the origins of the relatively low current density as compared to the state-of-the-art, we carried out external quantum efficiency (EQE) measurements. FIG. 48(b) shows the EQEs of the solar cells, which display light harvesting up to 770 nm covering all the visible range of solar spectrum. The short wavelength (350-500 nm) is mainly contributed by PCBM while the longer wavelength region by the polymers. The higher lying EQEs of the pBodipy- T/PCBM contributed by PCBM while the longer wavelength region by the polymers. The higher lying EQEs of the pBodipy-T/PCBM device explain the higher J_sc- Meanwhile, the EQE values are 20% or less in the whole light absorption range, which is significantly lower than typical 60-70% for those devices with efficiencies of 4-6%. Though not wishing to be bound by any particular theory, this relatively low value of EQEs for BHJ solar cells is likely due to (i) the non-ideal nanoscale phase separation between the polymers and PCBM, and (ii) the low hole mobilities of the active films.

[00226] Tapping mode atomic force microscopy ("AFM") measurements on the blend films were carried out to investigate film morphology. AFM images of the active layerfilms are shown in FIG. 49 which displays a somewhat rough and coarse phase separation on the polymer/PCBM blends. The surface root-mean-square roughness is 2.55 nm for the pBodipy/PCBM (1 :4) film and 4.33 nm for pBodipy-T/PCBM (1 :3) film. The phase separation formed between the polymer and PCBM exhibit domain size of hundreds of nanometers, which is much larger than exciton diffusion length (<10 nm) and that of ideal thermally annealed P3HT/PCBM system. In other words, the photo-generated excitons would often recombine before reaching the interfaces, leading to relatively low charge carrier generation at the interfaces and a concomitant loss of photocurrent. Therefore, further improvement of the device performance is highly feasible if the BHJ domain size can be controlled to smaller scale in less than 20 nm.

[00227] The hole mobilities of the polymer/PCBM blends were also measured under dark in the structure of ITO/PEDOT:PSS/ active layer (polymer:PCBM)/Au. The active film thickness was around 200 nm to ensure the hole mobility measurement on bulk films. Mobility values were calculated from current-voltage characteristics based on the space charge limited current model. By assuming a dielectric constant of 3.0 for polymer blends, a hole mobility of 1.7 * 10⁷ cm² V¹ s^'1 for the pBodipy:PCBM (1 :4) blend film and 4.4 * 10^"6 cm² V¹ s^"1 for the pBodipy-T:PCBM (1 :3) was obtained. It is therefore believed that the higher hole mobility leads to the higher J₅₁; and FF values in the pBodipy-T blend device. Furthermore, increasing the hole carrier mobility of the BODIPY polymers by optimizing device morphology or chemical modification would likely be an effective way to achieve higher efficiencies.

[00228] Various features and advantages of the invention are set forth in the following claims.

Claims

CLAIMSWhat is claimed is:

1. A solar cell comprising: an anode; a hole injection layer; an active layer; and a cathode; wherein the active layer comprises a BODIPY-based backbone polymer.

2. A solar cell according to claim 1 , wherein the anode comprises ITO.

^'3. A solar cell according to any one of the preceding claims, wherein the hole injection layer comprises PEDOT: PSS.

4. A solar cell according to any one of the preceding claims, wherein the cathode comprises aluminum.

5. A solar cell according to any one of the preceding claims, wherein the active layer comprises PCBM.

6. A solar cell according to any one of the preceding claims, wherein active layer comprises a weight ratio of polymer to PCBM of about 1 :1 to about 1.6.

7. A solar cell according to any one of the preceding claims, wherein the active layer .has a thickness of about 60 nm to about 100 nm.

8. A solar cell according to any one of claims 1 to 7, wherein the BODIPY-based backbone polymer comprises a polymer according to formula (I):

(I) wherein each -A- is independently selected from -AR- -AR ===== = -AR- ^", or

-AR- wherein each -AR- is independently selected from arylene or heteroarylene; wherein each R₃ is independently selected from R, alkyl, aryl or heteroaryl wherein each R₂ and R₄ are independently selected from alkyl or H; wherein each R₁ and R₅ are independently selected from hydrogen, alkyl,

wherein each R₀ is -F, -OR, -R, aryl, heteroaryl, — ≡≡=- -Aryl , or ΞΞΞΞΞ Heteroaryl . wherein each R is independently selected from -H, -(CH₂)_mRio, -(CH₂)_mCOO(CH₂)_pCH₃, -(CH₂)_mSO₃Na, -(CH₂)_mPO₃Na, -(CH₂)_mN(CH₃)₃ ⁺Br, -(CH₂)_mCOH(CH₂)_pCH₃, - (CH₂)_mOR₁₀, -(CH₂)_mOR₈, -CH₂CH₂(OCH₂CH₂)_mOR₁₀, -CH₂CH₂(OCH₂CH₂)_mOR₈, -

CH₂CH₂(OCH₂CH₂)_mSR_β, or

\ /\ Λ / ; and wherein each R₈ is independently selected from a carbohydrate residue; and wherein each Ri₀ is independently selected from hydrogen, alkyl, heteroalkyl, hydroxy, amino, amnionic acid, thiol, carboxylic acid, nitrile, azide, ethynylene, halo, and tosylate; wherein m is from 0 to 100; wherein n is from 2 to 300 and wherein p is from 0 to 20.

9. A solar cell according to any one of claims 1 to 7, wherein the BODIPY-based backbone polymer comprises a polymer according to formula (II):

(H) wherein each -A- is independently selected from AR-

-AR- -AR- or

-AR- wherein each -AR- is independently selected from arylene or heteroarylene; wherein each R₃ is independently selected from R, alkyl, aryl or heteroaryl wherein each R₂ and R₄ are independently selected from alkyl or H; wherein each R₆ is independently selected from H or alkyl; wherein each R₀ is -F, -OR, -R, aryl, heteroaryl, — ≡= — R , ^{== Ar}V' , or ΞΞ≡Ξ Heteroaryl . wherein each R is independently selected from -H, -(CH₂)_mR₁₀, -(CH₂)_mCOO(CH₂)_pCH₃, -(CH₂)_mSO₃Na, -(CH₂)_mPO₃Na, -(CH₂)_mN(CH₃)₃ ⁺Br-, -(CH₂)_mCOH(CH₂)_PCH₃, - (CH₂)_mORio, -(CH₂)_mOR₈, -CH₂CH₂(OCH₂CH₂)_mOR_10l -CH₂CH₂(OCH₂CH_z)_mOR₈, -

CH₂CH₂(OCH₂CH₂)_mSR₈, or

^■ and wherein each R₈ is independently selected from a carbohydrate residue; and wherein each R₁₀ is independently selected from hydrogen, alkyl, heteroalkyl, hydroxy, amino, ammonic acid, thiol, carboxylic acid, nitrile, azide, ethynylene, halo, and tosylate; wherein m is from 0 to 100;

^•wherein n is from 2 to 300 and wherein p is from 0 to 20.

10. A solar cell according to any one of claims 1 to 7, wherein the BODIPY-based backbone polymer comprises a polymer according to formula (III):

(III) wherein each -A- is independently selected from -AR- = AR - AR- ^", or

wherein each -AR- is independently selected from arylene or heteroarylene; wherein each R₃ is independently selected from R, alkyl, aryl or heteroaryl ■wherein each R₂ and R₄ are independently selected from alkyl or H; wherein each R₆ is independently selected from H or alkyl; wherein each R₀ is -F, -OR, -R, aryl, heteroaryl, — ≡≡≡ — R , = Aryl _or ΞEΞEΞ Heteroaryl . wherein each R is independently selected from -H, -(CH₂^R_1O, -(CH₂)_mCOO(CH₂)_pCH₃, -(CH₂)_mSO₃Na, -(CH₂)_mPO₃Na, -(CH₂)_mN(CH₃)₃ ⁺Br, -(CH₂)_mCOH(CH₂)_pCH₃, - ^'(CH₂)JDR₁O. -(CH₂)_mOR₈. -CH₂CH₂(OCH₂CH₂)_mOR_10l -CH₂CH₂(OCH₂CH₂)_mOR₈, -

CH₂CH₂(OCH₂CH₂)_mSR₈, or

\ — Λ — Λ — / ; and wherein each R₈ is independently selected from a carbohydrate residue; and wherein each Ri₀ is independently selected from hydrogen, alkyl, heteroalkyl, hydroxy, amino, ammonic acid, thiol, carboxylic acid, nitrile, azide, ethynylene, halo, and tosylate; wherein m is from O to 100; wherein n is from 2 to 300 and wherein p is from 0 to 20.

11. A solar cell according to any one of claims 1 to 7, wherein the BODIPY-based backbone polymer comprises a polymer according to formula (IV):

(IV)

ΞEEEΞE≡ AR wherein each -AR- is independently selected from arylene or heteroarylene; wherein each R₃ is independently selected from R, alkyl, aryl or heteroaryl wherein each R₂ and R₄ are independently selected from alkyl or H; wherein each R₆ is independently selected from H or alkyl; wherein each R₀ is -F, -OR, -R, aryl, heteroaryl, — ≡≡ — R , -⁼⁼⁼ ^ryl _or EEΞΞΞEΞ Heteroaryl . wherein each R is independently selected from -H, -(CH₂)_mR₁₀, -(CH₂)_mCOO(CH₂)pCH₃, -(CH₂VSO₃Na, -(CH₂)J³O₃Na, -(CH₂)_mN(CH₃)₃ ⁺Bf, -(CH₂)_mCOH(CH₂)_pCH₃, - (CH₂)_mORio. -(CH₂)_mOR_8, -CHzCH^OCHzCH^OR™, -CH₂CH₂(OCH₂CH₂)_mOR_βl -

wherein each R₈ is independently selected from a carbohydrate residue; and wherein each Ri₀ is independently selected from hydrogen, alkyl, heteroalkyl, hydroxy, amino, ammonic acid, thiol, carboxylic acid, nitrile, azide, ethynylene, halo, and tosylate; wherein m is from 0 to 100; wherein n is from 2 to 300 and wherein p is from 0 to 20.

12. A solar cell according to any of claims 8 to 11, wherein each AR is independently selected from

87

wherein each R_A, R_B, R_c and R₀ is independently selected from R, OR, hydrogen, alkyl, heteroalkyl, hydroxy, amino, thiol, carboxylic acid, nitrile, azide, halo or R_A and R_B may together form an aromatic ring, or R_c and R_D may together form an aromatic ring or both

RA and R₈ and Rc and R₀ may together form an aromatic ring; wherein each R_E, R_F and R_G is independently selected from R, OR, hydrogen, alkyl, heteroalkyl, aryl, heteroaryl, hydroxy, amino, thiol, carboxylic acid, nitrile, azide, halo, or

R_E and R_F may together form a ring; wherein each R_H, Ri, Rj, RK, RL, RM, R_N. and R₀ is independently selected from R, OR, hydrogen, alkyl, heteroalkyl, hydroxy, amino, thiol, carboxylic acid, nitrile, azide, halo, or

Ri and Rj may together form a ring, or R_M and R_N may together form a ring; wherein each R_P and R₀ is independently selected from hydrogen or together form an aromatic ring; wherein each R_s is independently selected from hydrogen or OR; wherein each X is independently a carbon atom or a heteroatom; wherein q is an integer from 1 to 3; wherein M is selected from Zn, Cu, Fe, and R; wherein M2 is selected from Ru or Ir;

wherein bpy is

wherein each R is independently selected from -H, -(CH₂)_mR₁₀, -(CH₂)mCOO(CH₂)pCH3, ^'-(CH₂)_mSO₃Na, -{CH₂)_mPO₃Na, -(CH₂)_mN(CH₃)₃ ⁺Br, -(CH₂)_mCOH(CH₂)_pCH₃, - (CH₂)_mOR_10, -(CH₂)_mOR₈. -CH₂CH₂(OCH₂CH₂)_mORio, -CH₂CH₂(OCH₂CH₂)_mOR₈, -

CH₂CH₂(OCH₂CH₂)_mSR₈, or

and wherein each R₈ is independently selected from a carbohydrate residue; and and wherein each Ri₀ is independently selected from hydrogen, alkyl, heteroalkyl, hydroxy, amino, ammonic acid, thiol, carboxylic acid, nitrile, azide, ethynylene, halo, and tosylate.

13. A solar cell according to any one of claims 8 to 11 , wherein each AR is independently selected from

wherein each R_A, R_B, R_c and RD is independently selected from R, OR, hydrogen, alkyl, heteroalkyl, hydroxy, amino^', thiol, carboxylic acid, nitrile, azide, halo or R_A and R_B may together form an aromatic ring, or R_c and R₀ may together form an aromatic ring or both R_A and R_B and Rc and R₀ may together form an aromatic ring; wherein each R_El R_F and R_G is independently selected from R, OR, hydrogen, alkyl, heteroalkyl, aryl, heteroaryl, hydroxy, amino, thiol, carboxylic acid, nitrile, azide, halo, or R_E and R_F may together form a ring; wherein each R_H, Ri, Rj, RK, RL. RM, R_N, and Ro is independently selected from R, OR, hydrogen, alkyl, heteroalkyl, hydroxy, amino, thiol, carboxylic acid, nitrile, azide, halo, or

Ri and R_J may together form a ring, or R_M and R_N may together form a ring; wherein each R_P and R_Q is independently selected from hydrogen or together form an aromatic ring; wherein each R₅ is independently selected from hydrogen or OR; wherein each X is independently a carbon atom or a heteroatom; wherein q is an integer from 1 to 3; wherein M is selected from Zn, Cu, Fe, or Pt; wherein M2 is selected from Ru or Ir; and

wherein bpy is

wherein each R is independently selected from -H, -(CH₂)_mRio, -(CH₂)mCOO(CH₂)pCH3, -(CH₂)mSO₃Na, -(CH₂)_mPO₃Na, -(CH₂)_mN(CH₃)₃ ⁺Br, -(CH₂)_mCOH(CH₂)_pCH₃, - (CH₂)_mOR,o. -{CH₂)_mOR₈, -CH₂CH₂(OCH₂CH₂)_mOR₁₀, -CH₂CH₂(OCH₂CH₂)_mOR₈, -

CH₂CH₂(OCH₂CH₂)_mSR_β, or

\ — IVJVJ _; and wherein each R₈ is independently selected from a carbohydrate residue; and wherein each Ri₀ is independently selected from hydrogen, alkyl, heteroalkyl,hydroxy, amino, ammonic acid, thiol, carboxylic acid, nitrile, azide, ethynylene, halo, and tosylate.

14. A solar cell according to any one of claims 8-13, wherein each R₃ is independently

selected from

wherein each R_F is independently selected from R, OR, hydrogen, alkyl, heteroalkyl, aryl, heteroaryl, hydroxy, amino, thiol, carboxylic acid, nitrile, azide or halo; and wherein each R is independently selected from -H, -(CH₂)_mRi₀, -(CH2)mCOO(CH2)pCH_3l

-(CH₂)_mSO₃Na, -(CH₂)_mPO₃Na, -(CH₂)_mN(CH₃)₃ ⁺Br\ -(CH₂)_mCOH(CH₂)_pCH₃, -

(CH₂)_mORi₀, -(CH₂)^OR₈, -CH₂CH₂(OCH₂CH₂)_mOR₁₀, -CH₂CH₂(OCH₂CH₂)_mOR₈, -

CH₂CH₂(OCH₂CH₂)_mSR₈, or

\ — Λ — A — / ; and wherein each R₈ is independently selected from a carbohydrate residue; and wherein each R₁₀ is independently selected from hydrogen, alkyl, heteroalkyl, hydroxy, amino, ammonic acid, thiol, carboxylic acid, nitrile, azide, ethynylene, halo, and tosylate.

15. A solar cell according to any one of claims 8-14, wherein each R₁ and R₅ is independently -CH₃ or -CH₂CH₃.

16. A solar cell according to any one of claims 8-15, wherein each R₀ is independently

wherein each R is independently selected from -H₁ -(CH₂)_mR₁₀, -(CH₂)_mCOO(CH₂)_pCH₃, -(CH₂)_mSO₃Na, -(CH₂)_mPO₃Na, -(CH₂)_mN(CH₃)₃*Br, -(CH₂)_mCOH(CH₂)_pCH₃, - (CH₂)_mOR₁₀. -(CH₂J_1nOR₈. -CH₂CH₂(OCH₂CH₂UOR₁O, -CH₂CH₂(OCH₂CH₂)_mOR₈, -

CH₂CH₂(OCH₂CH₂)_mSR₈, or

\ A A / ; and wherein each R₈ is independently selected from a carbohydrate residue; and wherein each Rio is independently selected from hydrogen, alkyl, heteroalkyl, hydroxy, amino, ammonic acid, thiol, carboxylic acid, nitrile, azide, ethynylene, halo, and tosylate.

17. A solar cell according to any one of claims 1 to 7, wherein the BODIPY-based backbone polymer comprises a polymer according to formula (V):

18. A solar cell of any one of claims 1 to 7, wherein the BODIPY-based backbone polymer comprises a polymer according to formula (Vl):

19. A solar cell according to any one of the preceding claims, wherein the solar cell has a Voc of at least about 0.8 eV.

20. A solar cell according to any one of the preceding claims, wherein the solar cell has a power conversion efficiency of at least about 2%.