US 20150207078A1 (19) United States (12) Patent Application Publication (10) Pub. No.: US 2015/0207078 A1 Sun (43) Pub. Date: Jul. 23, 2015

(54) FLUORINATED AROMATIC MATERIALS Publication Classification AND THEIR USE IN OPTOELECTRONICS (51) Int. Cl. (71) Applicant: The University of South Dakota, HOIL 5L/00 (2006.01) Vermillion, SD (US) CD7C4I/22 (2006.01) CD7C 43/12 (2006.01) (72) Inventor: Haoran Sun, Vermillion, SD (US) C07C 17/20 (2006.01) CD7C22/08 (2006.01) (21) Appl. No.: 14/675,133 (52) sh;to (2006.01) CPC ...... HOIL 51/0052 (2013.01); C07C 22/08 (22) Filed: Mar. 31, 2015 (2013.01); C07D 471/04 (2013.01); C07C 43/126 (2013.01); C07C 17/202 (2013.01); O O C07C4I/22 (2013.01); HOIL 51/0072 Related U.S. Application Data (2013.01); HOIL 51/0558 (2013.01) (62) Division of application No. 13/391,375, filed on May (57) ABSTRACT 2, 2012, now Pat. No. 9,024,094, filed as application Fluorinated aromatic materials, their SVnthesis and their use No. PCT/US2010/046207 on Aug. 20, 2010. in optoelectronics. In some cases,s they fluorinated aromatic (60) Provisional application No. 61/235,970, filed on Aug. materials are perfluoroalkylated aromatic materials that may 21, 2009. include perfluoropolyether substituents.

2 Patent Application Publication Jul. 23, 2015 Sheet 1 of 3 US 2015/0207078A1

GE

FGE Patent Application Publication Jul. 23, 2015 Sheet 2 of 3 US 2015/0207078A1

2,8,9,8-tetrakis-perforgocy-anthracete O : 8 8 : 8 ?, 3. : $. 8 a 3, Q-bis-perforoocty anthracers 60 3 * Š 8. 9,10-dipod-attracese C 2,8,9,8-tetraordic-attracters

ge 4) go inefites

RE3

:00 8 st 8. i,3,8,8-tetrakis-perfuorooctyl- 8

80 : s a 60

8 4 S 20

2 - so inefites

GE Patent Application Publication Jul. 23, 2015 Sheet 3 of 3 US 2015/0207078A1

RES

FGURE 6

GURE US 2015/0207078 A1 Jul. 23, 2015

FLUORINATED AROMATIC MATERALS 0009 FIG. 3 is a graph illustrating the photostability of AND THEIR USE IN OPTOELECTRONICS perfluoroalkylated . 0010 FIG. 4 is a graph illustrating the photostability of CROSS-REFERENCE TO RELATED perfluoroalkylated . APPLICATION 0011 FIG. 5 is a schematic illustration of a heterojunction 0001. This application is a divisional application of U.S. organic blue light emitting diode (OLED). application Ser. No. 13/391,375, filed on May 2, 2012, which 0012 FIG. 6 is a schematic illustration of a homojunction is a National Stage Entry of PCT/US2010/046207, filed on organic blue light emitting diode (OLED). Aug. 20, 2010, which claims the benefit of provisional patent 0013 FIG. 7 is a schematic illustration of a heterojunction application Ser. No. 61/235,970, entitled “FLUORINATED flexible organic solar cell (OSC). AROMATIC MATERIALS AND THEIR USE IN OPTO ELECTRONICS. filed on Aug. 21, 2009. The entire disclo DETAILED DESCRIPTION sures of which are hereby expressly incorporated by refer CCC. 0014 Fluorinated materials such as fluorinated aromatic materials have strongly enhanced luminescence, higher STATEMENT REGARDING FEDERALLY chemical stability and higher photostability when compared SPONSORED RESEARCH ORDEVELOPMENT to corresponding non-fluorinated aromatic materials. Fluori nated aromatic materials are also highly hydrophobic and 0002 The United States government may have certain oleophobic, which may be useful in limiting proton-related rights to this invention. reduction of the aromatic. FIG. 1 illustrates the hydrophobic nature of fluorinated materials. In FIG. 1, a water drop is seen TECHNICAL FIELD on a solid perfluoroalkylated dye covered glass slide. FIG. 2 0003. The disclosure pertains generally to fluorinated aro illustrates the luminescence. In FIGS. 2A and 2B, the photo matic materials, their synthesis and their use in optoelectron luminescence of from left to right, anthracence, 9,10-di ics. bromo anthracene and 9,10-bis(perfluorooctyl)anthracene is seen. FIG.2C provides a graphical representation of lumines BACKGROUND cence intensity for anthracene and 9,10-bis(perfluorooctyl) 0004 Fluorinated aromatics and related materials offer anthracene. many advantages over non-fluorinated materials in a variety 0015 FIGS. 3 and 4 illustrate the photostability of the of different optoelectronic devices such as, but not limited to, fluorinated aromatic materials described herein. In FIGS. 3 organic light emitting diodes, organic field-effect transistors, and 4, the materials were tested with a 300W Xe light with a organic Solar cells, and dye-sensitized solar cells. These flu 1.5 AM filter. The Y axis shows the percentage of the tested orinated materials have processing advantages and are ther compounds remaining after being exposed to light for a par mally and photochemically stable. They have reduced flam ticular amount of time. FIG. 3 compares fluorinated and non mability tolerance to extreme environmental conditions, fluorinated anthracene derivatives while FIG. 4 compares including superhydrophobicity and oleophobicity. Fluori fluorinated and non-fluorinated pyrene derivatives. nated materials also have advantages in tuning the electronic 0016. In some embodiments, the fluorinated aromatic and optical properties of these devices. For example, these materials have fluorinated side chains that include sphydrid materials can be used to produce oxygen stable n-type semi ized carbon atoms. In some embodiments, C F func conductors that can be used in organic Solar cells, dye-sensi tional groups are much more chemically resistant than tized Solar cells, polymer Solar cells, organic light emitting C F functional groups, which in some cases are suscep diodes (OLEDs), organic thin-film field-effect transistors tible to nucleophilic aromatic Substitution when strong (OFETs). nucleophiles are present. Although the C F bond is stable against oxidation, it can undergo reductive defluorination, SUMMARY especially when reducing metals and reagents are present or 0005. The invention is directed to fluorinated aromatic under electrochemical reducing conditions. materials, their synthesis and their use in optoelectronics. In 0017. In some embodiments, the fluorinated aromatic Some embodiments, the fluorinated aromatic materials are materials are perfluoroalkylated aromatic materials that may perfluoroalkylated aromatic materials that may include per include perfluoropolyether substituents. These materials may fluoropolyether substituents. include at least one perfluoroalkyl group or semi-perfluoro alkyl group on the aromatic core structure. Illustrative but 0006 While multiple embodiments are disclosed, still non-limiting examples of aromatic core structures include other embodiments of the present invention will become pyrroles, thiophenes, , , anthracenes, apparent to those skilled in the art from the following detailed , , , , phenan description, which shows and describes illustrative embodi threne, benzoa anthracene, benzoafluorine, benzoc ments of the invention. Accordingly, the drawings and , , , pyrenes, tetracenes, detailed description are to be regarded as illustrative in nature , , , benzoapyrene, and not restrictive. benzoepyrene, benzob fluoranthene, benzo fluoran thene, benzokfluoranthene, benzoghilperylene, corannu BRIEF DESCRIPTION OF THE DRAWINGS lene, , , , , 0007 FIG. 1 is an electronic image illustrating hydropho , hexacene, , , , bicity. , , tetraphenylenepentacenes, fullerenes, bi 0008 FIG. 2 is an electronic image illustrating lumines pyridines, ter-pyridines, quinolines, phenanthrolines, por CCCC. phyrins, benzoporphyrins, and phthalocyanines. US 2015/0207078 A1 Jul. 23, 2015

0.018. In some embodiments, fluorinated aromatic materi -continued als may be of the formula: N

N where Ar is an aromatic core including 3 to about 120 sp hybridized carbon atoms or a total of 3 to about 120 sp M hybridized carbon atoms, nitrogenatoms, oxygen atoms and sulfur atoms; R is a perfluoroalkyl group of the formula CF3(CF)n O C.F., n is an integer ranging from 1 to about 30; Q is a perfluoropolyether group of the formula CFO, k is an 3 integer ranging from 1 to about 1000, his an integer less than or equal to k-1; G is an organic functional group selected from the group consisting of hydrogen, Clso alkyl, Cs-so aryl, in which n may be between about 1 and about 30. halogen, nitro, cyano, ester, ether, hydroxyl, aryl group bear 0021. In some embodiments, a fluorinated aromatic mate ing Subsituents including one or more of carbon, fluorine, rial may be one or more molecules selected from the group chlorine, bromine, nitro or methoxy, or an aryl group includ consisting of: ing a heteroatom such as N, O and S, X, y and Z are integers Such that x+y+Zis less than or equal to the total number of sp hybridized carbon atoms, nitrogenatoms, oxygen atoms and (a) Sulfur atoms within the aromatic core, and y and Z may CF24+1 - CF24+1 independently be zero. 0019. In some embodiments, the aromatic core may be selected from the group consisting of , , anthracene, pyrene, coronene, phenanthroline, bi-pyridine and ter-pyridine. In some embodiments, R may be CF, and CF21+1 8 CnF2n+1, X is in the range of 2 to 6. In some embodiments, G may be (b) hydrogen, Clso alkyl, C-so aryl, halogen, nitro, cyano, ester, CF24+1 CF24+1 ether or hydroxyl. 0020. In some embodiments, the perfluoroalkylated het erocyclic aromatics may form metal complexes with metals such as Li, Na, K, Mg, Ca, Al, P. S. Se. As, Ge. Ga, In, Sn, Sb, T1, Pb, Bi, Sr., Ba, Sc,Y,Ti,V, Cr, Mn, Zr, Nb, Mo, Ru, Rh, Pd, Ag, Cd, Fe, Co, Ni, Cu, Au, Hf, Ta, W. Re, Os, Ir, Pt, Au, Hg, CF24+1 CF24+1 and lanthanides with formal oxidation states from +1 to +6. In Some embodiments, the heterocyclic aromatic cores may be selected from the group consisting of phenanthroline, bi pyridine, ter-pyridine, and quinoline. In some embodiments, a metal complex may be one or more molecules selected from CF24+1 CF24+1 the group consisting of

CF24+1 CnF2n+1, CF3(CF2)n n1n-O COO TBA N N (d) CF24+1 CnF2n+1,

CFCF)1\1\o COO TBA CF24+1

CF24+1 CF3(CF). N (e) CF24+1 21 M3+ 21 NN 3PF N CF3(CF). US 2015/0207078 A1 Jul. 23, 2015

-continued (f) (c) CF2(OCFCF). OCF

CC F17Cs CSF17. 0025. In some embodiments, a fluorinated aromatic mate (g) rial may be 2,6,9,10-tetrakis-heptadecafluorooctyl-an CF24+1 thracene, which has the structure:

(b) CSF17 CF24+1 1Nene1N1S CSF17. OH

(h) CSF17 CFO(CFCFO)CF CF2(OCFCF)nOCF 0026. In some embodiments, a fluorinated aromatic com COO and pound may be 5,6-bisperfluorooctyl-1,10-phenanthroline, CF (OCFCF)nOCF, COO which has the structure:

() OCOCF24+1 (d) 0027. In some embodiments, perfluoroalkylated and semi 0022. In some embodiments, n is between about 1 and perfluoroalkylated aromatics and heterocyclic aromatics and about 30. In other embodiments, n is between about 2 and related polymers may be synthesized via transition metal about 30. mediated/catalyzed cross-coupling reactions from corre 0023. In some embodiments, a fluorinated aromatic mate sponding halogenated aromatic precursors (Ar—X, where X rial may be 9,10-bis-perfluorooctyl anthracene, which has the is F, Cl, Br or I) and perfluoroalkylhalide (Rf)x, where X is Cl, Structure: Br or I). In some embodiments, the perfluoroalkylation reac tion may be copper mediated and may be carried out under a nitrogen atmosphere. In some embodiments, the perfluoro alkyl group may be abbreviated as CF in which n is an integer between 1 and 18 and the semi-perfluoroalkyl group may be abbreviated as CHCF2. in which m is an integer between 1 and 3 and n is an integer between 1 and 17. 0028. In some embodiments, polar aprotic solvents, such as DMSO or DMF, with cupper mediator, work well for many aromatic halides (bromide and iodide). However, since DMSO and DMF are fluorophobic instead of fluorophilic, the reaction intermediates of perfluoroalkylated compounds are almost insoluble in these fluorophobic solvents. The insolu 0024. In some embodiments, a fluorinated aromatic mate bility of the reaction intermediates lead to an incomplete rial may be 1,3,6,8-tetrakis perfluorooctyl pyrene, which has reaction and multiple side products, including isomers that the structure: are very difficult to separate. US 2015/0207078 A1 Jul. 23, 2015 4

0029. In some embodiments, polar fluorophilic solvents fluoroalkylated aromatic materials may be synthesized (e.g. benzotrifluoride) may be used as co-solvents to dissolve through a stepwise bromination, perfluoroalkylation, further the reaction intermediates. As a result, the perfluoroalkylation bromination and so on. reaction goes to completion and gives almost exclusively the target product for most of the reactions under optimized con- 0032 The fluorinated arOmat1C materials described herein ditions. Examples of suitable polar fluorophilic solvents may be used in a variety of optoelectronic devices. Illustrative include benzotrifluoride and the fluorinated ethers available but non-limiting examples of Suitable uses include organic commercially from 3M under the tradenames HFE-7100R), Solar cells, dye-sensitized Solar cells, polymer Solar cells, HFE-72OOOR) and HFE-75OOCR). organic light emitting diodes (OLEDs), organic thin-film 0030. In some embodiments, perfluoroalkylated aromatic field-effect transistors (OFETs), laser diodes, two-photon materials may be made in accordance with the following absorption materials, multifunctional biomedical imaging reaction scheme: reagents including reagents for MRI, ultrasounds, NIR fluo

CSF17 Br CSF17 CSF17 CSF17 DBI, AIBr3 CSF17I, Cu -e- -e- HFE-7500, 130° C. HFE-7500, DMSO, F17Cs F17Cs 130° C. CSF17 F17C1s Br F17Cs CSF17 CSF17

F17Cs F17Cs CSF17 Br Br CSF17

Br C&F17. N DBI, fume H2SO4 N CSF17I, Cu N187 -e- Hos heat HFE-7500, DMSO, 2 2 130° C. 2 Br N Br N F17Cs N

OH OH OH

CSF17I, Cu benzotrifluoride, CSF17 CSF17 CSF17I, Cu DMSO 130° C. HFE-7500, DMSO Br 130° C. N DBI, fume H2SO4 N -es

el HFE-7500, heat 2 N F17Cs N

OH

0.031 In some embodiments, perfluoroalkylated aromatic rescence, photodynamic therapy and others. In some embodi materials may be directly synthesized by perfluoroalkylating ments, these materials may be used to form air stable and abrominated aromatic molecule. In some embodiments, per moisture resistant n-type semiconductors. US 2015/0207078 A1 Jul. 23, 2015

0033 FIG. 5 is a schematic illustration of a heterojunction formed of any of the fluorinated aromatic materials discussed organic blue light emitting diode (OLED) 10 that utilizes both herein. The OSC 36 includes a non-fluorinated p-type semi fluorinated and non-fluorinated materials. The OLED 10 may conductor 42 and a perfluoroalkylated conducting polymer be constructed via chemical vapor deposition, physical vapor anode 44. The OSC 36 includes a conducting substrate 46. deposition and a thickness-controlled spin coating method in Printed silver wire is used as the electrical connectors 48. The which the thickness of each element and layer is controlled. perfluoroalkylated conducting polymer anode 44 may be The OLED 10 includes a conducting carbon fiber cathode 12 formed of the poly 3.4-perfluoroalkylpyrroles and poly 3,4- and a fluorinated n-type semiconductor 14. Commercial car perfluoroalkyl thiophenes described above with respect to bonfiber may be used for the conducting carbon fiber cathode FIG.S. 12. The fluorinated n-type semiconductor 14 may be formed of a perfluoroalkylated pyrene of the structure shown, in EXAMPLES which n may be an integer ranging from about 0 to about 17. The OLED 10 includes a p-type non-fluorinated semiconduc Example 1 tor 16 that may, in some embodiments, beformed of the same material as the n-type semiconductor 14 but without the per Synthesis of 1,3,6,8-Tetrakis-perfluorooctyl-pyrene fluoroalkyl substituent groups. The OLED 10 may include a 0036 Perfluorooctyl iodide (CFI, 1.10 ml, 4.13 mmol) perfluoroalkylated conducting polymer anode 16 and a con was added into a mixture of 1,3,6,8-Tetrabromopyrene (0.146 ducting glass or polymer substrate 18. Printed silver wire is g, 0.25mmol) and copper powder (0.525 g, 8.26mmol) in used as the electrical connectors 22. The perfluoroalkylated C.O.C.-trifluorotoluene and anhydrous DMSO under nitrogen conducting polymer anode 16 may be formed of poly 3,4- protection at 130-135° C. 1,3,6,8-Tetrabromopyrene was pre perfluoroalkyl pyrroles and/or poly 3,4-perfluoroalkyl pared from pyrene through direct bromonation. The reaction thiophenes having the following structures: was monitored by TLC and quenched after 5 hours with acidic ice water. The mixture was suction filtered and the precipitate was washed at least three times with hydrochloric acid and D.I. water, then the Solid crude product (ash gray) was further extracted with HFE-7200R) to yield white crys talline 1,3,6,8-tetrakis-perfluorooctyl-pyrene (0.363 g, 75%) with bright blue fluorescence. Characterization data: 1H-NMR: 8.65 ppm (1H) and 8.82 ppm (2H). Example 2 in which n is in the range of about 1 to about 30 and mi is in the range of about 1 to about 10,000. Synthesis of 0034 FIG. 6 is a schematic illustration of a homojunction 2.6,9,10-tetrakis-heptadecafluorooctyl-anthracene organic blue light emitting diode (OLED) 24 that includes fluorinated aromatic materials such as those discussed above. 0037 Perfluorooctyl iodide (CFI, 3.28 ml, 12.4 mmol) The OLED 24 may be constructed via chemical vapor depo was added into a mixture of 2,6,9,10-tetrabromoanthracene sition, physical vapor deposition and a thickness-controlled (0.494g, 1 mmol) and copperpowder (1.576g, 24.8 mmol) in spin coating method in which the thickness of each element C.O.C.-trifluorotoluene and anhydrous DMSO under nitrogen and layer is controlled. The OLED 24 includes a conducting protection at 130-135° C. 2.6.9,10-tetrabromoanthracene carbon fiber cathode 26 formed of commercial conducting was prepared from anthracene through direct bromonation. carbon fiber and a fluorinated n-type semiconductor 28. The The reaction was monitored by TLC and quenched after 4 fluorinated n-type semiconductor 28 may be formed of a hours with ice water. The mixture was worked up with stan perfluoroalkylated anthracene of the structure shown. The dard extraction methylene chloride and and filtration OLED 24 may include a perfluoroalkylated conducting poly to give 2.6.9,10-tetrakis-heptadecafluorooctyl-anthracene in meranode 30 and a conducting glass or polymer Substrate 32. good yield. mp 94-96° C. Printed silver wire is used as the electrical connectors 34. The 0038 Characterization data: 1H NMR (CDC1): 8 9.00 perfluoroalkylated conducting polymer anode 30 may be ppm (s. 2H), 8.75 ppm (d. 2H), 7.85 ppm (d. 2H); 19F NMR formed of the poly 3,4-perfluoroalkylpyrroles and poly 3,4- (CDC1): 8 -80.57 ppm (t, 23.34 Hz, 12F), -90.91 ppm (m, perfluoroalkyl thiophenes described above with respect to 8F), -111.62 ppm (m, 8F), -116.81 ppm (m, 8F), -121.46 FIG.S. ppm (m, 8F), -121.84 ppm (m, 8F), -122.86 ppm (m, 8F), 0035 FIG. 7 is a schematic illustration of a heterojunction -126.08 ppm (m, 8F); MS (LRFAB posion); m/z (m+) flexible organic solar cell (OSC) 36 that is constructed using 1850.0 (calcd for CHFes: 1850.4): C, H analysis; Calcd fluorinated aromatic materials (e.g. perfluoroalkylated por (%) for CHF is C 29.85, H0.32; found C 29.67, H 0.19 phyrins, perfluoroalkylated benzoporphyrins, and perfluoro Example 3 alkylated phthalocyanines), fluorinated polymers, and non fluorinated materials as p-type semiconductors (e.g. Synthesis of 9,10-bis-perfluorooctyl-anthracene benzoporphyrins, phthalocyanines). The OSC 36 may be constructed via chemical vapor deposition, physical vapor 0039) Perfluorooctyl iodide (CFI, 2.36 ml, 8.93 mmol) deposition and a thickness-controlled spin coating method in was added into a mixture of 9,10-dibromoanthracene (0.6 g. which the thickness of each element and layer is controlled. 1.78 mmol) and copper powder (1.14 g. 17.8 mmol) in trif The OSC 36 includes a perfluoroalkylated (e.g. poly 3,4- luorotoluene and anhydrous DMSO under nitrogen protec perfluoroalkyl thiophene) conducting polymer cathode 38 tion at 130° C. 9.10-dibromoanthrocene is commercially and a fluorinated n-type semiconductor 40 that may be available. The reaction was monitored by TLC and quenched US 2015/0207078 A1 Jul. 23, 2015

after 4 hours with ice water. The mixture was worked up with based non-halogen solvents, and stable under standard extraction with methylene chloride to give 9,10-bis sunlight (tested with 1.5 AM solar simulator). perfluorooctyl-anthracene in good yield. 0040 Characterization data: mp 128-132° C.; 1H NMR Prophetic Example (CDC1): 88.42 ppm (d. 4H), 7.61 ppm (d. 4H); 19F NMR (CDC1): 8-80.56 ppm (t, 21.36 Hz,6F), -90.86 ppm (m, 4F), Synthesis of -116.68 ppm (m, 4F), -121.21 ppm (m, 4F), -121.57 ppm 2,4,6,8,9,10-hexa-heptadecafluorooctyl-anthracene (m, 4F), -122.88 ppm (m, 4F), -125.88 ppm (m, 4F), -125.91 ppm (m, 8F); MS (LRFAB posion); m/z (m+) 1014.0 (calcd 0045 Step one: 2.6.9,10-tetrakis-heptadecafluorooctyl for CoHF: 1014.3): C, H analysis; Calcd (%) for anthracene (1 mmol) is dissolved into 50 ml of HFE-7500R CHFis C 35.52, H 0.78; found C 35.17, H 0.74 and heated up in a 130° C. oil bath Anhydrous AlBr (0.05 mmol) and DBI solid (1.2 mmol) are added into the reaction Example 4 mixture under string. After 24 hours at 130° C. the reaction mixture will be cooled down to room temperature, and Synthesis of 5, washed with water. The HFE-7500R solution is evaporated to 6-bisperfluorooctyl-1,10-phenanthroline yield 4,8-dibromo-2,6,9,10-tetrakis-heptadecafluorooctyl anthracene. 0041 0.5 g (1.47 mmol) of 5,6-dibromo-1,10-phenanthro 0046 Step two: Perfluorooctyl iodide (CF.I., 2.5 mmol) line, 1.13 g (17.78 mmol) of copper powder were added into is added into a mixture of 4,8-dibromo-2,6,9,10-tetrakis-hep a three neck round bottom flask with C.C.C.-trifluorotoluene tadecafluorooctyl-anthracene (0.5 mmol) and copper powder and DMSO. When the temperature inside the reaction mix (5.0 mmol) in HFE-7500 and anhydrous DMSO under nitro ture reached 106°C., 2.4 ml (8.9 mmol) of CF, I was added gen protection at 130°C. The reaction is monitored by TLC drop wise over 45 min and the reaction was run for 3 hrs. The and cooled down to room temperature after 72 hours. The reaction mixture was allowed to cool to room temperature and mixture will be separated directly to give a HFE-7500 solu 200 ml of chloroform was added. The mixture was then tion of 2,4,6,8,9,10-hexa-heptadecafluorooctyl-anthracene. washed with 6x100ml of concentrated ammonium hydroxide Removal of HFE-7500 will give solid compound 2,4,6,8,9, solution, followed by washing with 3x100 ml of D.I. water. 10-hexa-heptadecafluorooctyl-anthracene. The chloroform layer was then collected, dried, and removed 0047 Various modifications and additions can be made to to yield crude product, which was further recrystallized from the exemplary embodiments discussed without departing methylene chloride. from the scope of the present invention. For example, while 0042 Characterization data: "H NMR (CDC1): 8 9.22 the embodiments described above refer to particular features, ppm, 8.69 ppm, 7.92 ppm; F NMR (CDC1): 8-80.62 ppm the scope of this invention also includes embodiments having (t, 6F), -104.61 ppm (m, 4F), -119.79 ppm (m, 4F), -121.09 different combinations of features and embodiments that do ppm (m, 4F), -121.58 ppm (m, 4F), -121.76 ppm (m, 4F), not include all of the above described features. -122.58 ppm (m, 4F), -125.98 ppm (m, 4F); MS (LRFAB); m/Z (m) 1016.8 (calcd for CHFN: 1016.3). 1. A fluorinated , wherein the fluori nated aromatic compound is selected from the group consist Example 5 ing of Synthesis of 2.6,9,10-tetrakis-heptadecafluorooctyl-anthracene in (b) HFE-72OO 0043 Perfluorooctyl iodide (CF.I., 3.28 ml, 12.4 mmol) was added into a mixture of 2,6,9,10-tetrabromoanthracene (0.494g, 1 mmol) and copper powder (1.576g, 24.8 mmol) in HFE-7200R and anhydrous DMSO under nitrogen protec tion at 90°C. The reaction was monitored by TLC and cooled down to room temperature after 24 hours. The mixture was separated directly to give a HFE-7200R solution of 2.6.9.10 tetrakis-heptadecafluorooctyl-anthracene. Removal of the HFE-7200R solvent yielded the solid product 2.6.9,10-tet rakis-heptadecafluorooctyl-anthracene having characteriza tion data matching that of Example 2. Example 6

Thin Film Production of 2.6,9,10-tetrakis-heptadecafluorooctyl-anthracene With HFE-72OO 0044) 5 mg of 2.6.9,10-tetrakis-heptadecafluorooctyl-an thracene was dissolved in 1.0 mL of HFE-7200 and spin coated onto a glass slide a room temperature and atmosphere pressure. The thin film was stable with treatment of water and US 2015/0207078 A1 Jul. 23, 2015

-continued -continued (f) (f) CF2(OCFCF). OCF

CF2(OCFCF)nOCF3 (h) (h) CFO(CFCFO)CF CFO(CFCFO)CF CF2(OCFCF)nOCF3 CF2(OCFCF)nOCF CF (OCFCF)nOCF, C c c CF (OCFCF)nOCF

where n is an integer in a range of about 1 to about 30. 3. The fluorinated aromatic compound of claim 1, wherein where n is an integer in a range of about 1 to about 30. the fluorinated aromatic compound comprises 2. An n-type semiconductor comprising the fluorinated aromatic compound, wherein said fluorinated aromatic com (b) pound is selected from the group consisting of CSF17 CSF17. (b) CF24+1 CF24+1

CSF17

4. The n-type semiconductor of claim 2, forming part of a CF24+1 CF24+1 device selected from the group consisting of an organic light (c) emitting diode, an organic Solar cell or an organic field effect CF24+1 CF24+1 transistor. 5. A method of making the fluorinated aromatic compound of claim 1, comprising: combining a brominated aromatic exemplified as 1.3.6.8- Tetrabromopyrene, and a perfluoroalkylhalide exempli fied as perfluorooctyl iodide in a solvent including a fluorinated solvent exemplified as C.C.C.-trifluorotolu (d) ene and anhydrous DMSO; and CF24+1 reacting the brominated aromatic and the perfluoroalkyl halide in a copper mediated cross-coupling reaction. 6. The method of claim 5, wherein the solvent includes one or more of DMF, DMSO, CHCN, trifluoromethylbenzene or a fluorinated ether. 7. The method of claim 6, further comprising reacting a CF24+1 perfluoropolyether group. k k k k k