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Full text of "DTIC AD1020452: Intramolecular Charge Transfer of Conjugated Liquid Crystal Ferrocene Macromolecules - Synthesis and Characterization"

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AFRL-AFOSR-CL-TR-2016-0012 



Intramolecular Charge Transfer of Conjugated Liquid Crystal Ferrocene Macromolecules 


Ronald Ziolo 
CIQA 


07/07/2016 
Final Report 


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Air Force Research Laboratory 
AF Office Of Scientific Research (AFOSR)/ IOS 
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Air Force Materiel Command 









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4. TITLE AND SUBTITLE 

Intramolecular Charge Transfer of Conjugated Liquid Crystal Ferrocene Macromolecules 


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Ronald Ziolo 


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CIQA 

BLVD ENRIQUE REYNA HERMOSILLO NO.140 
SALTILLO, 25252 MX 


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14. ABSTRACT 

The design, synthesis dnd characterization of a new series of conjugated macromolecules bearing 
ferrocene as a highly efficient electron donor material coupled to 2,5-di(alcoxy) benzene ethynylene(s) as a 
pi-conjugated connector and benzoate or phenyl carboxylic acid as termini and electron attractor groups to 
create a push-pull effect with efficient charge transfer, D-pi-A, are reported. The rigid, rod-like 
phenyleneethynylene chain bears flexible dodecanoxy group chains to impart liquid crystal properties. 


15. SUBJECT TERMS 

chromophores, liquid crystal. 


Liquid Crystal" AND "two-photon absorption", ferrocene AND "phenyleneethynylene, SOARD 


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10/19/2016 































Final Report 


Intramolecular Charge Transfer of Conjugated 
Liquid Crystal Ferrocene Macromolecules 
- Synthesis and Characterization - 


Eduardo Arias, Ivan Moggio, Ronald Ziolo 
Centro de Investigacion en Qmmica Aplicada (CIQA) 
Blvd. Enrique Reyna, No. 140 
Saltillo, Coahuila, Mexico 25294 

rziolo@cs.com 


AFOSR FA9550-14-1 -0253 
April 12, 2016 


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Background. Our group at CIQA has been designing, synthesizing and characterizing 
organic as well as hybrid organic materials that consist of monomers and their related 
oligomers and polymers with nonlinear optical ‘push-pull’ and thermotropic properties 
that have given rise, along with other works, to several publications that underscore the 
successful and sustainable dynamic of the CIQA-AFRL/AFOSR/SOARD collaboration 
[1-7]. To date, acetylide, phenyleneethynylene and arylenvinylidene series of 
macromolecules have been shown to exhibit strong two-photon absorption and 
thermotropic properties with mesophases dependent on the oligomer’s length as seen in 
the polycrystalline nature of dimmers, Smectic A (Sa) or C (Sc) phases of tetramers and 
pentamers, to the fluidic Nematic (N) phase of the heptamers and octamers. These liquid 
crystalline properties are of interest because polarized light emitters or light absorption 
devices, such as OLEDS, solar cells or wave guides, fdters and Faraday isolators can be 
fabricated as nanometric films. The challenge consists of obtaining thermotropic materials 
with strong two photon absorption and very efficient intramolecular charge transfer (ICT). 

As a first step, we have designed, synthesized and characterized a new series of 
conjugated macromolecules illustrated in Figure 1, which bear ferrocene [( if-CsHsjFetrf- 
C5//5)] as a highly efficient electron donor material. The ferrocene group is coupled to 2,5- 
di(alcoxy) benzene ethynylene(s) as a ^-conjugated connector (tc) and benzoate or phenyl 
carboxylic acid as termini and electron attractor groups (A) to create a push-pull effect 
with efficient intramolecular charge transfer (D—>7t—>A). The rigid, rod-like 
phenyleneethynylene bears flexible dodecanoxy chains which can impart liquid crystal 
properties. This series of materials incrementally increases the distance between the 
electron withdrawing and the electron donor groups, making it possible to study the 
relationship between, for example, the change of electric dipole moment in charge transfer 
transitions of these oligomers studied by ultrafast two-photon absorption and 
intermolecular distance. 

Here, we report the synthesis and characterization of the oligomers that are 
presently being studied at AFRL (T. Cooper, et al.), Montana State University (A. Rebane, 
et al.) and CIQA by linear absorption and emission spectroscopy, laser flash photolysis, 
ultrafast laser femtosecond time-resolved absorption spectra and Z-scan experiments for 
two photon cross section measurements. Results of the spectroscopic studies will appear in 
subsequent reports. 


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4FeDAc 


6FeDAc 


Figure 1 . Molecular structure of the symmetrical and unsymmetrical ferrocenyl- 
ethynylene oligomers synthesized and characterized in this work. 


Experimental. 

Materials. The following chemical reagents: ethynylferrocene, cuprous iodide, 
bis(triphenyl phosphine) palladium (II) dichloride, tetrabutylamonium fluoride (TBAF, 
1M in THF), trimethylsilylacetylene (TMSA), were purchased from Aldrich and used 
without further purification. CHCI 3 , CH 2 CI 2 and hexanes were purchased from J.T. 
Backer. Triethylamine (Et 3 N) (Aldrich) was distilled from KOH, THF (Aldrich) was also 
first distilled from KOH and then from sodium benzophenone until the typical blue 
complex was formed. All solvents used for optical characterization were spectroscopic 
grade from Aldrich. 

Equipment. 'H and 13 C NMR data were obtained at room temperature with a Jeol 
Eclipse spectrometer at 300 MHz for X H and 75.4 MHz for 13 C using CDCI3 as 
solvent and internal reference. Differential scanning calorimetry (DSC) analyses 
were carried out on a DuPont 951 instrument under nitrogen at a heating rate of 10 
°C/min. Small and wide angle X ray scattering patterns were obtained with a Anton 
Paar SAXSess me 2 SWAXS instrument using CuKa radiation at a wavelength of 
0.1542 nm. Fluorescence lifetimes were obtained using the Time Correlated Single 
Photon Counting technique (TCSPC) with a TemPro (Horiba Scientific) instrument. 

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A nanoLED laser at 295 nm was used for the excitation; the probe measurement 
was obtained with a 0.01% ultrapure water suspension of LUDOX (Aldrich). 
Calibration of the equipment was realized with a POPOP [l,4-bis(4-methyl-5-fenil- 
2-oxazolyl)benzene] methanol solution (optical density <0.1 and lifetime of 
0.93ns). Data were fit with the DAS6 software available with the equipment. 

Synthesis. 

The synthesis of the materials is illustrated in Scheme 1; yields, m.p. and solution state 
NMR data follow the synthesis details. 




Scheme 1 . Reagents and conditions: (a) [(CePhOsPbPdCb (2.5 mol %), Cul (1.5 mol %), 
Et 3 N,THF, 0 °C to r.t.; (b) KOH, toluene, N 2 , 110°C, 2h; (c) [(C 6 H 5 ) 3 P] 2 PdCl 2 
(2.5 mol %), Cul (3.0 mol %), Et 3 N, THF, 80 °C; (d) F + NBu 4 , THF, rt. 


General procedure for the Sonogashira-Heck crosscoupling of an acetylene with a 
bromo- or iodoaryl. To a two neck round bottomed flask containing [(CeHsbPbPdCb, 
Cul and the bromoaryl, under nitrogen previously degassed triethylamine (and ~5 % of 
THF in the Godt’s procedure for iodoaryls) is added via cannula. The mixture is heated at 
40-45 °C for 15 min (by the Godt’s method for iodoaryls, it is then cooled to ~0 °C). Then, 
the acetylene monomer is added (in degassed Et 3 N, by the Godt’s procedure in degassed 
THF) under nitrogen atmosphere and stirred vigorously overnight at 70-80 °C (by the 
GodCs method after adding the acetylene, the reaction is left to reach the room 


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temperature and stirred for 48 h). The mixture is filtered off to eliminate the ammonium 
salt, washed with THF and later the solvent evaporated. The crude product is ready for the 
next purification step. 

General procedure for the desilylation. A round bottomed flask charged with the 
(thrimethylsilyl)ethynyl compound, THF, two drops of water, and TBAF (0.2 equivalents 
per silyl group, 1M solution in THF) is stirred at room temperature for 30 minutes and 
then the reaction is stopped by passing it thought a plug of silica gel. After the THF 
evaporation, the product is dried in vacuum for two hours and then used without further 
purification. 

General procedure for the hydrolysis of the (benzyl) benzoate group. To a round 
bottomed flask containing, the (benzyl)benzoate terminated oligomer (1 eq.) and 
pulverized KOH (20 eq. per carboxylic acid), under nitrogen is added anhydrous toluene 
via cannula. After degassing the reactive mixture by bubbling nitrogen into the solution 
for 25 min, the reaction is refluxed for 90 min under nitrogen atmosphere pressure (using 
a rubber balloon). After cooling to room temperature, 1M HC1 solution is added up to 
reach a pH of 2, and a precipitate formation is observed. Then, the solution is filtered, 
washed with toluene and H 2 O and the precipitated is used without more purification. The 
un-hydrolyzed (benzyl) benzoate terminated oligomer is recuperated by evaporating the 
toluene. 

Compound 2FeBz (3). Applying the general procedure for the Sonogashira cross-coupling 
reaction (Godt’s method): To a two neck flask containing 65 mg (0.09 mmol) of 
[(C6H5)3P]2PdCl2, 6 mg (0.027 mmol) of Cul and 690 mg (2.04 mmol) of 2 under 
nitrogen, 70 mL of degassed Et 3 N were added. The mixture was heated at 45°C for 15 min 
and then cooled to 0°C. Later, 390 mg (1.85 mmol) of ethynylferrocene 1 dissolved in 
dried and nitrogen bubbled THF (3 mL) were added via syringe. The mixture was left to 
react to r.t. for 48 h, then the ammonium salt was filtered off and the solvent evaporated, 
the crude product was purified by chromatography (SiC> 2 , CH 2 CI 2 , rf = 0.7, 
CH^CkiHexanes 1:1 rf = 0.4) to obtain a deep red dust in 80 % yield, mp 128-131°C. 'H 
NMR (300 MHz, CDCI 3 ): 8 (ppm) 8.02 (d, 2H, Ar-H), 7.54 (d, 2H, Ar-H), 7.41 (m, 5H, 
Bz), 5.37 (s, 2H, -CH 2 -), 4.52 (t, 2H, ArLe), 4.27 (t, 2H, ArLe), 4.25 (s, 5H, ArLe). 13 C 
NMR (125 MHz, CDCI 3 ): 8 (ppm) 166.03 (C=0), 135.99 (Ar-C), 131.19 (Ar-CH), 129.62 
(Ar-CH), 128.92 (Ar-C), 128.76 (Ar-C), 128.63 (Ar-CH), 128.31 (Ar-CH), 128.24 (Ar- 
CH), 92.20 (-C=C-), 85.27 (-C=C-), 71.60 (ArLe-CH), 70.05 (ArLe-CH), 69.18 (ArLe- 


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CH), 66.82 (-CH 2 -Ar), 64.45 (ArFe-C). UV-Vis (THF): Us <nm) (e, M” 1 cm” 1 ) = 273 
(21,200), 311 (20,500), 365 (4,000), 448 (1,300). 

Compound 2FeAc (4). Applying the general procedure for the hydrolysis of the (benzyl) 
benzoate group: In a 100 mL flask, 200 mg (0.48 mmol) of 3 and 535 mg (9.54 mmol) of 
dry and pulverized KOH were dissolved in 15 mL of dry toluene. The mixture was 
bubbled with nitrogen for 30 min, and refluxed for 90 min keeping a nitrogen pressure by 
using a rubber balloon. After cooling to room temperature, an 1M HC1 water solution was 
added, up to obtain a precipitate that was filtered off and washed with toluene FLO to 
obtain a pale orange powder in 82 % yield, mp 210-220°C. *H NMR (300 MHz, CDCb): 
8 (ppm) 7.59 (d, 2H, Ar-H), 7.10 (d, 2H, Ar-H), 4.12 (bs, 2H, ArFe), 3.89 (bs, 2H, ArFe), 
3.84 (bs, 5H, ArFe). UV-Vis (THF): U s( nm) (e, M” 1 cm” 1 ) = 271 (16,400), 310 (15,400), 
361 (3,000), 448 (920). 

Compound 6. Applying the general procedure for the Sonogashira cross-coupling 
reaction (Godt’s method): To a two neck flask containing 67 mg (0.096 mmol) of 
[(CeHsLPLPdCL, 6 mg (0.029 mmol) of Cul, 1.36 mg (2.094 mmol) of 5 under nitrogen, 
70 mL of degassed Et 3 N were added. The mixture was heated at 45°C for 15 min and then 
cooled at 0°C. Later, 400 mg (1.90 mmol) of ethynylferrocene 1 in THF (3 mL) was 
added. The mixture was left to react at r.t. for 48 h, then filtered and the salts washed with 
THF. After the solvents evaporation, the crude product was purified by chromatography 
(Si0 2 , CHCI 3 : hexanes 1:2, rf = 0.5) to obtain a deep red powder in 60% yield, mp 64- 
66°C. ‘H NMR (300 MHz, CDCI 3 ): 8 (ppm) 7.08 (s, 1H, Ar-H), 6.97 (s, 1H, Ar-H), 4.42 
(t, 2H, ArFe), 4.17 (m, 7H, ArFe), 3.97 (bt, 4H, -CH 2 -a-0), 1.82 (m, 4H, -CH 2 -p-0), 1.48 
(m, 4H, -CH 2 -y-0), 1.26 (bs, 32H, -CH 2 -), 0.87 (t, 6H, -CH 3 ). 13 C NMR (125 MHz, 
CDCb): 8 (ppm) 154.24 (Ar-C-O), 149.60 (Ar-C-O), 118.10 (Ar-CH), 117.85 (Ar-CH), 
113.48 (Ar-C), 112.63 (Ar-C), 93.09 (-C=C-), 81.54 (-C=C-), 71.56 (ArFe-CH), 70.28 (- 
CH 2 -a-0), 70.17 (ArFe-CH), 69.94 (-CH 2 -a-0), 69.36 (ArFe-CH), 65.43 (ArFe-C), 32.07, 
29.83, 29.78, 29.73, 29.71, 29.56, 29.50, 29.37 (-CH 2 -), 26.20 (-CH 2 -y-0), 26.13 (-CH 2 -y- 
O), 22.83 (-CH 2 -), 14.26 (-CH 3 ). 

Compound 7. Applying the general procedure for the Sonogashira cross-coupling 
reaction: To a two neck flask containing 48 mg (0.068 mmol) of [(CeHsLPLPdCh, 4 mg 
(0.020 mmol) of Cul, 1000-mg (1.36 mmol) of 6 under nitrogen, 100 mL of degassed Et 3 N 

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were added. The mixture was heated at 45°C for 15 min and then, 0.267g (0.38 mL, 2.73 
mmol) of TMSA was added via syringe. The mixture was left to react overnight at 60 °C. 
After filtering the ammonium salt and the solvent evaporation, the crude product was 
purified by silica gel by chromatography (SiC> 2 , CH 2 CI 2 : hexanes, 1:3, rf = 0.3) to obtain a 
deep red powder in 78 % yield, mp 68-70°C. 'H NMR (300 MHz, CDCI 3 ): 8 (ppm) 6.91 
(s, 1H, Ar-H), 6.90 (s, 1H, Ar-H), 4.49 (t, 2H, ArFe), 4.24 (s, 5H, ArFe), 4.23 (t, 2H, 
ArFe), 3.96 (2t, 4H, -CH 2 -a-0), 1.81 (m, 4H, -CH 2 -p-0), 1.51 (m, 4H, -CTH-y-O), 1.25 
(bs, 32H, -CH 2 -), 0.87 (t, 6H, -CH 3 ), 0.26 (s, 9H, -SiCH 3 ). 13 C NMR (125 MHz, CDC1 3 ): 8 
(ppm) 154.23 (Ar-C-O), 153.36 (Ar-C-O), 117.24 (Ar-CH), 116.97 (Ar-CH), 114.99 (Ar- 
C), 113.02 (Ar-C), 101.36 (-C=C-), 99.67 (-C=C-), 93.93 (-C=C), 81.95 (-C=C-), 71.45 
(ArFe-CH), 70.03 (ArFe-CH), 69.55 (-CH 2 -a-0), 69.53 (-CH 2 -a-0), 68.87 (ArFe-CH), 
65.30 (ArFe-C), 31.92, 29.68, 29.65, 29.46, 29.43, 29.42, 29.40, 29.36 (-CH 2 -), 26.09 (- 
CH 2 -Y-O), 26.05 (-CH 2 -Y-O), 22.69, 22.55 (-CH 2 -), 14.11 (-CH 3 ), 0.22 (-SiCH 3 ). 

Compound 8. Applying the procedure for the desilylation: To a balloon containing 400 
mg (0.53 mmol) of 7, 20 mL of THF and two drops of water were added. Later, 0.5 mL of 
TBAF (1M solution in THF) was added and stirred for 30 min. Then, the mixture was 
passed through a plug of silica gel using THF as eluent. After the solvent evaporation, the 
product was dried in vacuum for 2 hours to obtain a deep red powder in 97 % yielding, mp 
66-69°C. *H NMR (300 MHz, CDC1 3 ): 8 (ppm) 6.94 (s, 1H, Ar-H), 6.93 (s, 1H, Ar-H), 
4.50 (t, 2H, ArFe), 4.26 (s, 5H, ArFe), 4.24 (t, 2H, ArFe), 3.98 (2t, 4H, -CH 2 -a-0), 3.33 
(s, 1H, -C=CH), 1.83 (m, 4H, -CH 2 -(3-0), 1.50 (m, 4H, -CH 2 -y- 0), 1.26 (bs, 32H, -CH 2 -), 
0.87 (t, 6H, -CH 3 ). 13 C NMR (125 MHz, CDC1 3 ): 8 (ppm) 154.24 (Ar-C-O), 153.36 (Ar- 
C-O), 117.81 (Ar-CH), 116.98 (Ar-CH), 115.46 (Ar-C), 111.90 (Ar-C), 94.06 (-C=C), 
81.95 (-C=C-), 81.82 (-C=C-), 80.21 (-C=CH), 71.47 (ArFe-CH), 70.05 (ArFe-CH), 69.71 
(-CH 2 -a-0), 69.61 (-CH 2 -a-0) 68.90 (ArFe-CH), 65.24 (ArFe-C), 31.92, 29.67, 29.65, 
29.59, 29.58, 29.44, 29.43, 29.36, 29.21 (-CH 2 -), 26.09 (-CH 2 - y -0), 25.94 (-CTL-y-O), 
22.69 (-CH 2 -), 14.11 (-CH 3 ). 

Compound 9. Applying the general procedure for the Sonogashira cross-coupling 
reaction (Godt’s method): To a two neck flask containing 22 mg (0.032 mmol) of 
[(C 6 H 5 ) 3 P] 2 PdCl 2 , 2 mg (0.0096 mmol) of Cul, 642 mg (1.90 mmol) of 2 under nitrogen, 
60 mL of degassed Et 3 N were added. The mixture was heated at 45°C for 15 min and then 
cooled at 0°C. Later, 430 mg (0.634 mmol) of 8 in THF (5 mL) were added. The mixture 

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was left to react at r.t. for 48 h, then filtered and the salts washed with THF. After the 
solvent evaporation, the crude product was purified first by precipitation in methanol, then 
by silica gel chromatography (CH 2 CI 2 : hexanes, 1:1, rf = 0.6) and finally passed through a 
preparative gel permeation chromatography column (Biorad, Bio-Beads SX1, toluene) to 
afford, after the solvent evaporation a red powder in 68 % yield, mp 49-54°C. *H NMR 
(300 MHz, CDCI 3 ): 8 (ppm) 8.05 (d, 2H, Ar-H), 7.57 (d, 2H, Ar-H), 7.41 (m, 5H, Bz), 
6.99 (s, 1H, Ar-H), 6.97 (s, 1H, Ar-H), 5.37 (s, 2H, -CH 2 -), 4.51 (t, 2H, ArFe), 4.26 (s, 5H, 
ArFe), 4.25 (t, 2H, ArFe), 4.02 (2t, 4H, -CH 2 -a-0), 1.85 (m, 4H, -CH 2 -p-0), 1.53 (m, 4H, 
-CH 2 -y-0), 1.25 (bs, 32H, -CH 2 -), 0.87 (t, 6H, -CH 3 ). 13 C NMR (125 MHz, CDCI 3 ): 8 
(ppm) 165.93 (C=0), 153.88 (Ar-C-O), 153.47 (Ar-C-O), 135.93 (Ar-C), 131.40 (Ar-CH), 
129.63 (Ar-CH), 129.28 (Ar-C), 128.64 (Ar-CH), 128.44 (Ar-C), 128.33 (Ar-CH), 128.25 
(Ar-CH), 116.86 (Ar-CH), 115.40 (Ar-C), 112.47 (Ar-C), 94.40 (-C=C-), 93.76 (-C=C-), 
89.39 (-C=C-), 81.94 (-C=C-), 71.49 (ArFe-CH), 70.07 (ArFe-CH), 69.60 (-CH 2 -a-0), 
69.56 (-CH 2 -a-0), 68.95 (ArFe-CH), 66.87 (-CH 2 -Ar), 65.20 (ArFe-C), 31.93, 31.92, 
29.68, 29.66, 29.64, 29.62, 29.45, 29.42, 29.37, 29.35 (-CH 2 -), 26.11 (-CH 2 -y-0), 26.08 (- 
CH 2 -y-0), 22.70 (-CH 2 -), 14.14 (-CH 3 -). UV-Vis (THF): Us ( nm) (s, M _1 cm" 1 ) = 306 
(28,800), 318 (28,700), 373 (31,800). 

Compound 10. Applying the general procedure for the hydrolysis of the (benzyl) 
benzoate group: 300 mg (0.332 mmol) of 9 and 373 mg (6.64 mmol) of pulverized KOH 
in 20 mL of dry toluene were refluxed for 2 h. After cooling to room temperature, 1M HC1 
solution was added up to obtain a precipitate that was filtered off and washed with toluene 
and H 2 0, to obtain a pale orange powder in 79 % yield, mp 133-137°C. 1 H NMR (300 
MHz, CDCI3): 8 (ppm) 8.08 (d, 2H, Ar-H), 7.60 (d, 2H, Ar-H), 7.0 (s, 1H, Ar-H), 6.93 (s, 
1H, Ar-H), 4.52 (t, 2H, ArFe), 4.26 (s, 7H, ArFe), 4.03 (t, 4H, -CH 2 -a-0), 1.86 (m, 4H, - 
CH 2 -P-O), 1.55 (m, 4H, -CH 2 -y- 0), 1.25 (bs, 32H, -CH 2 -), 0.87 (t, 6H, -CH 3 ). UV-Vis 
(THF): Us(nm) (e, M _1 cm" 1 ) = 305 (24,500), 316 (25,300), 371 (26,900). 13 C NMR (125 
MHz, CDCI3): 8 (ppm) 153.94 (Ar-C-O), 153.46 (Ar-C-O), 131.50 (Ar-CH), 130.17 (Ar- 
CH), 129.29 (Ar-C), 116.87 (Ar-CH), 116.83 (Ar-CH), 115.52 (Ar-C), 112.36 (Ar-C), 
94.48 (-C=C-), 93.66 (-C=C-), 89.89 (-C=C-), 81.92 (-C=C-), 71.50 (ArFe-CH), 70.07 
(ArFe-CH), 69.60 (-CH 2 -a-0), 69.56 (-CH 2 -a-0), 68.96 (ArFe-CH), 65.17 (ArFe-C), 
31.94, 31.93, 29.71, 29.70, 29.69, 29.67, 29.46, 29.43, 29.38, 29.36 (-CH 2 -), 26.12 (-CH 2 - 
Y-O), 26.11 (-CHo-y-O), 22.71 (-CH 2 -), 14.14 (-CH 3 -). UV-Vis (THF): Us <nm) (e, M” 1 
cm" 1 ) = 306 (28,800), 318 (28,700), 373 (31,800). 


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Compound 11. Applying the general procedure for the Sonogashira cross-coupling 
reaction: To a two-neck round-bottomed flask containing 5.0 mg (7.4 X 10~ 3 mmol) of 
[(C6H5)3P]2PdCl2, lmg (4.4 X 10" 3 mmol) of Cul (3.0 % mol) and 100 mg (0.147 mmol) 
of 8 , Et 3 N/THF 49:2.5 (v/v). The reaction was heated to 70 °C and stirred under nitrogen 
for 16 h. After filtering the ammonium salt and the solvent evaporated, the crude product 
was first precipitated in methanol, purified by column chromatography (Si0 2 , hexanes: 
CH 2 CI 2 , 1:1, rf=0.4) and then by preparative gel permeation chromatography column 
(Biorad, Bio-Beads SX1, toluene) to afford, after solvent evaporation, a pale orange 
powder in 92 % yield, mp. 99-101 °C. 'H NMR (300 MHz, CDCI 3 ): 8 (ppm) 6.98 (s, 2H, 
Ar-H), 6.95 (s, 2H, Ar-H), 4.53 (bs, 4H, ArFe), 4.27 (s, 14H, ArFe), 4.01 (2t, 8H, -CH 2 -a- 
O), 1.86 (m, 8H, -CH 2 -p-0), 1.54 (m, 8H, -CH 2 -y-0), 1.28 (bs, 64H, -CH 2 -), 0.90 (t, 12H, 
-CH 3 ). 13 C NMR (125 MHz, CDCI 3 ): 8 (ppm) 155.03 (Ar-C-O), 153.34 (Ar-C-O), 117.59 
(Ar-CH), 116.90 (Ar-CH), 115.80 (Ar-C), 111.83 (Ar-C), 94.76 (-C=C-), 81.96 (-C=C-), 
79.61 (-C=C-), 79.11 (-C=C-), 71.50 (ArFe-CH), 70.07 (ArFe-CH), 69.80 (-CH 2 -a-0), 
69.51 (-CH 2 -a-0), 68.97 (ArFe-CH), 65.16 (ArFe-C), 31.94, 29.72, 29.71, 29.68, 29.66, 
29.46, 29.39, 29.18 (-CH 2 -), 26.11 (-CH 2 -y-0), 25.96 (-CH 2 -y-0), 22.71 (-CH 2 -), 14.14 (- 
CH 3 ). UV-Vis (THF): Us ( nm) (s, M” 1 cm” 1 ) =287 (26,500), 304 (25,800), 315 (26,000), 
395 (45,700). 

Compound 12. Applying the general procedure for the Sonogashira cross-coupling 
reaction (Godt’s method): To a two-neck round-bottomed flask containing 27 mg (3.8 X 
10~ 2 mmol) of [(C 6 H 5 ) 3 P] 2 PdCl 2 ,2 mg (1.2 X 10 -3 mmol) of Cul (3.0 % mol) and 497 mg 
(0.764 mmol) of 5, Et 3 N/THF 49:2.5 (v/v) were added. The mixture was heated at 45°C 
for 15 min and then cooled to 0°C. Eater, 518 mg (0.764 mmol) of 8 in THF (5 mF) were 
added. The mixture was left to react at r.t. for 48 h, then filtered and the salts washed with 
THF. After the solvent evaporation, the crude product was purified first by precipitation in 
methanol, then by silica gel chromatography (CH 2 C1 2 : hexanes, 1:1, rf = 0.7) to afford a 
pale orange powder in 87 % yield, mp 53-57°C. ‘H NMR (300 MHz, CDCI 3 ): 8 (ppm) 
7.09 (s, 1H, Ar-H), 7.0 (s, 1H, Ar-H), 6.97 (s, 1H, Ar-H), 6.95 (s, 1H, Ar-H), 4.50 (t, 2H, 
ArFe), 4.25 (m, 7H, ArFe), 3.98 (bt, 8H, -CH 2 -a-0), 1.82 (m, 8H, -CH 2 -p-0), 1.49 (m, 
8H, -CH 2 -y-0), 1.26 (bs, 64H, -CH 2 -), 0.87 (t, 12H, -CH 3 ). 13 C NMR (125 MHz, CDCI 3 ): 8 
(ppm) 154.00 (Ar-C-O), 153.51 (Ar-C-O), 149.48 (Ar-C-O), 118.24 (Ar-CH), 117.69 (Ar- 
CH), 117.16 (Ar-CH), 116.96 (Ar-CH), 114.70 (Ar-C), 113.49 (Ar-C), 113.16 (Ar-C), 
113.06 (Ar-C), 93.95 (-C=C-), 90.76 (-C=C-), 90.55 (-C=C-), 82.03 (-C=C-), 71.48 (ArFe- 


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CH), 70.07 (-CH 2 -a-0), 70.05 (ArFe-CH), 69.99, 69.74, 69.49 (-CH 2 -a-0), 68.89 (ArFe- 
CH), 65.34 (ArFe-C), 31.94, 29.68, 29.62, 29.60, 29.49, 29.48, 29.44, 29.38, 29.27, 29.23, 
26.15, 26.02, 26.01, 25.95, 22.70 (-CH 2 -), 14.14 (-CH 3 ). 

Compound 13. Applying the general procedure for the Sonogashira cross-coupling 
reaction: 10 mg (1.37 X 10“ 2 mmol) of [(C 6 H 5 ) 3 P] 2 PdCl 2 , 1 mg (4.11 X 10‘ 3 mmol) of Cul, 
330-mg (1.36 mmol) of 12, 100 mL of degassed Et 3 N. The mixture was heated at 45°C for 
15 min and then, 81 mg (114 pL, 0.823 mmol) of TMSA was added via syringe. The 
mixture was left to react overnight at 60 °C. After filtering the ammonium salt and the 
solvent evaporation, the crude product was purified by silica gel by chromatography 
(Si0 2 , CH 2 C1 2 : hexanes, 1:2, rf = 0.4) to obtain a red-brown powder in 83 % yield, mp 58- 
62°C. ‘H NMR (300 MHz, CDC1 3 ): 8 (ppm) 6.90 (s, 1H, Ar-H), 6.89 (s, 1H, Ar-H), 6.88 
(s, 1H, Ar-H), 6.87 (s, 1H, Ar-H), 4.44 (t, 2H, ArFe), 4.18 (s, 5H, ArFe), 4.17 (t, 2H, 
ArFe), 3.93 (2t, 8H, -CH 2 -a-0), 1.76 (m, 8H, -CH 2 -p-0), 1.45 (m, 8H, -CH 2 -y-0), 1.18 
(bs, 64H, -CH 2 -), 0.81 (t, 12H, -CH 3 ), 0.19 (s, 9H, -SiCH 3 ). 13 C NMR (125 MHz, CDCb): 
8 (ppm) 154.20 (Ar-C-O), 153.53 (Ar-C-O), 153.50 (Ar-C-O), 153.30 (Ar-C-O), 117.45 
(Ar-CH), 117.14 (Ar-CH), 116.97 (Ar-CH), 114.71 (Ar-C), 114.68 (Ar-C), 113.57 (Ar- 
C), 113.52 (Ar-C), 101.24 (-C=C-), 100.03 (-C=C-), 93.97 (-C=C-), 91.70 (-C=C-), 91.12 
(-C=C-), 82.05 (-C=C-), 71.47 (ArFe-CH), 70.06 (ArFe-CH), 69.74, 69.69, 69.46, 69.42 (- 
CH 2 -a-0), 68.89 (ArFe-CH), 65.34 (ArFe-C), 31.94, 29.69, 29.66, 29.50, 29.47, 29.42, 
29.39, 29.36, 29.33, 26.16, 26.10, 26.02, 25.99, 22.71 (-CH 2 -), 14.15 (-CH 3 ), -0.01 (- 
SiCH 3 ). 

Compound 14. Applying the procedure for the desilylation; 175 mg (0.144 mmol) of 13, 
10 mL of THF, two drops of water and 0.3 mL of TBAL (1M solution in THL). The 
mixture was stirred for 30 min, then passed through a plug of silica gel using THL as 
eluent. The product was dried in vacuum for 2 hours to obtain a deep red powder in 98 % 
yielding, mp 54-62 °C. *H NMR (300 MHz, CDC1 3 ): 8 (ppm) 6.92 (s, 1H, Ar-H), 6.91 (s, 
1H, Ar-H), 6.90 (s, 1H, Ar-H), 6.89 (s, 1H, Ar-H), 4.44 (t, 2H, ArLe), 4.19 (s, 5H, ArLe), 
4.17 (t, 2H, ArLe), 3.93 (2t, 8H, -CH 2 -a-0), 3.26 (s, 1H, -C=CH), 1.76 (m, 8H, -CH 2 -p- 
O), 1.42 (m, 8H, -CH 2 -y-0), 1.28 (bs, 64H, -CH 2 -), 0.81 (t, 12H, -CH 3 ). 

13 C NMR (125 MHz, CDC1 3 ): 8 (ppm) 154.16 (Ar-C-O), 153.56 (Ar-C-O), 153.50 (Ar-C- 
O), 153.26 (Ar-C-O), 117.99 (Ar-CH), 117.12 (Ar-CH), 116.98 (Ar-CH), 116.97 (Ar-CH), 
115.08 (Ar-C), 114.78 (Ar-C), 113.42 (Ar-C), 112.43 (Ar-C), 94.01 (-C=C-), 91.75 (- 

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C=C-), 90.89 (-C=C-), 82.23 (-C=CH-), 82.03 (-C=C-), 80.09 (-C=CH), 71.46 (ArFe-CH), 
70.05 (ArFe-CH), 69.75, 69.73, 69.58, 69.47 (-CH 2 -a-0), 68.89 (ArFe-CH), 65.32 (ArFe- 
C), 31.94, 29.69, 29.63, 29.61, 29.48, 29.39, 29.30, 29.20, 26.15, 26.01, 25.97, 22.71 (- 
CH 2 -), 14.14 (-CH 3 ). 

Compound 15. Applying the general procedure for the Sonogashira cross-coupling 
reaction (Godt’s method): 7 mg (1.1 X 10 2 mmol) of [(C6H5)3P]2PdCl 2 , 1 mg (3.1 X 10" 3 
mmol) of Cul, 212-mg (0.63 mmol) of 2, 50 mL of degassed Et 3 N. The mixture was 
heated at 45°C for 15 min and then, 245 mg (0.209 mmol) of 14 was added via syringe. 
The mixture was left to react at r.t. for 48 h, then filtered and the salts washed with THF. 
The crude product was first precipitated in methanol, purified by column chromatography 
(Si0 2 , hexanes: CH 2 C1 2 , 1:1, rf=0.4) and then by preparative gel permeation 
chromatography column (Biorad, Bio-Beads SX1, toluene) to afford, after solvent 
evaporation, a pale orange powder in 71 % yield, mp 54-58°C. 'H. 8 (ppm) 8.05 (d, 2H, 
Ar-H), 7.58 (d, 2H, Ar-H), 7.42 (m, 5H, Bz), 7.02 (s, 1H, Ar-H), 7.01 (s, 1H, Ar-H), 6.98 
(s, 1H, Ar-H), 6.96 (s, 1H, Ar-H), 5.38 (s, 2H, -CH 2 -), 4.51 (t, 2H, ArFe), 4.26 (s, 5H, 
ArFe), 4.25 (t, 2H, ArFe), 4.02 (2t, 8H, -CH 2 -a-0), 1.85 (m, 8H, -CH 2 -p-0), 1.52 (m, 8H, 
-CH 2 -y- 0), 1.24 (bs, 64H, -CH 2 -), 0.87 (bt, 12H, -CH 3 ). UV-Vis (THF): Us ( nm) (s, M' 1 
cm" 1 ) = 318 (34,500), 398 (49,500). 13 C NMR (125 MHz, CDC1 3 ): 8 (ppm) 165.91 (C=0), 
153.85 (Ar-C-O), 153.57 (Ar-C-O), 153.51 (Ar-C-O), 153.43 (Ar-C-O), 135.93 (Ar-C), 
131.43 (Ar-CH), 129.64 (Ar-CH), 129.33 (Ar-C), 128.64 (Ar-CH), 128.39 (Ar-C), 128.33 
(Ar-CH), 128.25 (Ar-CH), 117.13 (Ar-CH), 116.98 (Ar-CH), 116.95 (Ar-CH), 115.11 
(Ar-C), 114.81 (Ar-C), 113.44 (Ar-C), 113.10 (Ar-C), 94.05 (-C=C-), 94.01 (-C=C-), 
92.06 (-C=C-), 91.07 (-C=C-), 89.29 (-C=C-), 82.05 (-C=C-), 71.47 (ArFe-CH), 70.06 
(ArFe-CH), 69.76 (-CH 2 -a-0), 69.74 (-CH 2 -a-0), 69.51 (-CH 2 -a-0), 69.48 (-CH 2 -a-0), 
68.90 (ArFe-CH), 66.88 (-CH 2 -Ar), 65.33 (ArFe-C), 31.94, 29.72, 29.65, 29.50, 29.48, 
29.45, 29.39, 29.36, 29.33, 26.16, 26.11, 26.03, 26.00, 22.71 (-CH 2 -), 14.15 (-CH 3 ). 

Compound 16. Applying the general procedure for the hydrolysis of the (benzyl) 
benzoate group: 260 mg (0.191 mmol) of 15 and 198 mg (3.82 mmol) of pulverized KOH 
in 20 mL of dry toluene were refluxed for 2 h. After cooling, 1M HC1 solution was added 
up to obtain a precipitate that was filtered off and washed with toluene and H 2 0, to obtain 
a pale orange powder in 79 % yield, mp 94-97 °C. 'H. 8 (ppm) 8.09 (d, 2H, Ar-H), 7.61 
(d, 2H, Ar-H), 7.02 (s, 1H, Ar-H), 7.01 (s, 1H, Ar-H), 6.99 (s, 1H, Ar-H), 6.96 (s, 1H, Ar- 


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11 



H), 4.51 (t, 2H, ArFe), 4.26 (s, 5H, ArFe), 4.25 (t, 2H, ArFe), 4.03 (2t, 8H, -CH 2 -a-0), 
1.86 (m, 8H, -CH 2 -P-O), 1.52 (m, 8H, -CH 2 -y-0), 1.25 (bs, 64H, -CH 2 -), 0.87 (bt, 12H, - 
CH 3 ). UV-Vis (THF): Us ( nm) (e, M -1 cm" 1 ) = 316 (34,600), 395 (49,400). 13 C NMR 
(125 MHz, CDCI 3 ): 8 (ppm) 153.60 (Ar-C-O), 153.50 (Ar-C-O), 153.41 (Ar-C-O), 131.53 
(Ar-CH), 130.90 (Ar-CH), 130.14 (Ar-CH), 129.19 (Ar-C), 128.81 (Ar-CH), 117.12 (Ar- 
CH), 117.01 (Ar-CH), 115.26 (Ar-C), 114.82 (Ar-C), 114.60 (Ar-C), 113.41 (Ar-C), 
113.04 (Ar-C), 94.06 (-C=C-), 93.94 (-C=C-), 92.13 (-C=C-), 91.05 (-C=C-), 89.81 (- 
C=C-), 82.04 (-C=C-), 71.47 (ArFe-CH), 70.06 (ArFe-CH), 69.75 (-CH 2 -a-0), 69.54 (- 
CH 2 -a-0), 69.48 (-CH 2 -a-0), 68.90 (ArFe-CH), 65.33 (ArFe-C), 31.94, 29.71, 29.67, 
29.51, 29.49, 29.40, 29.37, 29.34, 26.16, 26.14, 26.07, 26.03, 26.02, 22.71 (-CH 2 -), 14.15 
(-CH 3 ). 

Compound 17. Applying the general procedure for the Sonogashira cross-coupling 
reaction: To a two-neck round-bottomed flask containing 7.0 mg (8.7 X 10‘ 3 mmol) of 
[(C 6 H 5 ) 3 P] 2 PdCl 2 , lmg (5.22 X 10~ 3 mmol) of Cul (3.0 % mol) and 200 mg (0.174 mmol) 
of 16 , Et 3 N/THF 49:3.0 (v/v). The reaction was heated to 70 °C and stirred under nitrogen 
for 16 h. After filtering the ammonium salt and the solvent evaporated, the crude product 
was first precipitated in methanol, purified by column chromatography (Si0 2 , hexanes: 
CH 2 C1 2 , 1:1, rf=0.3) and then by preparative gel permeation chromatography column 
(Biorad, Bio-Beads SX1, toluene) to afford a pale orange powder in 93 % yield, mp. 90- 
93°C. *H NMR (300 MHz, CDCI 3 ): 8 (ppm) 6.99 (bs, 8H, Ar-H), 4.53 (bs, 4H, ArFe), 
4.27 (bs, 14H, ArFe), 4.03 (bs, 16H, -CH 2 -a-0), 1.86 (bs, 16H, -CH 2 -p-0), 1.52 (bs, 16H, 
-CH 2 -y- 0), 1.27 (bs, 128H, -CH 2 -), 0.89 (bs, 24H, -CH 3 ). 13 C NMR (125 MHz, CDCI 3 ): 8 
(ppm) 155.00 (Ar-C-O), 153.59 (Ar-C-O), 153.51 (Ar-C-O), 153.30 (Ar-C-O), 117.89 
(Ar-CH), 117.13 (Ar-CH), 117.02 (Ar-CH), 117.00 (Ar-CH), 115.53 (Ar-C), 114.86 (Ar- 
C), 113.41 (Ar-C), 112.47 (Ar-C), 94.08 (-C=C-), 92.38 (-C=C-), 91.07 (-C=C-), 82.06 (- 
C=C-), 79.63 (-C=C-), 79.35 (-C=C-), 71.47 (ArFe-CH), 70.05 (ArFe-CH), 69.73 (-CH 2 - 
a-O), 69.49 (-CH 2 -a-0), 68.91 (ArFe-CH), 65.34 (ArFe-C), 31.94, 29.73, 29.48, 29.39, 
29.36, 29.30, 29.19, 26.16, 26.00, 22.71 (-CH 2 -), 14.14 (-CH 3 ). UV-Vis (THF): Us <nm) 
(s, M^ 1 cm" 1 ) = 310 (41,400), 397 (61,600), 409 (61,900). 

Results of linear absorption and emission spectroscopy, laser flash photolysis, ultrafast 
laser femtosecond time-resolved absorption spectra and Z-scan experiments for two 
photon cross section measurements will appear in subsequent reports. 

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References. 


1. Synthesis and Optoelectronic Properties of Phenylenevinylenequinoline 
Macromolecules. Reyes Noria, Rosa Vazquez, Eduardo Arias, Ivana Moggio, Marlene 
Rodriguez, Ronald F. Ziolo, Oliverio Rodriguez, Dean R. Evans, Carl Liebig, New J. 
Chem. 2014, 38 (3), 974-984. 

2. Drect Synthesis of 2,5-Bis(Dodecanoxy)Phenyleneethynylene-Butadiynes by 
Sonogashira Coupling Reaction. Eduardo Arias, Ivana Moggio, Roman Torres, Ronald 
F. Ziolo, Jose-Luis Maldonado, Kirk Green, Thomas M. Cooper, Geoffrey Wicks, 
Aleksander Rebane, Mikhail Drobizhev, Nikolay S. Makarov, Massimo Ottonelli, 
Giovanna Dellepiane, Eur. J. Org. Chem. 2013 (2013) 5341-5352. 

3. Synthesis, Optical and Structured Properties of Sanidic Liquid Crystal 
(Cholesteryl)Benzoate-Ethynylene Oligomers and Polymer. Griselda Castruita, Vladimir 
Garcia, Eduardo Arias, Ivana Moggio, Ronald Ziolo, Arturo Ponce, Virgilio Gonzalez, 
Joy E. Haley, Jonathan L. Flikkemad and Thomas Cooper, J. Mater. Chem. 2012 (22) 
3770-3780. 

4. Cholesteric Liquid Crystal Glass Platinum Acetylides. Cooper, Thomas; Burke, 

Aaron; Krein, Douglas; Ziolo, Ronald; Arias, Eduardo; Moggio, Ivana; Fratini, Albert; 
Garbovskiy, Yuriy; Glushchenko, Anatoliy. Materials Research Society Proceedings. 
1698 mrssl4-1698-jj05-01 doil0.1557opl.2014.820.doc 

5. Glassy Cholesteric Liquid Crystalline Metal Acetylides. Thomas M. Cooper, Ronald F. 
Ziolo, Aaron R. Burke, Anatoliy V. Glushchenko, U.S. Patent No. 8,968,599 B2, March 
3, 2015. 

6 . Asymmetric Freedericksz Transitions from Symmetric Liquid Crystal Cells Doped 
with Harvested Ferroelectric Nanoparticles. G. Cook, V. Yu. Reshetnyak, R. F. Ziolo, 

S. A. Basun, P. P. Banerjee, D. R. Evans, Optics Express 2010 (18) 17339-17445. 

7. Harvesting Single Ferroelectric Domain Stressed Nanoparticles for Optical and 
Ferroic Applications. G. Cook, J. L. Barnes, S. A. Basun, D. R. Evans, R. F. Ziolo, A. 
Ponce, V. Yu. Reshetnyak, A. Glushchenko, P. P. Banerjee. J. Appl. Phys. 2010 (108) 
064309-064309-5. 


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