Supporting Information
Ground and Excited State Properties of Chalcogenol Esters: A Combined
Theoretical and Experimental Study
Daniel da Silveira Rampon,a Fabiano da Silveira Santos,b Rodrigo Roceti Descalzo,c Josene Maria
Toldo,c Paulo Fernando Bruno Gonçalves,*c Paulo Henrique Schneider*a and Fabiano Severo
Rodembusch*b
Instituto de Química, Departamento de Química Orgânica, Universidade Federal do Rio Grande do Sul,
Av. Bento Gonçalves 9500. CEP 91501-970, Porto Alegre-RS, Brazil. aLaboratório de Síntese Orgânica
e Materiais Inteligentes - LASOMI; Phone: +55 51 3308 6293; bGrupo de Pesquisa em Novos Materiais
Orgânicos e Fotoquímica; Phone: +55 51 3308 6299; cGrupo de Química Teórica; Phone: +55 51 3308
7197. E-mail: paulos@iq.ufrgs.br (P.H. Schneider), paulo@iq.ufrgs.br (P.F.B. Gonçalves) and
rodembusch@iq.ufrgs.br (F.S. Rodembusch).
Contents
1. General Experimental Procedures
S-3
2. NMR Spectra
S-10
3. Infrared Spectra
S-38
4. Lippert-Mataga Data
S-42
5. Theoretical Calculation Data
S-44
6. References
S-48
S-1
1. General Experimental Procedures
Synthesis
4’-(4-octyloxyphenyl)-2-methylbut-3-yn-2-ol (5a)
Alkylation Reaction. 1 4-Bromophenol (26 g, 150 mmol) and potassium hydroxide (10 g, 178 mmol)
were added to benzene and DMF (1:1, 200 mL) and heated at 50ºC for 15 min. Then, noctylbromide (31 mL, 178 mmol) was added dropwise and the mixture heated under reflux for 6 h.
The solid formed was filtered off and the filtrate concentrated. The residue was dissolved in diethyl
ether (200 mL), washed with 10 % sodium bicarbonate solution (2 x 100 mL), and water (100 mL),
then dried over anhydrous sodium sulfate. The solvent was removed by evaporation and the product
purified by distillation under reduced pressure. The compound 1-bromo-4-(octyloxy)benzene (1a)
was obtained as pale yellow viscous liquid. Yield: 34.6 g, 81%. B.p.: 117 oC (1 mmHg). 1H NMR
(300 MHz, CDCl3):  = 0.88 (t, 3H, CH3), 1.28 (m, 10H, (CH2)5), 1.72 (m, 2H, CH2CH2O), 3.83 (t, J
= 6.5 Hz, 2H, CH2O), 6.71 (d, J = 8.9 Hz, 2H, Ar), 7.32 (d, J = 8.9 Hz, 2H, Ar);
13
C NMR (75 MHz,
CDCl3):  = 14.0, 22.6, 25.9, 29.1, 29.2, 29.3, 31.7, 68.1, 112.4, 116.1, 117.2, 132, 132.2, 158.1.
Sonogashira Coupling Reaction.1 A test tube was charged with Et 3N (100 mL), 2-methyl-3-butyn-2ol (7 mL, 70 mmol), and 1-bromo-4-(octyloxy)benzene (6a) (9 g, 32 mmol) under argon. To the
solution were added CuI (4 mol %, 0.24 mg), PPh3 (8 mol %, 0.67 g), and PdCl2(PPh3)2 (4 mol %,
0.9 g). The mixture was heated for 24 h at 90 oC. After cooling, the solid was filtered and washed
with CH2Cl2 (100 mL). The filtered mixture was evaporated, and the resulting dark yellow oil was
dissolved in CH2Cl2 (200 mL) and washed with water (3 x 80 mL), cold 5 N hydrochloric acid (80
mL), and water (80 mL). The organic layer was dried over anhydrous sodium sulfate. The solvent
was evaporated and the remaining solid was purified by chromatography. A yellow solid of 4’-(4octyloxyphenyl)-2-methylbut-3-yn-2-ol (5a) was obtained in 80% yield.
Yield: 7.4 g, 80%. M.p.: 60.2 oC. 1H NMR (300 MHz, CDCl 3):  = 0.89 (t, 3H, CH3), 1.30 (m, 10H,
(CH2)5), 1.60 (s, 6H, CH3), 1.80 (m, 2H, CH2CH2O), 2.20 (s, 1H, OH), 3.90 (t, J = 6.6 Hz, 2H,
CH2O), 6.80 (d, J = 8.8 Hz, 2H, Ar), 7.30 (d, J = 8.8 Hz, 2H, Ar).
13
C NMR (75 MHz, CDCl 3):  =
14.0, 22.6, 25.9, 29.1, 29.2, 29.3, 29.4, 31.5, 31.8, 65.7, 68.0, 82.1, 92.2, 114.4, 114.5, 133.0, 159.1.
4’-(4-decyloxyphenyl)-2-methylbut-3-yn-2-ol (5b)
Alkylation Reaction. 1 An experimental procedure identical to prepare 6a was applied for synthesis of
S-2
1-bromo-4-(decyloxy)benzene (6b). Yield: 39.0 g, 83%. B.p.:146 oC (1 mmHg). 1H NMR (300
MHz, CDCl3):  = 0.89 (t, 3H, CH3), 1.35 (m, 14H, (CH2)7), 1.73 (m, 2H, CH2CH2O), 3.86 (t, J =
5.6 Hz, 2H, CH2O), 6.51 (d, J = 8.5 Hz, 2H, Ar), 7.30 (d, J = 8.9 Hz, 2H, Ar);
13
C NMR (75 MHz,
CDCl3):  = 14.0, 22.6, 25.9, 29.1, 29.2, 29.5, 30.9, 31.5, 31.8, 68.0, 112.3, 116.1, 117.3, 131.9,
132.2, 158.1
Sonogashira Coupling Reaction.1 An experimental procedure identical to prepare 5a was applied for
synthesis of 4’-(4-decyloxyphenyl)-2-methylbut-3-yn-2-ol (5b). Yield: 8.6 g, 85%. M.p.: 49.6 oC. 1H
NMR (300 MHz, CDCl 3):  = 0.86 (t, 3H, CH3), 1.27-1.79 (m, 14H, (CH2)7), 1.61 (s, 6H, CH3), 1.77
(t, 2H, CH2CH2O), 2.11 (s, 1H, OH), 3.94 (t, J = 6.6 Hz, 2H, CH2O), 6.81 (d, J = 8.8 Hz, 2H, Ar),
7.33 (d, J = 8.8 Hz, 2H, Ar).
13
C NMR (75 MHz, CDCl 3):  = 14.1, 22.6, 26.0, 29.1, 29.3, 29.4,
29.5, 29.5, 30.9, 31.5, 31.9, 65.6, 68.0, 82.0, 92.2, 114.4, 114.5, 133.0, 159.1.
4´-[4-(Octyloxyphenyl)ethynyl]benzoic acid (2a)
Deprotection and Coupling Reaction.1 Potassium hydroxide (0.5 g, 9 mmol) and isopropyl alcohol
(40 mL) were added to a round bottomed flask and heated at 50 oC for 15 min. Then, a solution of
4’-(4-octyloxyphenyl)-2-methylbut-3-yn-2-ol (5a) (0.9 g, 3 mmol) in isopropyl alcohol (10 mL) was
added. The mixture was heated under reflux for 2 h. The solvent was evaporated, the residue
dissolved in CH2Cl2 (50 mL), and washed with water (3 x 30 mL). The organic layer was dried over
anhydrous sodium sulfate. The solvent was evaporated and a yellow oil of 1-Ethynyl-4(octyloxy)benzene (4a) was obtained in 99% yield. This oil was used to another Sonogashira
coupling with methyl 4-bromobenzoate. After cooling of reaction test tube, the solid was filtered and
washed with CH2Cl2 (100 mL). The filtered mixture was evaporated, and the resulting dark yellow
oil was dissolved in CH 2Cl2 (200 mL) and washed with water (3 x 80 mL), cold 5 N hydrochloric
acid (80 mL), and water (80 mL). The organic layer was dried over anhydrous sodium sulfate. The
solvent was evaporated and the remaining solid was purified by chromatography and
recrystallization from hexane. Yield: 0.66 g, 60%. M.p.: 112.6 oC. 1H NMR (300 MHz, CDCl 3):  =
0.89 (t, 3H, CH3), 1.33 (m, 10H, (CH2)5), 1.80 (m, 2H, CH2CH2O), 3.92 (s, 3H, CH3O), 3.97 (t, J =
6.6 Hz, 2H, CH2O), 6.90 (d, J = 8.8 Hz, 2H, Ar), 7.40 (d, J = 8.8 Hz d, 2H, Ar), 7.60 (d, J = 8.1 Hz,
2H, Ar), 8.00 (d, J = 8.1 Hz, 2H, Ar).
13
C NMR (75 MHz, CDCl 3):  = 14.1, 22.7, 26.0, 29.1, 29.2,
29.3, 31.8, 52.2, 68.1, 77.2, 87.4, 92.7, 114.4, 114.6, 128.5, 129.0, 129.5, 131.3, 133.2, 159.6, 166.6.
Hydrolysis Reaction. 2 Methyl-4´-(4-octyloxyphenyl)ethynyl benzoate (3a) (0.8 g, 2.3 mmol) was
S-3
dissolved in THF (30 mL) and 1 mol.L-1 aq KOH (12 mL) was added. After heating the reaction
mixture at 60 oC for 24 h, the resulting solution was evaporated to dryness. The solid was dissolved
in water (60 mL) and then the aqueous solution was acidified by conc HCl (pH = 1). White
precipitate
was
filtered,
washed
with
water,
and
then
dried.
The
product
4´-[4-
(Octyloxyphenyl)ethynyl]benzoic acid (2a) was obtained by recrystallization from EtOH. Yield: 0.7
g, 90%. Dc > 250 oC. 1H NMR (300 MHz, DMSO-d6):  = 0.89 (t, 3H, CH3), 1.30 (m, 10H, (CH2)5),
1.70 (m, 2H, CH2CH2O), 2.50 (s, 1H, OH), 4.00 (t, J = 6.4 Hz, 2H, CH 2O), 7.00 (d, J = 8.6 Hz, 2H,
Ar), 7.50 (d, J = 8.8 Hz, 2H, Ar), 7.60 (d, J = 8.2 Hz, 2H, Ar), 8.00 (d, J = 8.2 Hz, 2H, Ar).
13
C
NMR (75 MHz, DMSO-d6):  = 13.6, 21.7, 25.2, 28.3, 28.3, 28.4, 30.9, 67.5, 87.1, 92.1, 113.4,
114.8, 126.9, 129.2, 130.0, 130.9, 132.9, 159.2, 164.0, 166.4.
4´-[4-(Decyloxyphenyl)ethynyl]benzoic acid (2b)
Deprotection and Coupling Reaction.1 An experimental procedure identical to prepare 3a was
applied for synthesis of Methyl-4´-(4-decyloxyphenyl)ethynyl benzoate (3b). Yield: 0.64 g, 56%.
M.p.: 104.1 oC. 1H NMR (300 MHz, CDCl 3):  = 0.90 (t, 3H, CH3), 1.36 (m, 14H, (CH2)7), 1.79 (m,
2H, CH2CH2O), 3.96 (m, 5H), 6.88 (d, J = 8.6 Hz, 2H, Ar), 7.45 (d, J = 8.5 Hz, 2H, Ar), 7.56 (d, J =
8.2 Hz, 2H, Ar), 8.00 (d, J = 8.2 Hz, 2H, Ar).
13
C NMR (75 MHz, CDCl 3):  = 14.4, 23.0, 26.2,
29.3, 29.4, 29.6, 29.7, 29.8, 32.2, 52.5, 68.4, 87.7, 93.0, 114.6, 114.9, 128.7, 129.3, 129.8, 131.5,
133.5, 134.3, 159.9, 164.9.
Hydrolysis Reaction. 2 An experimental procedure identical to prepare 2a was applied for synthesis
of 4´-[4-(Decyloxyphenyl)ethynyl]benzoic acid (2b). Yield: 0.65 g, 75%. Dc > 250 oC. 1H NMR
(300 MHz, DMSO-d6):  = 0.87 (broad, 3H, CH3), 1.27 (broad, 14H, (CH2)7), 1.73 (broad, 2H,
CH2CH2O), 4.00 (broad, 2H), 6.94 (broad, 2H, Ar), 7.47 (broad, 2H, Ar), 7.58 (broad, 2H, Ar), 7.94
(broad, 2H, Ar).
13
C NMR (75 MHz, DMSO-d6):  = 11.9, 20.2, 23.6, 26.8, 26.9, 27.1, 27.1, 27.2,
29.4, 66.0, 85.5, 90.5, 113.1, 113.2, 127.6, 128.4, 129.2, 131.2, 132.0, 157.6, 164.8.
4-Methoxyphenyl 4´-[(4-octyloxyphenyl)ethynyl]benzoselenoate (1a)3
Tributylphosphine (0.15 mL, 0.6 mmol) was slowly added to dichalcogenide (0.3 g, 0.8 mmol) in
anhydrous
CH2Cl2
(30
mL)
and
the
mixture
left
to
stir
for
15
min.
4´-[4-
(Octyloxyphenyl)ethynyl]benzoic acid (2a) (0.14 g, 0.4 mmol) was then added and the reaction
stirred for 24 h at room temperature till no precipitate was visible. The reaction mixture was diluted
S-4
with CH2Cl2 and washed with water (50 mL), sat. sodium bicarbonate (2 x 50 mL), and water (50
mL). The organic layer was dried over anhydrous sodium sulfate. The solvent was evaporated and
the remaining solid was purified by chromatography and recrystallization from hexane. Yield: 0.1 g,
50%. Cr 118.1 oC N 218.8 oC I. 1H NMR (300 MHz, CDCl 3):  = 0.89 (t, 3H, CH3), 1.30 (m, 10H,
(CH2)5), 1.80 (m, 2H, CH2CH2O), 3.85 (s, 3H, CH3O), 3.98 (t, J = 6.6 Hz, 2H, CH2O), 6.90 (d, J =
8.6 Hz, 2H, Ar), 7.00 (d, J = 8.5 Hz d, 2H, Ar), 7.48 (d, J = 8.6 Hz, 2H, Ar), 7.50 (d, J = 8.4 Hz, 2H,
Ar). 7.60 (d, J = 8.2 Hz, 2H, Ar), 7.90 (d, J = 8.1 Hz, 2H, Ar).
13
C NMR (75 MHz, CDCl 3):  =
14.8, 23.3, 26.7, 29.8, 29.9, 29.9, 30.0, 32.5, 56.0, 68.8, 88.0, 94.3, 115.0, 115.3, 115.9, 116.7,
127.9, 130.2, 132.4, 134.0, 137.8, 138.5, 160.4, 161.2, 194.2. Anal. calcd. for C 30H32O3Se: C, 69.35;
H, 6.21, found: C, 68.95; H, 6.65. IR (KBr,  = cm-1): 2919, 2854, 2281, 1672, 1591, 1515, 1493.
4-Methoxyphenyl 4´-[(4-octyloxyphenyl)ethynyl]benzothioate (1b)4
To
a
solution
of
4-methoxythiophenol
(0.25
mL,
2.1
mmol)
and
4´-(4-
(octyloxyphenyl)ethynylbenzoic acid (2a) (0.3 g, 0.85 mmol) in dry CH 2Cl2 (50 ml) under argon,
was added 4-(dimethylamino)pyridinium p-toluenesulfonate (DPTS) (0.02 g, 0.08 mmol, 10 mol%)
and N,N’-dicyclohexylcarbodiimide (DCC) (0.2 g, 0.93 mmol). The reaction mixture was stirred for
24 h at r.t. The crude solution was filtered and washed with CH 2Cl2 (100 mL). The filtered mixture
was washed with water (50 mL), sat. sodium bicarbonate (2 x 50 mL), and water (50 mL) and the
organic layer was dried over anhydrous sodium sulfate. The solvent was evaporated and the
remaining solid was purified by chromatography and recrystallization from hexane. Yield: 0.12 g,
30%. Cr1 64.3 oC Cr2 116.9 oC N 248.8 oC I. 1H NMR (300 MHz, CDCl 3):  = 0.82 (t, 3H, CH 3),
1.30 (m, 10H, (CH2)5), 1.70 (m, 2H, CH2CH2O), 3.78 (s, 3H, CH3O), 3.91 (t, J = 6.6 Hz, 2H,
CH2O), 6.80 (d, J = 8.8 Hz, 2H, Ar), 6.90 (d, J = 8.9 Hz d, 2H, Ar), 7.30 (d, J = 8.8 Hz, 2H, Ar),
7.40 (d, J = 8.8 Hz, 2H, Ar), 7.50 (d, J = 8.6 Hz, 2H, Ar), 7.90 (d, J = 8.5 Hz, 2H, Ar). 13C NMR (75
MHz, CDCl3):  = 14.1, 22.6, 26.0, 29.1, 29.2, 29.3, 31.8, 55.3, 68.1, 87.3, 93.4, 114.3, 114.6,
115.0, 117.6, 127.3, 129.2, 131.5, 133.2, 135.3, 136.6, 159.7, 160.8, 190.2. HRMS -ESI: m/z calcd.
for C30H33O3S [M + H]+ 473.6562, found: 473.6541. IR (KBr,  = cm-1): 2920, 2852, 2216, 1667,
1587, 1513, 1494.
4-Methoxyphenyl 4´-[(4-octyloxyphenyl)ethynyl]benzoate (1c)
An experimental procedure identical to prepare 1b was applied.4 Yield: 0.5 g, 72%. Cr 128.6 oC N
S-5
219.3 oC I. 1H NMR (300 MHz, CDCl 3):  = 0.82 (t, 3H, CH3), 1.40 (m, 10H, (CH2)5), 1.70 (m, 2H,
CH2CH2O), 3.76 (s, 3H, CH3O), 3.91 (t, J = 6.6 Hz, 2H, CH2O), 6.80 (d, J = 8.9 Hz, 2H, Ar), 6.90
(d, J = 9.0 Hz d, 2H, Ar), 7.10 (d, J = 9.1 Hz, 2H, Ar), 7.40 (d, J = 8.9 Hz, 2H, Ar), 7.50 (d, J = 8.6
Hz, 2H, Ar), 8.10 (d, J = 8.6 Hz, 2H, Ar). 13C NMR (75 MHz, CDCl 3):  = 14.1, 22.6, 25.9, 29.1,
29.2, 29.3, 31.8, 55.6, 68.1, 87.4, 93.2, 114.3, 114.5, 114.6, 122.4, 128.4, 129.1, 130.0, 131.3, 133.2,
144.3, 157.3, 159.7, 165.0. HRMS-ESI: m/z calcd. for C30H33O4 [M + H]+ 457.5856, found:
457.5842. IR (KBr,  = cm-1): 2876, 2808, 2167, 1692, 1556, 1458, 1427.
Se-Phenyl 4´-[(4-decyloxyphenyl)ethynyl]benzoselenoate (1d)
An
experimental
procedure
identical
to
prepare
1a
was
applied
with
4´-[4-
(Decyloxyphenyl)ethynyl]benzoic acid (2b).3 Yield: 0.16 g, 78%. Cr 100.3 oC SmA 129.4 oC N
149.4 oC I. 1H NMR (300 MHz, CDCl 3):  = 0.81 (t, 3H, CH3), 1.21 (m, 14H, (CH2)7), 1.72 (m, 2H,
CH2CH2O), 3.91 (t, J = 6.4 Hz, 2H, CH2O), 6.81 (d, J = 8.6 Hz, 2H, Ar), 7.37 (m, 5H, Ar), 7.51 (m,
4H, Ar), 7.83 (d, J = 8.2 Hz, 2H, Ar).
13
C NMR (75 MHz, CDCl 3):  = 14.8, 23.3, 26.7, 29.8, 29.9,
29.9, 30.0, 32.5, 56.0, 68.8, 88.0, 94.3, 115.0, 115.3, 115.9, 116.7, 127.9, 130.2, 132.4, 134.0, 137.8,
138.5, 160.4, 161.2, 194.2. Anal. calcd. for C 31H34O2Se: C, 71.94; H, 6.62, found: C, 72.97; H, 6.68.
IR (KBr,  = cm-1): 2919, 2847, 2213, 1678, 1589, 1508, 1473.
S-Phenyl 4´-[(4-decyloxyphenyl)ethynyl]benzothioate (1e)
An
experimental
procedure
identical
to
prepare
1b
was
applied
with
4´-[4-
(Decyloxyphenyl)ethynyl]benzoic acid (1b).4 Yield: 0.11 g, 54%. Cr 100.7 oC SmX 114.1 oC SmA
139.2 oC N 175.8 oC I. 1H NMR (300 MHz, CDCl 3):  = 0.80 (t, 3H, CH3), 1.20-1.36 (m, 14H,
(CH2)7), 1.69 (m, 2H, CH2CH2O), 3.86 (t, J = 6.6 Hz, 2H, CH2O), 6.80 (d, J = 8.9 Hz, 2H, Ar), 7.37
(m, 7H, Ar), 7.50 (d, J = 8.5 Hz, 2H, Ar), 7.90 (d, J = 8.5 Hz, 2H, Ar).
13
C NMR (75 MHz, CDCl 3):
 = 14.8, 23.3, 26.7, 29.8, 29.9, 30.0, 30.1, 30.2, 32.5, 68.7, 88.0, 94.2, 114.9, 115.3, 127.8, 128.1,
129.9, 130.0, 130.2, 132.2, 134.0, 135.7, 135.8, 160.4, 189.9. Anal. calcd. for C 31H34O2S: C, 79.11;
H, 7.28, found: C, 77.41; H, 6.94. IR (KBr,  = cm-1): 2930, 2850, 2208, 1671, 1591, 1512, 1466.
O-Phenyl 4´-[(4-decyloxyphenyl)ethynyl]benzoate (1f)
An
experimental
procedure
identical
to
prepare
1b
was
applied
with
4´-[4-
(Decyloxyphenyl)ethynyl]benzoic acid (2b).4 Yield: 0.28 g, 74%. Cr 98.0 oC SmA 123.3 oC N 142.5
S-6
o
C I. 1H NMR (300 MHz, CDCl 3):  = 0.89 (t, 3H, CH3), 1.29 (m, 12H, (CH2)6), 1.46 (m, 2H,
(CH2)), 1.79 (m, 2H, CH2CH2O), 3.98 (t, 2H, CH2O), 6.89 (d, J = 8.8 Hz, 2H, Ar), 7.30 (m, 3H, Ar),
7.46 (m, 4H, Ar), 7.62 (d, J = 8.4 Hz, 2H, Ar), 8.16 (d, J = 8.4 Hz, 2H, Ar).
13
C NMR (75 MHz,
CDCl3):  = 14.1, 22.6, 26.0, 29.1, 29.2, 29.3, 29.5, 31.8, 31.9, 68.1, 87.4, 93.3, 114.3, 114.6, 121.6,
125.9, 128.4, 129.2, 129.5, 130.0, 131.4, 133.3, 150.9, 159.7, 164.7. Anal. calcd. for C 31H34O3: C,
81.90; H, 7.54, found: C, 81.91; H, 7.22. IR (KBr,  = cm-1): 2922, 2850, 2218, 1739, 1600, 1519,
1495.
S-7
2. NMR Spectra
Figure SI1. 1H NMR spectrum of compound 1-bromo-4-octyloxybenzene (6a) (CDCl3, 300 MHz).
S-8
Figure SI2. 13C NMR spectrum of compound 1-bromo-4-octyloxybenzene (6a) (CDCl3, 75 MHz).
S-9
Figure SI3. 1H NMR spectrum of compound 1-bromo-4-decyloxybenzene (6b) (CDCl3, 300 MHz).
S - 10
Figure SI4. 13C NMR spectrum of compound 1-bromo-4-decyloxybenzene (6b) (CDCl3, 75 MHz).
S - 11
Figure SI5. 1H NMR spectrum of compound 4´-(4-octyloxyphenyl)-2-methylbut-3-yn-2-ol (5a) (CDCl3, 300 MHz).
S - 12
Figure SI6. 13C NMR spectrum of compound 4´-(4-octyloxyphenyl)-2-methylbut-3-yn-2-ol (5a) (CDCl3, 75 MHz).
S - 13
Figure SI7. 1H NMR spectrum of compound 4´-(4-decyloxyphenyl)-2-methylbut-3-yn-2-ol (5b) (CDCl3, 300 MHz).
S - 14
Figure SI8. 13C NMR spectrum of compound 4´-(4-decyloxyphenyl)-2-methylbut-3-yn-2-ol (5b) (CDCl3, 75 MHz).
S - 15
Figure SI9. 1H NMR spectrum of compound Methyl-4´-(4-octyloxyphenylethynyl)benzoate (3a) (CDCl3, 300 MHz).
S - 16
Figure SI10. 13C NMR spectrum of compound Methyl-4´-(4-octyloxyphenylethynyl)benzoate (3a) (CDCl3, 75 MHz).
S - 17
Figure SI11. 1H NMR spectrum of compound Methyl-4´-(4-decyloxyphenylethynyl)benzoate (3b) (CDCl3, 300 MHz).
S - 18
Figure SI12. 13C NMR spectrum of compound Methyl-4´-(4-decyloxyphenylethynyl)benzoate (3b) (CDCl3, 75 MHz).
S - 19
Figure SI13. 1H NMR spectrum of compound 4´-[4-(Octyloxyphenyl)ethynyl]benzoic acid (2a) (DMSO-d6, 300 MHz).
S - 20
Figure SI14. 13C NMR spectrum of compound 4´-[4-(Octyloxyphenyl)ethynyl]benzoic acid (2a) (DMSO-d6, 75 MHz).
S - 21
Figure SI15. 1H NMR spectrum of compound 4´-[4-(Decyloxyphenyl)ethynyl]benzoic acid (2b) (DMSO-d6, 300 MHz).
S - 22
Figure SI16. 13C NMR spectrum of compound 4´-[4-(Decyloxyphenyl)ethynyl]benzoic acid (2b) (DMSO-d6, 75 MHz).
S - 23
Figure SI17. 1H NMR spectrum of compound 4-Methoxyphenyl 4´-[(4-octyloxyphenyl)ethynyl]benzoselenoate (1a) (CDCl3, 300
MHz).
S - 24
Figure SI18. 13C NMR spectrum of compound 4-Methoxyphenyl 4´-[(4-octyloxyphenyl)ethynyl]benzoselenoate (1a) (CDCl3, 75
MHz).
S - 25
Figure SI19. 1H NMR spectrum of compound 4-Methoxyphenyl 4´-[(4-octyloxyphenyl)ethynyl]benzothioate (1b) (CDCl3, 300 MHz).
S - 26
Figure SI20 13C NMR spectrum of compound 4-Methoxyphenyl 4´-[(4-octyloxyphenyl)ethynyl]benzothioate (1b) (CDCl3, 75 MHz).
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Figure SI21. 1H NMR spectrum of compound 4-Methoxyphenyl 4´-[(4-octyloxyphenyl)ethynyl]benzoate (1c) (CDCl3, 300 MHz).
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Figure SI22. 13C NMR spectrum of compound 4-Methoxyphenyl 4´-[(4-octyloxyphenyl)ethynyl]benzoate (1c) (CDCl3, 75 MHz).
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Figure SI23. 1H NMR spectrum of compound Se-Phenyl 4´-[(4-decyloxyphenyl)ethynyl]benzoselenoate (1d) (CDCl3, 300 MHz).
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Figure SI24. 13C NMR spectrum of compound Se-Phenyl 4´-[(4-decyloxyphenyl)ethynyl]benzoselenoate (1d) (CDCl3, 75 MHz).
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Figure SI25. 1H NMR spectrum of compound S-Phenyl 4´-[(4-decyloxyphenyl)ethynyl]benzothioate (1e) (CDCl3, 300 MHz).
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Figure SI26. 13C NMR spectrum of compound S-Phenyl 4´-[(4-decyloxyphenyl)ethynyl]benzothioate (1e) (CDCl3, 75 MHz).
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Figure SI27. 1H NMR spectrum of compound O-Phenyl 4´-[(4-decyloxyphenyl)ethynyl]benzoate (1f) (CDCl3, 300 MHz).
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Figure SI28. 13C NMR spectrum of compound O-Phenyl 4´-[(4-decyloxyphenyl)ethynyl]benzoate (1f) (CDCl3, 75 MHz).
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3. Infrared Spectra
100
Transmittance (%)
90
80
70
60
50
40
4000
3500
3000
2500
2000
1500
1000
500
-1
Wavenumber (cm )
Figure SI29. Infrared spectrum of compound 4-Methoxyphenyl 4´-[(4octyloxyphenyl)ethynyl]benzoselenoate (1a).
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Transmittance (%)
100
90
80
70
4000
3500
3000
2500
2000
1500
1000
-1
Wavenumber (cm )
Figure SI30. Infrared spectrum of compound 4-Methoxyphenyl 4´-[(4octyloxyphenyl)ethynyl]benzothioate (1b).
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500
Transmittance (%)
100
90
80
70
4000
3500
3000
2500
2000
1500
1000
500
-1
Wavenumber (cm )
Figure SI31. Infrared spectrum of compound 4-Methoxyphenyl 4´-[(4-octyloxyphenyl)ethynyl]benzoate
(1c).
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Transmittance (%)
100
90
80
70
4000
3500
3000
2500
2000
1500
1000
500
-1
Wavenumber (cm )
Figure SI32. Infrared spectrum of compound Se-Phenyl 4´-[(4-decyloxyphenyl)ethynyl]benzoselenoate
(1d).
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Transmittance (%)
100
90
80
4000
3500
3000
2500
1500
2000
1000
500
-1
Wavenumber (cm )
Figure SI33. Infrared spectrum of compound S-Phenyl 4´-[(4-decyloxyphenyl)ethynyl]benzothioate
(1e).
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100
Transmittance (%)
90
80
70
60
50
4000
3500
3000
2500
2000
1500
-1
1000
500
Wavenumber (cm )
Figure SI34. Infrared spectrum of compound O-Phenyl 4´-[(4-decyloxyphenyl)ethynyl]benzoate (1f).
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4. Lippert-Mataga Data
Figure SI35. Solvent effect on the spectral position of the absorption maxima for the chalcogenol esters
1a-f. The Lippert–Mataga solvent polarity function Δf is given in Equation (4).
Figure SI36. Solvent effect on the spectral position of the fluorescence emission maxima for the
chalcogenol esters 1a-f. The Lippert–Mataga solvent polarity function Δf is given in Equation (4).
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Table SI1. Data from the linear fit of the Lippert-Mataga correlation.
Compd.
1a
1b
1c
1d
1e
1f
R2 (Absorbance)
0.23
0.10
0.50
0.05
0.21
0.24
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R2 (Emision)
0.68
0.70
0.92
0.48
0.73
0.98
5. Theoretical Calculation Data
Figure SI37. Optimized geometries of the chalcogenol esters 1a-c in the ground (bottom) and
excited state (top).
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Figure SI38. HOMO (bottom) and LUMO (top) orbitals of the chalcogenol esters 1a-c.
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Figure SI39. Electrostatic potential surfaces of the chalcogenol esters 1a-c in the ground electronic
state (S0) (bottom) and first electronic excited state (S 1) (top). The most negative (electron-rich)
potential is depicted in red, and the most positive (electron-poor) is depicted in blue.
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Table SI2. The Onsager radius obtained using the Gaussian 09 package.
Compound
1a
1b
1c
1d
1e
1f
a0 recmd.
6.34
6.31
6.23
6.43
6.36
6.33
a0 real
5.84
5.81
5.73
5.93
5.86
5.83
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7. References
1. (a) Vasconcelos, U. B.; Dalmolin, E.; Merlo, A. A. Org. Lett. 2005, 7, 1027. (b) Vasconcelos, U. B.;
Merlo, A. A. Synthesis. 2006, 7, 1141. (c) Vasconcelos, U. B.; Vilela, G. D.; Schrader, A.; Borges, A. C.
A.; Merlo, A. A. Tetrahedron. 2008, 64, 4619. (d) Merlo, A. A.; Gallardo, H.; Taylor, T. R. Quim. Nova.
2001, 24, 354
2. Suzuki, M.; Sato, T.; Kurose, A.; Shirai, H.; Hanabusa, K. Tetrahedron Lett. 2005, 46, 2741.
3. Rampon, D. S.; Rodembusch, F. S.; Schneider, J. M. F. M.; Bechtold, I. H.; Gonçalves, P. F. B.;
Merlo, A. A.; Schneider, P. H. J. Mater. Chem. 2010, 20, 715.
4. (a) Rampon, D. S.; Rodembusch, F. S.; Lourega, R.; Gonçalves, P. F. B.;Merlo, A. A.; Schneider, P.
H. J. Braz. Chem. Soc. 2010, 21, 2100. (b) Neises, B.; Steglich, W. Angew. Chem., Int. Ed. 1978, 17,
522. (c) Tavares, A.; Arruda, B. C.; Boes, E. S.; Stefani, V.; Stassen, H. K.; Campo, L. F.; Bechtold, I.
H.;Merlo, A. A. J. Braz. Chem. Soc. 2012, 23, 880.
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