S. Kotowicz et al.
Dyes and Pigments 180 (2020) 108432
–
–
–
C); 1573 (C–C stretching in the aromatic ring); 1197
various groups, including also dicyanovinylene unit as sensitizers for
dye-sensitized solar cells (DSSC). Paramaguru et al. [21] also reported
pyrene dyes with various electron withdrawing groups, among them
(-C
–
N), 1604 (C
(C–N stretching); 689 (C–N deformation). Anal. Calcd for C16
(230.26 g/mol): C, 83.46; H, 4.38; N, 12.17; Found: C, 83.13; H, 4.68; N,
10 2
H N
�
2
-[(pyren-1-yl)methylene)malononitrile was presented and their optical
properties in various solvents were measured. Binding affinity with
TiO , and its dependence on the structure of the compounds was
12.11. DSC T
m
¼ 144 C.
2
2.1.3. 2-((naphthalen-1-yl)methylene)malononitrile (3)
Yellow powder. Yield: 87%. 1H NMR (400 MHz, CDCl
investigated. Experimental results were combined with theoretical cal-
culations. Breffke et al. [22] studied malononitrile derivatives bearing
naphthalene units in order to determine their potential utility as fluidity
probes. Katritzky et al. [23] synthesized compounds with dicyanoviny-
3
) δ 8.66 (s,
1H), 8.28 (d, J ¼ 7.3 Hz, 1H), 8.12 (d, J ¼ 8.2 Hz, 1H), 7.96 (d, J ¼ 8.3
1
3
Hz, 2H), 7.72–7.60 (m, 3H). C NMR (100 MHz, CDCl ) δ 157.65,
3
134.97, 133.81, 131.31, 129.59, 128.69, 128.62, 127.78, 127.43,
À 1
lene unit with phenyl,
α
-naphthyl, anthracene, phenanthrene and pyr-
125.52, 122.48, 113.81, 112.59, 85.59. FT-IR (KBr, v, cm ): FTIR (KBr,
À 1
–
–
ene moieties, and investigated their optical properties (UV–vis, PL) in
various solvents (toluene, diethyl ether, 1,4-dioxane, THF, ethyl acetate,
v, cm ): 3028 (C–H aromatic); 2227 (-C
–
N), 1590 (C C); 1566 (C–C
–
stretching in the aromatic ring); 1244 (C–N stretching); 778 (C–N
CH
2
Cl
2
, DMF and CH
3
CN). Intermolecular charge transfer properties
deformation). Anal. Calcd for C14
8
H N
2
(204.27 g/mol): C, 82.33; H,
�
and photoluminescence ability were discussed in relation to the solvents
polarity.
3.92; N, 13.72; Found: C, 82.48; H, 4.16; N, 13.90. DSC T
m
¼ 170 C.
In this paper the selected properties of seven aromatic malononitrile
2.1.4. 2-((naphthalen-2-yl)methylene)malononitrile (4)
1
derivatives with phenyl, biphenyl,
α-naphthyl, β-naphthyl, anthracene,
Light yellow-green powder. Yield: 84%. H NMR (400 MHz, CDCl
3
)
phenanthrene and pyrene moieties are presented. Even though these
compounds have been presented in the literature, their optical proper-
ties were not measured in the solid state and their electroluminescence
ability was not examined. The aim of this work focuses on the rela-
tionship between their aromatic part structure and properties important
for applications in optoelectronics. Geometric structures and frontier
molecular orbitals of the studied molecules, and the UV–Vis and PL
spectra were calculated using DFT and TD-DFT methods. Selected
δ 8.29 (s, 1H), 8.08 (dd, J ¼ 8.7, 1.8 Hz, 1H), 7.96 (d, J ¼ 8.4 Hz, 2H),
13
7.92–7.86 (m, 2H), 7.71–7.66 (m, 1H), 7.64–7.59 (m, 1H). C NMR
(100 MHz, CDCl
) δ 159.69, 136.07, 134.34, 132.86, 130.07, 129.79,
129.78, 128.77, 128.16, 127.86, 124.45, 114.07, 112.95, 82.66. FT-IR
3
À 1
À 1
–
(KBr, v, cm ): FTIR (KBr, v, cm ): 3031 (C–H aromatic); 2226 (-C
–
N),
C); 1585 (C–C stretching in the aromatic ring); 1183(C–N
(204.27
–
–
1623 (C
stretching); 743 (C–N deformation). Anal. Calcd for C14
g/mol): C, 82.33; H, 3.95; N, 13.72; Found: C, 82.60; H, 4.12; N, 13.69.
8 2
H N
0
�
compounds, that is, 2-((1,1 -biphenyl)-4-yl-methylene)malononitrile
DSC T
m
¼ 141 C.
and 2-((phenanthren-9-yl)methylene)malononitrile were tested in light
emitting diodes with guest-host configuration. Additionally, the com-
pound which showed the highest light harvesting efficiency (LHE), that
is, 2-((pyren-1-yl)methylene)malononitrile was tested with N719 in
DSSC device.
2.1.5. 2-((Anthracen-9-yl)methylene)malononitrile (5)
1
Red powder. Yield: 71%. H NMR (400 MHz, CDCl
3
) δ 8.95 (s, 1H),
8.66 (s, 1H), 8.10 (d, J ¼ 8.4 Hz, 2H), 7.93 (d, J ¼ 8.8 Hz, 2H), 7.71–7.65
1
3
(m, 2H), 7.62–7.56 (m, 2H). C NMR (100 MHz, CDCl
3
) δ 160.70,
1
32.60, 131.02, 129.65, 129.21, 128.45, 126.17, 124.00, 123.51,
À 1
2
. Experimental section
113.12, 111.51, 92.45. FT-IR (KBr, v, cm ): 3056 (C–H aromatic); 2229
–
–
–
C); 1575 (C–C stretching in the aromatic ring); 1211
(
-C
–
N), 1621 (C
All chemicals utilized in this work were purchased from Sigma
(C–N stretching); 722 (C–N deformation). Anal. Calcd for C18
(254.29 g/mol): C, 85.02; H, 3.96; N, 11.02; Found: C, 85.08; H, 4.18; N,
10 2
H N
Aldrich (Merck). The aluminum oxide 90 active neutral (CAS 1344-28-
�
1
) was purchased from Merck.
11.00. DSC T
m
¼ 213 C.
Characterization methods, films, OLED and DSSC preparations and
photovoltaic measurements are described in Supplementary Material.
2.1.6. 2-((Phenanthren-9-yl)methylene)malononitrile (6)
1
Yellow powder. Yield: 75%. H NMR (400 MHz, CDCl
3
) δ 8.77 (d, J
2
.1. Typical procedure for the synthesis of malononitrile derivatives
¼ 8.1 Hz, 1H), 8.70 (d, J ¼ 8.3 Hz, 1H), 8.64 (s, 1H), 8.48 (s, 1H), 8.02
d, J ¼ 7.9 Hz, 1H), 7.94 (d, J ¼ 8.2 Hz, 1H), 7.85–7.77 (m, 2H),
(
1
3
Into a solution of malononitrile (8.00 mmol) in methylene chloride
7.75–7.67 (m, 2H). C NMR (100 MHz, CDCl ) δ 158.65, 132.66,
3
(
(
20 mL), aluminum trioxide (800 mg) and the appropriate aldehyde
4.00 mmol) were added. The reaction mixture was stirred at room
131.37, 130.67, 130.26, 130.14, 128.84, 128.14, 128.08, 127.90,
126.76, 123.84, 123.53, 122.95, 113.72, 112.50, 85.97. FT-IR (KBr, v,
À 1
–
–
–
cm ): 3029 (C–H aromatic); 2226 (-C
–
N), 1613 (C C); 1569 (C–C
temperature for 24 h. After this time, the crude product was purified
using column chromatography (SiO , CH Cl ). All compounds were
prepared according to the method described in our previous paper [24].
stretching in the aromatic ring); 1197 (C–N stretching); 689 (C–N
2
2
2
deformation). Anal. Calcd for C18
H
10
N
2
(254.29 g/mol): C, 85.02; H,
�
3
.96; N, 11.02; Found: C, 85.08; H, 4.20; N, 11.03. DSC T
m
¼ 204 C.
2
.1.1. 2-((Phen-1-yl)methylene)malononitrile (1)
1
White powder. Yield: 89%. H NMR (400 MHz, CDCl
3
) δ 7.91 (d, J
2.1.7. 2-((Pyren-1-yl)methylene)malononitrile (7)
1
¼
7.5 Hz, 2H), 7.78 (s, 1H), 7.66–7.61 (m, 1H), 7.55 (t, J ¼ 7.6 Hz, 2H).
Orange powder. Yield: 61%. H NMR (400 MHz, CDCl
3
) δ 8.91 (s,
1
3
C NMR (100 MHz, CDCl
3
) δ 159.91, 134.63, 131.16, 130.78, 129.73,
1H), 8.82 (d, J ¼ 8.3 Hz, 1H), 8.38–8.32 (m, 3H), 8.31–8.24 (m, 3H),
À 1
13
1
13.76, 112.62, 83.20. FT-IR (KBr, v, cm ): 3031 (C–H aromatic); 2223
8.16–8.11 (m, 2H). C NMR (100 MHz, CDCl ) δ 156.46, 135.98,
3
–
–
–
C); 1567 (C–C stretching in the aromatic ring); 1186
(
-C
–
N), 1591 (C
131.58, 131.33, 131.30, 130.92, 130.58, 127.96, 127.66, 127.52,
127.20, 126.04, 125.35, 124.89, 124.35, 124.08, 121.31, 114.59,
(
C–N stretching); 677 (C–N deformation). Anal. Calcd for C10
6 2
H N
À 1
(
154.16 g/mol): C, 77.91; H, 3.92; N, 18.17; Found: C, 77.90; H, 4.11; N,
113.44, 83.40. FT-IR (KBr, v, cm ): 3039 (C–H aromatic); 2220
�
–
–
–
–
N), 1582 (C C); 1560 (C–C stretching in the aromatic ring); 1198
1
7.00. DSC T
m
¼ 88 C.
(-C
(
C–N stretching); 711 (C–N deformation). Anal. Calcd for C20
12 2
H N
0
2
.1.2. 2-((1,1 -biphenyl)-4-yl-methylene)malononitrile (2)
(280.32 g/mol): C, 85.69; H, 4.31; N, 9.99; Found: C, 85.60; H, 4.03; N,
1
�
Light yellow-green powder. Yield: 73%. H NMR (400 MHz, CDCl
3
)
9.61. DSC T
m
¼ 248 C.
δ 8.00 (d, J ¼ 8.3 Hz, 2H), 7.81–7.73 (m, 3H), 7.68–7.61 (m, 2H),
1
3
7
1
1
.53–7.41 (m, 3H). C NMR (100 MHz, CDCl ) δ 159.33, 147.46,
3
39.00, 131.51, 129.91, 129.30, 129.13, 128.14, 127.36, 114.03,
À 1
12.93, 82.12. FT-IR (KBr, v, cm ): 3063 (C–H aromatic); 2225
2