European Journal of Organic Chemistry
10.1002/ejoc.201700711
FULL PAPER
was synthesized by well-known literature methods[45] for the synthesis of
Yield: 72 % (3.74 g, 7.21 mmol). m.p. = 139 °C. H-NMR (500 MHz, CDCl
1
,
3
7.
30 °C, δ [ppm]): 0.94 (s, 24 H, CH
3
), 3.08 (d, 3JHH = 42.4 Hz, 16 H, CH
.44 (dd, 3JHH = 8.3 Hz, 3JHH = 8.3 Hz, 2 H, CHarom), 8.18 (dd,
2
),
7
3
HH = 8.3 Hz, 4JHH = 1.6 Hz, 2 H, CHarom), 8.93 (dd, 3JHH = 4.3 Hz,
Cl , 30 °C, δ [ppm]):
), 7.49 (dd, 3JHH = 8.3 Hz,
HH = 8.3 Hz, 4
HH = 1.6 Hz, 2 H,
HH = 1.6 Hz, 2 H, CHarom). 13C-NMR
, 30 °C, δ [ppm]): 12.8 (CH ), 41.4 (CH ), 121.8 (CHarom),
), 131.6 (CHarom), 133.8 (C ), 143.5 (C ), 146.5 (CHarom), 159.6
gua). 13C-NMR (125 MHz, CD
Cl , 30 °C, δ [ppm]): 12.6 (CH ), 41.4
CH ), 121.6 (CHarom), 127.0 (C ), 131.4 (CHarom), 133.7 (C ), 143.5 (C ),
46.0 (CHarom), 159.4 (Cgua). MS-ES+ (MeCN, m/z (%)): 519.39 (100)
J
Physical Measurements: Spectra were recorded using the following
spectrometers. NMR: Bruker Avance 500. The NMR signals were
referenced to residual solvents measured relative to TMS. Line shape
analysis with Bruker Topspin 2.1 Line Shape Fitting. MS (ESI): Waters
Synapt 2G (QTOF). UV: Varian Cary 50. Fluorescence: Jasco
Spectrofluorometer FP-8300. IR: Bruker Vertex 70. Melting point: Büchi
B-545. Elemental analysis: vario MICRO Cube Elementar. Electrochem-
istry: Cyclic (CV) and square-wave voltammograms (SWV) were recorded
at ambient temperature with the PAR101 potentiostat from Metrohm using
the following three electrode arrangement: Pt working electrode (1 or
4JHH = 1.6 Hz, 2 H, CHarom). 1H-NMR (500 MHz, CD
2
2
1
J
.00 (s, 24 H, CH
3
), 3.16 (m, 16 H, CH
HH = 8.3 Hz, 2 H, CHarom), 8.23 (dd, 3
HH = 4.3 Hz, 4
2
3
J
J
CHarom), 8.90 (dd, 3
125 MHz, CDCl
27.0 (C
J
J
(
1
3
3
2
q
q
q
(
(
C
2
2
3
2
q
q
q
1
[
+
+
-1
M+H] , 1037.78 (9) [2M+H] . IR (KBr, 휈̃ [cm ]): 3057w, 2962m, 2930m,
866m, 1574s (C=N), 1543s (C=N), 1466m, 1416m, 1383m, 1350m,
1338m, 1294w, 1267s, 1225m, 1207w, 1136m, 1103w, 1074w, 1053w,
3
1.6 mm diameter), Ag/ 0.01 M AgNO / MeCN reference electrode and a Pt
2
wire counter electrode. Unless otherwise noted, the concentration of
analyte and supporting electrolyte ([Bu N]PF or [Bu N][B(C F )
1
038m, 1003m, 949w, 933w, 908w, 831w, 822w, 806w, 795w, 746m,
1
mM and 0.1 M, respectively. Ferrocene was added as an internal
7
2 2
19w, 654w, 615w, 548w, 492w, 455w, 436w, 395w. UV/Vis (CH Cl , λmax
standard after the measurements and all potentials are referenced relative
to the Fc/Fc+ couple. All measurements were carried out under argon
atmosphere, with absolute and vented solvents.
nm] (ε [M- cm ])): 360 (8590), 276 (27710). UV/Vis (MeCN, λmax [nm] (ε
1
-1
[
M-1 cm ])): 368 (10800), 277 (33960), 221 (42210). Fluorescence (CH
-1
,
[
2
Cl
2
excited at 277 nm, λEmission [nm]): 490, 531. Elemental analysis: calculated
-
1
for C30H N
46 8
(M = 518.75 g mol ) (%): C 69.46, N 21.60, H 8.94; found: C
General Method for the Synthesis of the Phenanthroline Bis-
guanidine Ligands: A suspension of 1,10-phenanthroline-5,6-diamine
69.37, N 21.41, H 8.75.
(
10 mmol, 4.21 g) and triethylamine (70 mmol, 7.08 g, 9.76 mL) in 250 mL
1
,10-Phenanthroline-5,6-bis(N,N,N´,N´-dipentyleneguanidine) (3): V3
acetonitrile was cooled down with an ice bath. The respective
chloroformamidinium chloride (20 mmol) was solved in 50 mL acetonitrile
and added dropwise to the reaction mixture. After 6 h at reflux and cooling
down to room temperature, the reaction mixture was treated with a solution
of NaOH (70 mmol, 2.80 g) in 5 mL water. Then the solvent and the
triethylamine were evaporated under reduced pressure. To the resulting
brown solid a 50 wt.-% aq. KOH (15 mL) was added to deprotonate the
bis-hydrochloride. It was diluted with water (50 mL) and extracted three
times with an organic solvent (50 mL). The collected organic layers were
(
20 mmol, 5.02 g) and methylene chloride for extraction were used. The
crude product was recrystallized with petroleum ether (80 - 110 °C). Yellow
powder. Yield: 81 % (4.60 g, 8.12 mmol). m.p. = 240 °C. 1H-NMR
(
7
2
CD
2
1
500 MHz, CDCl
3
, 30 °C, δ [ppm]): 1.35 (m, 24 H, CH
.47 (dd, 3JHH = 8.2 Hz, 3JHH = 8.2 Hz, 2 H, CHarom), 8.17 (d, 3JHH = 8.1 Hz,
H, CHarom), 8.95 (d, 3 HH = 2.8 Hz, 2 H, CHarom). 1H-NMR (500 MHz,
Cl , 30 °C, δ [ppm]): 1.42 (m, 24 H, CH ), 3.11 (s, 16 H, CH ), 7.51 (m,
H, CHarom), 8.20 (d, 3
HH = 7.5 Hz, 2 H, CHarom), 8.91 (m, 2 H, CHarom).
C-NMR (125 MHz, CDCl , 30 °C, δ [ppm]): 24.8 (CH ), 25.9 (CH ), 48.8
CH ), 122.0 (CHarom), 127.1 (C ), 131.6 (CHarom), 133.7 (C ), 143.4 (C ),
46.6 (CHarom), 160.2 (Cgua). 13C-NMR (125 MHz, CD
Cl , 30 °C, δ [ppm]):
4.9 (CH ), 25.9 (CH ), 48.8 (CH ), 121.8 (CHarom), 127.1 (C ), 131.3
), 143.4 (C
), 146.1 (CHarom), 159.9 (Cgua). MS-ES+
MeCN, m/z (%)): 567.39 (100) [M+H] , 1133.77 (23) [2M+H] . IR (KBr, 휈̃
2 2
), 3.05 (s, 16 H, CH ),
J
2
2
2
2
J
3
2 4
dried with Na SO and the solvent was removed under vacuum.
3
2
2
(
1
2
(
(
2
q
q
q
2
2
1
(
,10-Phenanthroline-5,6-bis(N,N,N´,N´-tetramethylguanidine) (1): V1
20 mmol, 3.42 g) and diethyl ether for extraction were used. The crude
2
2
2
q
CHarom), 133.7 (C
q
q
product was recrystallized with petroleum ether (80 - 110 °C). Yellow
powder. Yield: 84 % (3.41 g, 8.39 mmol). m.p. = 186 °C. 1H-NMR
(
3
+
+
-
1
[
cm ]): 3063w, 2932s, 2849m, 2361w, 2341w, 1591s (C=N), 1574s (C=N),
1551s (C=N), 1493w, 1468m, 1448m, 1421s, 1389m, 1367m, 1344m,
296w, 1248s, 1217m, 1192w, 1175w, 1157w, 1132m, 1080w, 1057w,
3 3
500 MHz, CDCl , 30 °C, δ [ppm]): 2.64 (s, 24 H, CH ), 7.45 (dd,
HH = 8.3 Hz, 3JHH = 8.3 Hz, 2 H, CHarom), 8.18 (dd, 3JHH = 8.4 Hz,
J
1
4JHH = 1.4 Hz, 2 H, CHarom), 8.93 (dd, 3JHH = 4.2 Hz, 4JHH = 1.7 Hz, 2 H,
CHarom). H-NMR (500 MHz, CD
7
3
1
1030w, 1016w, 966w, 920w, 879w, 852w, 800w, 744w, 660w, 617w, 582w,
2
Cl
2
, 30 °C, δ [ppm]): 2.69 (s, 24 H, CH
3
),
544w, 528w, 444w, 399w, 376w. UV/Vis (CH
2
Cl
2
, λmax [nm] (ε [M-1 cm ])):
-1
.49 (dd, 3JHH = 8.3 Hz, 3JHH = 8.3 Hz, 2 H, CHarom), 8.21 (dd,
61 (7490), 276 (25540). UV/Vis (MeCN, λmax [nm] (ε [M-1 cm ])): 367
-1
3
J
HH = 8.3 Hz, 4JHH = 1.6 Hz, 2 H, CHarom), 8.90 (dd, 3JHH = 4.2 Hz,
, 30 °C, δ [ppm]):
), 131.4 (CHarom), 133.2 (C ), 143.5
, 30 °C, δ
4JHH = 1.7 Hz, 2 H, CHarom). 13C-NMR (125 MHz, CDCl
9.3 (CH ), 122.0 (CHarom), 127.0 (C
(9130), 277 (29010), 223 (38260). Fluorescence (CH
2
Cl
2
, excited at
3
277 nm, λEmission [nm]): 490, 530. Elemental analysis: calculated for
3
(
3
q
q
-
1
C
34 46 8
H N (M = 566.80 g mol ) (%): C 72.05, N 19.77, H 8.18; found: C
), 146.7 (CHarom), 160.3 (Cgua). 1 C-NMR (125 MHz, CD
3
C
q
2
Cl
2
71.97, N 19.78, H 8.22.
[
ppm]): 39.0 (CH
3
), 121.8 (CHarom), 127.1 (C
q
), 131.2 (CHarom), 133.1 (C
q
),
+
1
43.4 (C
q
), 146.1 (CHarom), 160.0 (Cgua). MS-ES (MeCN, m/z (%)): 407.27
+
+
-1
1,10-Phenanthroline-5,6-bis(N,N´-ethylene-N,N´-dimethylguanidine)
4): V4 (20 mmol, 3.38 g) and methylene chloride for extraction were used.
(100) [M+H] , 813.53 (46) [2M+H] . IR (KBr, 휈̃ [cm ]): 3061w, 2991w,
(
2
1
9
5
922m, 2878m, 2806w, 1597s (C=N), 1574s (C=N), 1551s (C=N), 1500s,
466s, 1421s, 1375s, 1317m, 1234w, 1142s, 1068w, 1007m, 986m, 930w,
18w, 903w, 829w, 808w, 773w, 760w, 739m, 725w, 679w, 660w, 613w,
The crude product was recrystallized in a small amount of acetonitrile.
Yellow slightly brownish powder. Yield: 88 % (3.54 g, 8.79 mmol).
1
-
1
-1
m.p. = 283 °C. H-NMR (500 MHz, CDCl
3
, 30 °C, δ [ppm]): 2.62 (s, 12 H,
), 7.50 (dd, 3JHH = 8.2 Hz, 3
HH = 8.2 Hz, 2 H,
CHarom), 8.52 (dd, 3JHH = 8.2 Hz, 4
HH = 1.7 Hz, 2 H, CHarom), 8.95 (dd,
3JHH = 4.3 Hz, 4 HH = 1.7 Hz, 2 H, CHarom). 1H-NMR (500 MHz, CD
Cl
30 °C, δ [ppm]): 2.64 (s, 12 H, CH ), 3.30 (m, 8 H, CH ), 7.53 (dd,
2 2
86w, 546w, 446w, 403w. UV/Vis (CH Cl , λmax [nm] (ε [M cm ])): 363
-
1
-1
CH
3
), 3.28 (m, 8 H, CH
2
J
(
2
λ
8830), 279 (32040). UV/Vis (MeCN, λmax [nm] (ε [M cm ])): 368 (10440),
79 (33230), 219 (38640). Fluorescence (CH Cl , excited at 277 nm,
Emission [nm]): 490, 531. Elemental analysis: calculated for C22
J
2
2
J
2
2
,
30 8
H N
-
1
3
2
(
2
M = 406.54 g mol ) (%): C 65.00, N 27.56, H 7.44; found: C 64.89, N
3JHH = 8.3 Hz, 3JHH = 8.3 Hz, 2 H, CHarom), 8.53 (dd, 3JHH = 8.2 Hz,
4JHH = 1.7 Hz, 2 H, CHarom), 8.90 (dd, 3JHH = 4.3 Hz, 4JHH = 1.7 Hz, 2 H,
7.18, H 7.35.
CHarom). 13C-NMR (125 MHz, CDCl
CH ), 122.2 (CHarom), 127.6 (C ), 130.4 (C
46.9 (CHarom), 154.1 (Cgua). 13C-NMR (125 MHz, CD
, 30 °C, δ [ppm]): 34.2 (CH
), 132.6 (CHarom), 143.4 (C
Cl , 30 °C, δ [ppm]):
), 48.5
3
3
1
,10-Phenanthroline-5,6-bis(N,N,N´,N´-tetraethylguanidine) (2): V2
(
1
2
q
q
q
),
(
20 mmol, 4.54 g) and hexane for extraction were used. The crude product
2
2
was recrystallized with petroleum ether (80 - 110 °C). Yellow powder.
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