Supporting Information Synthesis and Characterization of New Self ...
Supporting Information
for
Synthesis and Characterization of New Self-Assembled Metallo-Polymers Containing Electron-withdrawing and Electron-donating Bis-Terpyridine Zn(II) moieties Florian Schlütter,1 Andreas Wild,1,2 Andreas Winter,2,3 Martin D. Hager,1,2 Anja Baumgaertel,1,2 Christian Friebe1,2 and Ulrich S. Schubert1,2,3,* 1
Laboratory of Organic and Macromolecular Chemistry, Friedrich-Schiller-University Jena,
Humboldtstr. 10, 07743 Jena, Germany 2 3
Dutch Polymer Institute (DPI), P.O. Box 902, 5600 AX Eindhoven, The Netherlands Laboratory of Macromolecular Chemistry and Nanoscience, Eindhoven University of
Technology, P.O. Box 513, 5600 MB Eindhoven, The Netherlands
Table of content: Materials and general experimental details
p
Instrumentation
pp 2 – 3
Synthesis of 4’-(4-ethynyl-phenyl)-[2,2’:6’,2’’]terpyridine (A)
p
Synthesis of the aromatic bromides (1–7)
pp 4 – 10
Synthesis of the bis-terpyridines (M1–M7)
pp 11 – 16
Synthesis of the metallo-polymers (P1–P7; R1+R2)
pp 17 – 20
1
H and 13C NMR spectra of the synthesized compounds
pp 21 – 31
MALDI-TOF mass spectra of the synthesized compounds
pp 32 – 35
1
2
3
Materials and general experimental details All chemicals and solvents were purchased from Biosolve, Aldrich, Acros Organics and Alfa Aesar and were of reagent grade and used as received unless otherwise specified. The solvents were dried and distilled according to standard procedures. Chromatographic separation was performed with standardized silica gel 60 (Merck) and aluminum oxide 90 neutral (Molekula). The reaction progress was controlled by thin layer chromatography (TLC) using aluminum sheets precoated with silica gel 60 F254 (Merck) and aluminum oxide 60 F254 neutral (Macherey-Nagel). 4,7-dibromo-[2,1,3]benzothiadiazole 1,1 4,7-diethynyl-[2,1,3]benzothiadiazole,2 2,5-dibromop-xylene,3 2,5-dibromo-terephthalic acid,4 2-bromo-5-iodo-terephthalic acid,5 2-(2-ethylhexyloxy-phenyl)acetonitrile,6 2,5-dibromo-3,4-dinitrothiophene,7,8 thiophene-3,4-diaminium dichloride,7,8
3,6-dibromo-1,2-phenylenediamine,9
1,2-bis(4-(octyloxyphenyl)ethane-1,2-
dione,10 and 5,10-diethyltetradecane-7,8-dione10 were prepared according to the literature.
Instrumentation 1D (1H,
13
C) and 2D (1H-1H gCOSY, HSQC, HMBC) nuclear magnetic resonance spectra
were recorded on a Bruker Cryomagnet BZH 400 (400 MHz), Bruker AC 300 (300 MHz) and Bruker AC 250 (250 MHz) instrument at 298 K. Chemical shifts are reported in parts per million (ppm, δ scale) relative to the residual signal of the deuterated solvent. Coupling constants are given in Hz. The reaction progress was controlled by GC-MS using a Shimadzu QP2010S. UV-vis absorption and PL emission spectroscopy were recorded on an Analytik Jena SPECORD 250 and Jasco FP-6500 spectrometer, respectively, at 298 K. Absolute photoluminescence quantum yields were evaluated at 298 K on a Hamamatsu Photonic MultiChannel Analyzer C 10027. For these techniques 10-6 M to 10-5 M solutions in chloroform or N,N-dimethylformamide (DMF) were used. Matrix-assisted laser desorption-ionization timeof-flight (MALDI-TOF) mass spectra were obtained from an Ultraflex III TOF/TOF mass 1
Pilgram, K.; Zupan, M.; Skiles, R. J. Heterocycl. Chem. 1970, 7, 629–640. Bangcuyo, C. G.; Evans, U.; Myrick, M. L.; Bunz, U. H. F. Macromolecules 2001, 34, 7592–7594. 3 Bonifacio, M. C.; Robertson, C. R.; Jung, J.-Y.; King, B. T. J. Org. Chem. 2005, 70, 8522–8526. 4 Yao, Y.; Tour, J. M. Macromolecules 1999, 32, 2455–2461. 5 Han, C.-C.; Balasubramanian, A. J. Polym. Sci., Part A: Polym. Chem. 2008, 46, 5483–5498. 6 Ahmed, A. M.; Feast, W. J.; Tsibouklis, J. Polymer 1993, 34, 1297–1302. 7 Kenning, D. D.; Mitchell, K. A.; Calhoun, T. R.; Funfar, M. R.; Sattler, D. J.; Rasmussen, D. C. J. Org. Chem. 2002, 67, 9073–9076. 8 Shahid, M.; Shahid, R. A.; Klemm, E.; Sensfuss, S. Macromolecules 2006, 7844–7853. 9 Huo, L. J.; Tan, Z. A.; Zhou, Y.; Zhou, E. J.; Han, M. F.; Li, Y. F. Macromol. Chem. Phys. 2007, 208, 1294– 1300. 10 Karsten, B. P.; Viani, L.; Gierschner, J.; Cornil, J.; Janssen, R. A. J. J. Phys. Chem. 2008, 112, 10764–10773. 2
2
spectrometer with dithranol as matrix in reflector mode. Elemental analysis was carried out on a CHN-932 Automat Leco instrument.
4’-(4-Ethynyl-phenyl)-[2,2’:6’,2’’]terpyridine (A)
To a solution of 4-ethynylbenzaldehyde (2.05 g, 15.8 mmol) in ethanol (41 mL) was added 2-acetylpyridine (4.10 g, 33.9 mmol) and sodium hydroxide (1.28 g, 32.0 mmol). After stirring (30 min) until complete dissolving of sodium hydroxide, ammonium hydroxide solution (25%, 41 mL) was slowly added. The resulting red suspension was stirred for 24 h at room temperature. Subsequent filtration of the formed precipitate, washing with methanol and water and three times recrystallization from ethanol yielded the desired product as a white powder (2.00 g, 38%). 1
H NMR (CDCl3, 250 MHz, δ): 3.19 (s, 1H, C≡C-H), 7.36 (m, 2H, H5,5’’), 7.65 (d, 3J =
7.9 Hz, 2H, Ha,b), 7.87 (m, 4H, H4,4’’, Ha,b), 8.66 (d, 3J = 8 Hz, 2H, H3,3’’), 8.73 (s, 2H, H3’,5’), 8.74 (m, 2H, H6,6’’). MALDI-TOF MS (dithranol): m/z = 334.11 (100%) [M+H]+. Anal. Calcd. for C23H15N3: C, 82.86%; H, 4.54%; N, 12.60%. Found: C, 82.78%; H, 4.48%; N 12.45%.
3
4,7-Dibromo-[2,1,3]benzothiadiazole (1)
Scheme 1 Schematic representation of the synthesis of 4,7-dibromo-[2,1,3]benzothiadiazole (1).1
Dioctyl 2,5-dibromo-terephthalate (2)
Scheme 2 Schematic representation of the synthesis of dioctyl 2,5-dibromo-terephtalate (2).4 2,5-Dibromo-terephthalic acid4 (2.60 g, 8.0 mmol) was dissolved in thionyl chloride (26 mL, large excess) and stirred at 80 °C for 3 h. The remaining thionyl chloride was removed under reduced pressure (first on a rotary evaporator, later on high vacuum) afterwards. A solution of n-octanol (2.11 g, 16.2 mmol) in CH2Cl2 (25 mL) was slowly dropped to the white solid accompanied by intensive evolution of HCl. The resulting suspension was heated under reflux and the reaction progress was monitored by GC-MS. After 5 h ice water (40 mL) was added in order to terminate the reaction. The organic phase was separated, washed three times with saturated aq. NH4Cl and dried over MgSO4. After evaporation of the solvent, the obtained oil was crystallized from ethanol yielding 2 as a white powder (3.50 g, 79%). 1H NMR (CDCl3, 400 MHz, δ): 0.88 (m, 6H, CH3), 1.22–1.48 (m, 20H, CH2), 1.74–1.81 (m, 4H, OCH2-CH2), 4.34 (mc, 4H, O-CH2), 8.01 (s, 2H, H1). Anal. Calcd. for C24H36Br2O4: C, 52.57%; H, 6.62%. Found: C, 52.48%; H, 6.55%. 4
5,8-Dibromo-2,3-bis(2-ethylhexyl)quinoxaline (3)
Scheme
3
Schematic
representation
of
the
synthesis
of
5,8-dibromo-2,3-bis(2-
ethylhexyl)quinoxaline (3).9,10 3,6-Dibromo-1,2-phenylendiamine9 (1.00 g, 3.8 mmol) and 5,10-diethyltetradecane-7,8dione10 (1.07 g, 3.8 mmol) were dissolved in ethanol (50 mL) and a catalytic amount of glacial acetic acid was added. The resulting mixture was heated under reflux and the reaction progress was monitored by GC-MS. After 19 h the reaction mixture was cooled to room temperature and the solvent was evaporated. Purification of the crude product by column chromatography (silica, n-heptane/CHCl3 3:1) yielded 3 as a yellow oil (1.01 g, 52%). 1
H NMR (CDCl3, 400 MHz, δ): 0.82–0.88 (m, 12H, CH3), 1.22–1.44 (m, 16H, CH2), 2.17
(mc, 2H, tC-H), 2.99 (d, 3J = 6.6 Hz, 4H, N=C-CH2), 7.81 (s, 2H, H1).
13
C NMR (CDCl3,
100 MHz, δ): 10.9 (CH3) , 23.1, 26.0, 28.8, 32.8, 38.0 (CH2), 38.8 (tCH), 118.3 (C-Br), 131.9 (C1-H), 142.9 (Ct,
aryl
), 158.1 (N=C-). Anal. Calcd. for C24H36Br2N2: C 56.26%, H 7.08.
Found: C 56.38%, H 7.23%.
5
2,5-Dibromo-1,4-(phenylene)bis(2-(4-(2-ethylhexyloxy)phenyl)acrylonitrile (4)
Scheme 4 Schematic representation of the synthesis of 2,5-dibromo-1,4-(phenylene)bis(2-(4(2-ethylhexyloxy)phenyl)acrylonitrile (4).6 To a solution of 2,5-dibromo-terephthalaldehyde (100 mg, 0.3 mmol) and 2-(4-(2-ethylhexyloxyphenyl)acetonitrile6 (196 mg, 0.8 mmol) in methanol (10 mL) was added sodium methanolate (25 mg, 0.5 mmol). The resulting solution was degassed with argon for 1 h and afterwards stirred under reflux for 12 h. During the reaction an orange solid precipitated. The precipitate was filtered off and washed intensively with methanol. Finally 4 was obtained as a yellow-orange solid (152 mg, 60%). 1
H NMR (CDCl3, 250 MHz, δ): 0.82–0.92 (m, 12H, CH3), 1.22–1.56 (m, 16H, CH2), 1.77
(mc, 2H, tC-H), 3.92 (d, 3J = 5.8 Hz, 4H, O-CH2), 6.99 (d, 3J = 8.8 Hz, 4H, Ha), 7.63 (d, 3
J = 5.0 Hz, 4H, Hb), 7.68 (s, 2H, H1), 8.34 (s, 2H, =C-H2). 13C NMR (CDCl3, 100 MHz, δ):
11.1, 14.0 (CH3), 23.0, 23.9, 29.1, 30.5 (CH2), 39.4 (tCH), 70.9 (O-CH2), 115.2 (Ca), 116.1 (C-Br), 116.8 (C≡N), 123.9 (NC-C-C), 125.6 (NC-C), 127.8 (Cb), 133.1 (C1-H), 135.8 (=C-C), 136.5 (NC-C=C), 161.2 (O-Caryl). Anal. Calcd. for C40H46Br2N2O2: C, 64.35%; H, 6.21%; N, 3.75%. Found: C, 64.12%; H, 5.88%; N, 3.52%.
6
5,7-Dibromo-2,3-bis(4-(octyloxyphenyl)thieno[3,4-b]pyrazine (5)
Scheme
5
Schematic
representation
of
the
synthesis
of
5,7-dibromo-2,3-bis(4-
(octyloxyphenyl)thieno[3,4-b]pyrazine.7,8,10 2,3-Bis(4-(octyloxyphenyl)thieno[3,4-b]pyrazine: To a suspension of thiophene-3,4-diaminohydrochloride7,8 (490 mg, 2.6 mmol) and 1,2-bis(4(octyloxyphenyl)ethane-1,2-dione10 (1.22 g, 2.6 mmol) in ethanol (40 mL) was slowly dropped triethylamine (556 mg, 5.5 mmol). The mixture was stirred for 48 h at room temperature in the absence of light. Afterwards the solvent was evaporated without heating. The black residue was washed with petrol ether and further purified by column chromatography (silica, CH2Cl2). The desired product was obtained as yellow oil, which crystallizes under cooling and decomposes in the presence of light (571 mg, 40%). 1
H NMR (CDCl3, 300 MHz, δ): 0.89 (mc, 6H, CH3), ), 1.22–1.46 (m, 20H, CH2), 1.66–1.82
(m, 4H, OCH2-CH2), 3.97 (mc, 4H, O-CH2), 6.85 (d, 3J = 8.7 Hz, 4H, Ha), 7.38 (d, 3
J = 8.7 Hz, 4H, Hb), 7.97 (s, 2H, H1). 13C NMR (CDCl3, 75 MHz, δ): 14.1 (CH3), 22.6, 26.0,
29.2, 29.4, 31.8 (CH2), 68.1 (O-CH2), 114.2 (Ca), 116.8 (C1-H), 131.1 (Cb), 131.6 (Ct, 141.6 (Ct,
aryl
),
aryl
), 153.1 (N=C), 159.8 (O-Caryl). Anal. Calcd. could not be obtained due to
decomposing in the presence of light.
5,7-Dibromo-2,3-bis(4-(octyloxyphenyl)thieno[3,4-b]pyrazine (5): A solution of 2,3-bis(4-(octyloxyphenyl)thieno[3,4-b]pyrazine (225 mg, 0.4 mmol) in dry DMF (10 mL) was degassed with argon for 1 h in the absence of light. The solution was cooled with an ice/CaCl2/NaCl mixture. At –15 °C N-bromosuccinimide (NBS, 148 mg, 0.8 mmol) dissolved in dry DMF (3 mL) was slowly added via a syringe. The solution was further 7
stirred in the absence of light for 3 h at –15 °C. Subsequently, the green solution was poured onto ice and extracted three times with diethyl ether. The organic layers were combined, washed with water and dried over MgSO4. Evaporation of the solvent and column chromatography (silica, CH2Cl2:n-hexane 2:1) yielded 5 as green-yellow solid which was highly light sensitive (154 mg, 53%). 1
H NMR (CDCl3, 300 MHz, δ): 0.89 (mc, 6H, CH3), 1.20–1.46 (m, 20H, CH2), 1.66–1.82 (m,
4H, OCH2-CH2), 3.97 (mc, 4H, O-CH2), 6.85 (d, 3J = 8.7 Hz, 4H, Ha), 7.46 (d, 3J = 8.7 Hz, 4H, Hb). 13C NMR (CDCl3, 75 MHz, δ): 14.1 (CH3), 22.6, 26.0, 29.2, 29.4, 31.8 (CH2), 68.1 (O-CH2), 114.2 (Ca), 118.7 (C1-Br), 131.1 (Cb), 131.6 (Ct, aryl), 141.6 (Ct, aryl), 153.1 (N=C), 159.8 (O-Caryl). Anal. Calcd. could not be obtained due to decomposing in the presence of light.
Tetraoctyl 5,5’-([2,1,3]benzothiadiazole-4,7-bis(ethyne-2,1-diyl))bis(2-bromo-terephthalate) (6)
Scheme
6
Schematic
representation
of
the
synthesis
of
tetraoctyl
([2,1,3]benzothiadiazole-4,7-bis(ethyne-2,1-diyl))bis(2-bromo-terephthalate) (6).3-5
8
5,5’-
A solution of dioctyl 2-bromo-5-iodo-terephthalate5 (A, 300 mg, 0.5 mmol) and 4,7diethynyl-[2,1,3]benzothiadiazole2 (B, 42 mg, 0.2 mmol) in THF (30 mL) and diisopropylamine (12 mL) was degassed with argon for 2 h and cooled to 0 °C. Tetrakis(triphenylphosphine)palladium(0) (3 mol%, 8 mg) and copper(I)iodide (3 mol%, 1.3 mg) were added to this solution and stirred 7 h at 0 °C. Afterwards the reaction mixture was allowed to warm up to room temperature and stirred overnight. Thereafter the solution was filtered in order to remove the precipitated ammonia salt and the precipitate was washed intensively with THF. Addition of dichloromethane (10 mL), washing the organic solution with sat. aq. NH4Cl/EDTA solution and evaporation of the solvents yielded the crude product. Finally, 6 was obtained after column chromatography (silica, CH2Cl2:n-hexane 2:1) and precipitation from methanol as intense yellow powder (116 mg, 45%). 1
H NMR (CDCl3, 250 MHz, δ): 0.87 (mc, 12H, CH3), ), 1.13–1.52 (m, 40H, CH2), 1.69–1.87
(m, 8H, OCH2-CH2), 4.32–4.45 (m, 8H, O-CH2), 7.87 (s, 2H, H3), 8.14 (s, 2H, H2) , 8.30 (s, 2H, H1). 13C NMR (CDCl3, 75 MHz, δ): 14.05 (CH3), 22.6, 26.0, 28.5, 28.6, 29.1, 29.1, 29.2, 31.8 (CH2), 66.3, 66.5 (O-CH2), 91.0 (C≡C), 95.1 (C≡C), 114.2 (≡C-C), 117,2 (C-Br), 117.4, 121.5, 122.1, 133.0, 134.9, 135.7, 136.2, 136.6, 140.3 (Caryl), 164.1 (C=O), 165.0 (C=O). Anal. Calcd. for C58H74Br2N2O8S: C 62.25%, H 6.67%, N 2.50% S 2.87%. Found: C 61.87%, H 6.35%, N 2.78%, S 2.49%.
Tetraoctyl 5,5’-(2,5-bis(octyloxy)-1,4-phenylene)bis(ethyne-2,1-diyl)bis(2-bromoterephthalate) (7)
Scheme 7 Schematic representation of the synthesis of tetraoctyl 5,5’-(2,5-bis(octyloxy)-1,4phenylene)bis(ethyne-2,1-diyl)bis(2-bromoterephthalate).4,5
9
A solution of dioctyl 2-bromo-5-iodo-terephthalate5 (A, 500 mg, 0.8 mmol) and 1,4diethynyl-2,5-bis(octyloxy)benzene (150 mg, 0.4 mmol) in THF (30 mL) and diisopropylamine (12 mL) was degassed with argon for 2 h and cooled to 0 °C. Tetrakis(triphenylphosphine)palladium(0) (2 mol%, 10 mg) and copper(I)iodide (2 mol%, 2.2 mg) were added to the solution and stirred 7 h at 0 °C. The reaction mixture was allowed to warm up to room temperature and stirring was continued overnight. Subsequently, the solution was filtered in order to remove the precipitated ammonia salt and the precipitate was washed intensively with THF. Addition of CH2Cl2 (10 mL), washing with sat. aq. NH4Cl/EDTA solution and evaporation of the solvents yielded the crude product. Finally, 7 was obtained after column chromatography (silica, CH2Cl2:n-hexane 1:1) and two times precipitation from methanol as yellow powder (116 mg, 45%). 1
H NMR (CDCl3, 300 MHz, δ): 0.87 (mc, 18H, CH3), 1.17–1.56 (m, 60H, CH2), 1.72–1.91
(m, 12H, OCH2-CH2), 4.03 (mc, 8H, O-CH2), 4.36 (mc, 4H, O-CH2), 7.04 (s, 2H, H3), 8.00 (s, 2H, H2), 8.24 (s, 2H, H1). 13C NMR (CDCl3, 75 MHz, δ): 14.1 (CH3), 22.6, 25.9, 26.0, 26.1, 28.5, 28.6, 29.1, 29.2, 29.2, 29.3, 31.8, 31.8 (CH2), 66.0, 66.4, 69.8 (O-CH2), 92.2 (C≡C), 93.0 (C≡C), 114.2 (≡C-C), 117.1 (C-Br), 120.4, 123.1, 134.5, 135.4, 136.0, 136.4, 153.9 (Caryl), 164.2 (C=O), 165.1 (C=O). Anal. Calcd. for C74H108Br2O10: C 67.46%, H 8.26%, Found: C 67.07%, H 7.88%.
10
General procedure for the synthesis of π-conjugaeted bis-terpyridines by Sonogashira coupling To an argon degassed mixture of 4’-(4-ethynylphenyl)-[2,2’:6’,2’’]terpyridine (A, 0.5 mmol) and an aromatic bromide (1–7, 0.25 mmol) in dry THF (30 mL) and dry triethylamine or diisopropylamine (10 mL) were added tetrakis(triphenylphospine)palladium(0) (10 mol%) and copper(I)iodide (10 mol%) and the reaction mixture was refluxed until TLC indicated complete conversion (5 to 48 h). After cooling to room temperature, the precipitated ammonia salt was filtered off and washed intensively with THF. Dichloromethane was added and the solution was washed with sat. aq. NH4Cl/EDTA solution and dried over MgSO4. After removal of the solvents, the product was precipitated from methanol. Further purification was achieved by column chromatography (aluminum oxide, CH2Cl2 as eluent). When applicable, deviations from this general protocol are given below.
4,7-Bis([2,2’:6’,2’’]terpyridine)-ethynyl-2,1,3-benzothiadiazole (M1)
According to the above mentioned general procedure, M1 was obtained after filtration from the reaction mixture, intensive washing with water and recrystallization (several times) from a large amount of chloroform as orange solid (169 mg, 85%). 1
H and
13
C NMR spectra could not be obtained due to the very low solubility of M1 in
organic solvents. MALDI-TOF MS (dithranol): m/z = 799.25 (100%, [M+H]+). UV-vis (CHCl3) (ε/M-1·cm-1): λmax/nm = 255 (64,350), 282 (81,400), 318 (58,000), 423 (20,700). Emission (CHCl3) (excitation in nm): λPL,max/nm = 503 (423). Anal. Calcd. for C52H30N8S: C, 78.18%; H, 3.78%; N, 14.03%; S, 4.01%. Found: C, 77.98%; H, 4.02%; N, 14.21%; S, 3.76%.
11
Dioctyl 2,5-bis([2,2’:6’,2’’]terpyridine)-ethynyl-terephthalate (M2)
According to the above mentioned general procedure M2 was obtained as a yellow solid (184 mg, 70%). 1
H NMR (CDCl3, 300 MHz, δ): 0.84 (mc, 6H, CH3), 1.19–1.51 (m, 20H, CH2), 1.78–1.88 (m,
4H, OCH2-CH2), 4.44 (mc, 4H, O-CH2), 7.37 (mc, 4H, H5,5’’), 7.73 (d, 3J = 7.5 Hz, 4H, Ha,b), 7.88 (mc, 8H, H4,4’’, Ha,b), 7.95 (d, 3J = 7.5 Hz, 4H, Ha,b), 8.26 (s, 2H, HA), 8.69 (d, 3
J = 7.8 Hz, 4H, H3,3’’), 8.75 (d, 3J = 3.9 Hz, 4H, H6,6’’), 8.76 (s, 4H, H3’,5’). 13C NMR (CDCl3,
75 MHz, δ): 14.1 (CH3), 22.6, 26.1, 28.7, 29.2, 29.3, 31.8 (CH2), 66.1 (O-CH2), 88.9 (C≡C), 96.4 (C≡C), 118.7 (≡C-C), 121.4, 122.9, 123.6, 123.9, 127.3, 132.4, 134.5, 136.1, 136.9, 138.8, 149.2, 149.3, 156.1, 156.1 (Caryl), 165.1 (C=O). MALDI-TOF MS (dithranol): m/z = 1053.51 (100%, [M+H]+). UV-vis (CHCl3) (ε/M-1·cm-1): λmax/nm = 254 (64,400), 279 (65,000), 326 (66,000), 373 (59,300). Emission (CHCl3) (excitation in nm): λPL,max/nm = 424 (373). Anal. Calcd. for C70H64N6O4: C, 79.82%; H, 6.12%; N, 7.98%. Found: C, 79.45%; H, 6.46%; N 7.79%.
5,8-Bis([2,2’:6’,2”]terpyridine)-ethynyl-2,3-bis(2-ethylhexyl)quinoxaline (M3)
According to the above mentioned general procedure M3 was obtained as a yellow-orange solid (164 mg, 65%).
12
1
H NMR (CDCl3, 300 MHz, δ): 0.87 (mc, 6H, CH3), 1.00 (mc, 6H, CH3), 1.23–1.58 (m, 16H,
CH2), 2.31 (mc, 2H, tC-H), 3.05 (d, 3J = 6.9 Hz, 4H, N=C-CH2), 7.38 (mc, 4H, H5,5’’), 7.81 (d, 3
J = 8.4 Hz, 4H, Ha,b), 7.91 (mc, 10H, H4,4’’, Ha,b, HA), 7.98 (d, 3J = 8.4 Hz, 4 H, Ha,b), 8.70 (d,
3
J = 8.1 Hz, 4H, H3,3’’), 8.76 (d, 3J = 4.2 Hz, 4H, H6,6’’), 8.79 (s, 4H, H3’,5’). 13C NMR (CDCl3,
75 MHz, δ): 10.9, 14.1 (CH3), 23.1, 26.0, 28.9, 32.9 (CH2), 38.1 (tCH), 39.1 (N=C-C), 88.5 (C≡C), 96.7 (C≡C), 118.7 (≡C-C), 121.4, 123.1, 123.9, 124.3, 127.3, 131.8, 132.4, 136.9, 138.4, 140.9, 149.2, 149.4, 156.1, 156.2, 157.4 (Caryl). MALDI-TOF MS (dithranol): m/z = 1017.53 (100% [M+H]+). UV-vis (CHCl3) (ε/M-1·cm-1): λmax/nm = 267 (42,600), 284 (39,800), 318 (33,750), 395 (30,000). Emission (CHCl3) (excitation in nm): λPL,max/nm = 443 (395). Anal. Calcd. for C70H64N8: C, 82.64%; H, 6.34%; N, 11.01%. Found: C, 82.85%; H, 5.97%; N, 11.01%.
2,5-Bis([2,2’:6’,2’’]terpyridine)-ethynyl-1,4-(phenylene)bis(2-(4-(2-ethylhexyloxyphenyl)-acrylonitrile (M4)
According to the above mentioned general procedure M4 was obtained as a yellow-orange solid (187 mg, 72%). 1 t
H NMR (CDCl3, 300 MHz, δ): 0.95 (mc, 12H, CH3), 1.22–1.58 (m, 16H, CH2), 1.75 (mc, 2H,
C-H), 3.94 (mc, 4H, O-CH2 E+Z isomer), 6.88–7.06 (d, 3J = 8.4 Hz, 4 H, Ha,b), 7.37 (mc, 8H,
H5,5’’, Ha,b), 7.73 (d, 3J = 5.7 Hz, 4H, Ha,b), 7.90 (mc, 8H, H4,4’’, Ha,b), 8.06 (s, 2H, HA), 8.46– 8.54 (s, 2H, C=C-HB E+Z isomer), 8.69 (d, 3J = 8.4 Hz, 4H, H3,3’’), 8.77 (mc, 8H, H6,6’’, H3’,5’). 13
C NMR (CDCl3, 75 MHz, δ): 11.1, 14.1 (CH3), 23.0, 23.8, 29.1, 30.5 (CH2), 39.4 (tCH),
70.8 (O-CH2), 87.9 (C≡C), 97.9 (C≡C), 114.2 (≡C-C), 115.1, 115.0, 117.5, 118.7, 118.8, 121.4, 123.1, 123.9, 126.3, 127.5, 127.6, 131.0, 132.1, 132.3, 132.5, 135.7, 136.3, 136.9, 139.0, 149.1, 156.1 (Caryl), 160.9 (O-C=). MALDI-TOF MS (dithranol): m/z = 1251.69 (100%, [M+H]+). UV-vis (CHCl3) (ε/M-1·cm-1): λmax/nm = 253 (72,700), 283 (84,750), 318 (33,750), 354 (88,100). Emission (CHCl3) (excitation in nm): λPL,max/nm = 484 (395), 510 (395). Anal. Calcd. for C86H74N8O2: C, 82.53%; H, 5.96%; N, 8.95%. Found: C, 82.18%; H, 5.58%; N 8.56%. 13
5,7-Bis([2,2’:6’,2’’]terpyridine)-ethynyl-2,3-bis(4-(octyloxy)phenyl)thieno[3,4-b]pyrazine (M5)
According to the above mentioned general procedure M5 was obtained as a red solid (225 mg, 75%). 1
H NMR (CDCl3, 300 MHz, δ): 0.90 (mc, 6H, CH3), 1.23–1.31 (m, 20H, CH2), 1.78–1.88 (m,
4H, OCH2-CH2), 4.00 (mc, 4H, O-CH2), 6.88 (d, 3J = 9.0 Hz, 4 H, Ha,b) 7.40 (mc, 4H, H5,5’’), 7.56 (d, 3J = 8.7 Hz, 4H, Ha,b), 7.78 (d, 3J = 8.4 Hz, 4H, Ha,b), 7.90 (mc, 4H, H4,4’’), 7.97 (d, 3
J = 8.4 Hz, 4H, Ha,b), 8.70 (d, 3J = 7.8 Hz, 4H, H3,3’’), 8.77 (mc, 8H, H6,6’’, H3’,5’). 13C NMR
(CDCl3, 75 MHz, δ): 14.1 (CH3), 22.7, 26.0, 29.2, 29.4, 29.5, 31.8 (CH2), 68.1 (O-CH2), 88.9 (C≡C), 96.5 (C≡C), 114.2, 115.2, 118.7, 121.4, 123.6, 123.9, 127.3, 131.2, 131.6, 132.3, 136.9, 138.6, 142.8, 149.2, 149.3, 156.1, 156.1 (Caryl), 160.3 (C=O). MALDI-TOF MS (dithranol): m/z = 1207.61 (100%, [M+H]+). UV-vis (CHCl3) (ε/M-1·cm-1): λmax/nm = 255 (76,400), 283 (93,500), 346 (61,250), 436 (20,400), 498 (20,200). Emission (CHCl3) (excitation in nm): λPL,max/nm = 587 (498). Anal. Calcd. for C80H70N8O2S: C, 79.57%; H, 5.84%; N, 9.28%; S, 2.66%. Found: C, 79.41%; H, 5.99%; N, 9.08%; S, 2.92%.
14
Tetraoctyl
5,5’-(2,1,3-benzothiadiazole-4,7-diylbis(ethyne-2,1-diyl))bis(2-((4-
([2,2’:6’,2’’]terpyridine-4’-yl)phenyl)ethynyl)terephthalate) (M6)
According to the above mentioned general procedure M6 was obtained after two times column chromatographic purification and three times precipitation from methanol as an orange solid (121 mg, 30%). 1
H NMR (CDCl3, 300 MHz, δ): 0.86 (mc, 12H, CH3), 1.19–1.52 (m, 40H, CH2), 1.77–1.89
(m, 8H, OCH2-CH2), 4.40–4.49 (m, 8H, O-CH2), 7.38 (mc, 4H, H5,5’’), 7.56 (d, 3J = 8.7 Hz, 4H, Ha,b), 7.75 (d, 3J = 8.4 Hz, 4H, Ha,b), 7.95 (mc, 6H, H4,4’’, HC), 7.97 (d, 3J = 9.0 Hz, 4H, Ha,b), 8.32 (s, 2H, HB), 8.40 (s, 2H, HA), 8.70 (d, 3J = 7.8 Hz, 4H, H3,3’’), 8.76 (mc, 4H, H6,6’’), 8.78 (s, 4H, H3’,5’).
13
C NMR (CDCl3, 75 MHz, δ): 14.1 (CH3), 22.6, 26.1, 28.6, 29.1, 29.2,
29.2, 31.8 (CH2), 66.2 (O-CH2), 88.9 (C≡C), 95.1 (C≡C), 116.0, 118.7, 118.7, 121.4, 123.2, 124.0, 127.3, 127.4, 132.4, 139.0, 139.3, 142.2, 146.90, 149.2, 154.3, (Caryl), 156.0, 156.1 (C=O). MALDI-TOF MS (dithranol): m/z = 1623.85 (100%, [M+H]+). UV-vis (CHCl3) (ε/M-1·cm-1): λmax/nm = 255 (55,500), 276 (64,450), 316 (48,300), 359 (30,300), 433 (32,300). Emission (CHCl3) (excitation in nm): λPL,max/nm = 498 (433). Anal. Calcd. for C104H102N8O8S: C, 76.91%; H, 6.33%; N, 6.90%; S, 1.97%. Found: C, 76.65%; H, 5.98%; N, 6.61%; S 1.80%.
15
Tetraoctyl
5,5’-(2,5-bis(octyloxy)-1,4-phenylene)bis(ethyne-2,1-diyl)bis(2-((4-
([2,2’:6’,2’’]terpyridine-4’-yl)phenyl)ethynyl)terephthalate) (M7)
According to the above mentioned general procedure M7 was obtained after two times column chromatographic purification and three times precipitation from methanol as an orange solid (141 mg, 31%). 1
H NMR (CDCl3, 300 MHz, δ): 0.82–1.00 (m, 18H, CH3), 1.21–1.65 (m, 60H, CH2), 1.76–
1.93 (m, 12H, OCH2-CH2), 3.99–4.09 (m, 4H, O-CH2), 4.34–4.54 (m, 8H, O-CH2), 7.05 (s, 2H, HC), 7.39 (mc, 4H, H5,5’’), 7.74 (d, 3J = 8.1 Hz, 4H, Ha,b), 7.94 (mc, 6H, H4,4’’, Ha,b), 8.25 (s, 2H, HB), 8.26 (s, 2H, HA), 8.70 (d, 3J = 7.8 Hz, 4H, H3,3’’), 8.76 (mc, 4H, H6,6’’), 8.78 (s, 4H, H3’,5’). 13C NMR (CDCl3, 75 MHz, δ): 14.1 (CH3), 22.6, 26.1, 28.6, 29.1, 29.2, 29.3, 31.8 (CH2), 66.2 (O-CH2), 88.9 (C≡C), 95.1 (C≡C), 116.0, 118.7, 118.7, 121.4, 123.2, 124.0, 127.3, 127.4, 132.4, 139.0, 139.3, 142.2, 147.0, 149.2, 154.3, (Caryl), 156.0, 156.1 (C=O). MALDI-TOF MS (dithranol): m/z = 1822.32 (100%, [M+H]+). UV-vis (CHCl3) (ε/M-1·cm-1): λmax/nm = 283 (34,450), 327 (34,000), 427 (23,900). Emission (CHCl3) (excitation in nm): λPL,max/nm = 490 (427). Anal. Calcd. for C120H136N6O10: C, 79.09%; H, 7.52%; N, 4.61%. Found: C, 78.71%; H, 7.58%; N, 4.32%.
16
General procedure for the metallo-polymerization To the bis-terpyridine monomers M1–M7 (0.025 mmol) in N-methylpyrrolidone (NMP, 5 mL), zinc(II) acetate (0.025 mmol) in NMP (1 mL) was added. The resulting solution was stirred at 105 °C under argon atmosphere for 24 h. An excess of NH4PF6 (50 mg) was added to the hot solution and stirring was continued for 1 h. The solution was poured into methanol (50 mL), and the resulting metallo-polymer was filtered off and washed with methanol (10 mL). Further purification was achieved by repeated dissolving of the metallo-polymer in NMP (2 mL) and precipitation from diethyl ether. Finally, the products were dried under vacuum at 40 °C for 24 h.
Metallo-homo polymer P1: {[Zn(M1)](PF6)2}n.
According to the above mentioned procedure, homo polymer P1 was obtained as a yellow solid (22 mg, 84%). 1
H NMR (DMSO-d6, 300 MHz, δ): 7.50 (mc, H5,5’’), 7.98 (mc, H6,6’’), 8.32 (mc, Haryl), 8.56
(mc, H4,4’’), 8.76 (mc, Haryl), 9.17 (mc, H3,3’’), 9.46 (mc, H3’,5’). Anal. Calcd. for C52H30F12N8P2SZn: C 54.11%, H 2.62%, N 9.71%, S 2.78%. Found: C 54.61%, H 2.34%, N 8.98%, S 2.12%.
Metallo-homo polymer P2: {[Zn(M2)](PF6)2}n.
According to the above mentioned procedure, homo polymer P2 was obtained as yellow solid (29 mg, 82%). 17
1
H NMR (DMSO-d6, 300 MHz, δ): 0.72 (mc, CH3), 1.09–1.22 (m, CH2), 4.44 (mc, O-CH2),
7.52 (mc, H5,5’’), 7.97 (mc, H6,6’’), 8.30 (mc, Haryl), 8.58 (mc, H4,4’’), 8.78 (mc, Haryl), 9.18 (mc, H3,3’’), 9.46 (mc, H3’,5’). Anal. Calcd. for C70H64F12N6O4P2Zn: C 59.69%, H 4.58%, N 5.97%. Found: C 58.91%, H 4.23%, N 4.98%.
Metallo-homo polymer P3: {[Zn(M3)](PF6)2}n.
According to the above mentioned procedure, homo polymer P3 was obtained as yellow solid (27 mg, 78%). 1
H NMR (DMSO-d6, 300 MHz, δ): 0.82 (mc, CH3), 1.01 (mc, CH3), 1.18–1.58 (mc, CH2),
3.09 (mc, N=C-CH2), 7.54 (mc, H5,5’’), 7.99 (mc, H6,6’’), 8.32 (mc, Haryl), 8.60 (mc, H4,4’’), 8.79 (mc, Haryl), 9.18 (mc, H3,3’’), 9.48 (mc, H3’,5’). Anal. Calcd. for C70H64F12N8P2Zn: C 61.25%, H 4.70%, N 8.16%. Found: C 60.71%, H 4.13%, N 7.58%.
Metallo-homo polymer P4: {[Zn(M4)](PF6)2}n.
According to the above mentioned procedure, homo polymer P4 was obtained after three times precipitation as yellow solid (8 mg, 20%).1H NMR (DMSO-d6, 300 MHz, δ): 0.85 (mc, CH3), 1.04–1.54 (m, CH2), 3.08 (mc, O-CH2), 7.05 (mc, Haryl), 7.52 (mc, H5,5’’), 7.93 (mc, H6,6’’), 8.30 (mc, Haryl), 8.60 (mc, H4,4’’), 8.79 (mc, Haryl), 9.13 (mc, H3,3’’), 9.34 (mc, H3’,5’). Anal. Calcd. for C86H74F12N8O2P2Zn: C 64.28%, H 4.64%, N 6.97%. Found: C 63.78%, H 4.04%, N 6.77%.
18
Metallo-homo polymer P5: {[Zn(M5)](PF6)2}n.
According to the above mentioned procedure, homo polymer P5 was obtained as orange solid (21 mg, 54%). 1
H NMR (DMSO-d6, 300 MHz, δ): 0.84 (mc, CH3), 0.99–1.47 (m, CH2), 3.99 (mc, O-CH2),
7.07 (mc, Haryl), 7.52 (mc, H5,5’’), 7.97 (mc, H6,6’’), 8.03 (mc, Haryl), 8.30 (mc, H4,4’’), 8.76 (mc, Haryl), 9.19 (mc, H3,3’’), 9.48 (mc, H3’,5’). Anal. Calcd. for C80H70F12N8O2P2SZn: C 61.48%, H 4.51%, N 7.17%, S 2.05%. Found: C 60.63%, H 3.58%, N 6.64%, S 1.65%.
Metallo-homo polymer P6: {[Zn(M6)](PF6)2}n.
According to the above mentioned procedure, homo polymer P6 was obtained after three times precipitation as yellow solid (23 mg, 48%). 1
H NMR (DMSO-d6, 300 MHz, δ): 0.75 (mc, CH3), 0.98–1.48 (m, CH2), 4.40 (mc, O-CH2),
7.52 (mc, H5,5’’), 8.06 (mc, H6,6’’), 8.08 (mc, Haryl), 8.30 (mc, H4,4’’), 8.68 (mc, Haryl), 8.77 (mc, Haryl), 9.15 (mc, H3,3’’), 9.41 (mc, H3’,5’). Anal. Calcd. for C104H102F12N8O8P2SZn: C 63.11%, H 5.19%, N 5.66%, S 1.62%. Found: C 62.47%, H 4.78%, N 5.37%, S 1.22%.
19
Metallo-homo polymer P7: {[Zn(7)](PF6)2}n.
According to the above mentioned procedure, homo polymer P7 was obtained as yellow solid (44 mg, 82%). 1H NMR (DMSO-d6, 300 MHz, δ): 0.76 (mc, CH3), 0.97–1.53 (m, CH2), 4.18 (mc, O-CH2), 4.40 (mc, O-CH2), 7.55 (mc, H5,5’’), 8.04 (mc, H6,6’’), 8.08 (mc, Haryl), 8.31 (mc, H4,4’’), 8.69 (mc, Haryl), 8.77 (mc, Haryl), 9.16 (mc, H3,3’’), 9.45 (mc, H3’,5’). Anal. Calcd. for C120H136F12N6O10P2Zn: C 66.18%, H 6.29%, N 3.86%. Found: C 65.35%, H 4.23%, N 3.37%.
Metallo-random copolymer R1: {[Zn(M1)](PF6)2}n{[Zn(MD1)](PF6)2}m According to the above mentioned procedure, random copolymer R1 was obtained as yellow solid (46 mg, 75%). 1
H NMR (DMSO-d6, 300 MHz, δ): 0.80 (mc, CH3), 0.94–1.57 (m, CH2), 3.14 (mc, O-CH2),
7.54 (mc, H5,5’’), 7.66 (mc, Haryl), 7.78 (mc, Haryl), 7.99 (mc, H6,6’’), 8.06 (mc, Haryl), 8.31 (mc, H4,4’’), 8.58 (mc, Haryl), 8.69 (mc, Haryl), 8.77 (mc, Haryl), 9.18 (mc, H3,3’’), 9.47 (mc, H3’,5’). Metallo-random copolymer R2: {[Zn(M3)](PF6)2}n{[Zn(MD2)](PF6)2}m According to the above mentioned procedure, random copolymer R2 was obtained as greenyellow solid (48 mg, 70%). 1
H NMR (DMSO-d6, 300 MHz, δ): 0.80 (mc, CH3), 0.94–1.57 (mc, CH2), 3.14 (mc, O-CH2),
7.54 (mc, H5,5’’), 7.66 (mc, Haryl), 7.78 (mc, Haryl), 7.99 (mc, H6,6’’), 8.06 (mc, Haryl), 8.31 (mc, H4,4’’), 8.58 (mc, Haryl), 8.69 (mc, Haryl), 8.77 (mc, Haryl), 9.18 (mc, H3,3’’), 9.47 (mc, H3’,5’).
20
1
H NMR spectra of the aromatic dibromides (2–7)
For all displayed spectra: CDCl3, 300 MHz (1H NMR), respectively 75 MHz (13C NMR), 25 °C
Figure 1 1H NMR of 2.
Figure 2 1H NMR of 3. 21
Figure 3 1H NMR of 4.
Figure 4 1H NMR of 5.
22
Figure 5 1H NMR of 6.
Figure 6 1H NMR of 7. 23
1
H NMR spectra of the bis-terpyridine monomers M2-7
For all displayed spectra: CDCl3, 300 MHz (1H NMR), respectively 75 MHz (13C NMR), 25 °C
Figure 7 1H NMR (top) and 13C NMR (bottom) of M2.
24
Figure 8 1H NMR (top) and 13C NMR (bottom) of M3.
25
Figure 9 1H NMR (top) and 13C NMR (bottom) of M4
26
Figure 10 1H NMR (top) and 13C NMR (bottom) of M5.
27
Figure 11 1H NMR (top) and 13C NMR (bottom) of M6.
28
Figure 12 1H NMR (top) and 13C NMR (bottom) of M7.
29
Representative 1H NMR spectra of metallo-homo polymer P1 and metallo-random polymers R1 and R2 For all displayed spectra: 300 MHz, DMSO-d6, 25 °C
Figure 13 1H NMR of P1.
Figure 14 1H NMR of R1. 30
Figure 15 1H NMR of R2.
31
MALDI-TOF mass spectra of bis-terpyridine monomers M1–M7 For all displayed spectra: dithranol as matrix
Figure 16 MALDI-TOF mass spectra of M1.
Figure 17 MALDI-TOF mass spectra of M2.
32
Figure 18 MALDI-TOF mass spectra of M3.
Figure 19 MALDI-TOF mass spectra of M4.
33
Figure 20 MALDI-TOF mass spectra of M5.
Figure 21 MALDI-TOF mass spectra of M6.
34
Figure 22 MALDI-TOF mass spectra of M7.
35
for
Synthesis and Characterization of New Self-Assembled Metallo-Polymers Containing Electron-withdrawing and Electron-donating Bis-Terpyridine Zn(II) moieties Florian Schlütter,1 Andreas Wild,1,2 Andreas Winter,2,3 Martin D. Hager,1,2 Anja Baumgaertel,1,2 Christian Friebe1,2 and Ulrich S. Schubert1,2,3,* 1
Laboratory of Organic and Macromolecular Chemistry, Friedrich-Schiller-University Jena,
Humboldtstr. 10, 07743 Jena, Germany 2 3
Dutch Polymer Institute (DPI), P.O. Box 902, 5600 AX Eindhoven, The Netherlands Laboratory of Macromolecular Chemistry and Nanoscience, Eindhoven University of
Technology, P.O. Box 513, 5600 MB Eindhoven, The Netherlands
Table of content: Materials and general experimental details
p
Instrumentation
pp 2 – 3
Synthesis of 4’-(4-ethynyl-phenyl)-[2,2’:6’,2’’]terpyridine (A)
p
Synthesis of the aromatic bromides (1–7)
pp 4 – 10
Synthesis of the bis-terpyridines (M1–M7)
pp 11 – 16
Synthesis of the metallo-polymers (P1–P7; R1+R2)
pp 17 – 20
1
H and 13C NMR spectra of the synthesized compounds
pp 21 – 31
MALDI-TOF mass spectra of the synthesized compounds
pp 32 – 35
1
2
3
Materials and general experimental details All chemicals and solvents were purchased from Biosolve, Aldrich, Acros Organics and Alfa Aesar and were of reagent grade and used as received unless otherwise specified. The solvents were dried and distilled according to standard procedures. Chromatographic separation was performed with standardized silica gel 60 (Merck) and aluminum oxide 90 neutral (Molekula). The reaction progress was controlled by thin layer chromatography (TLC) using aluminum sheets precoated with silica gel 60 F254 (Merck) and aluminum oxide 60 F254 neutral (Macherey-Nagel). 4,7-dibromo-[2,1,3]benzothiadiazole 1,1 4,7-diethynyl-[2,1,3]benzothiadiazole,2 2,5-dibromop-xylene,3 2,5-dibromo-terephthalic acid,4 2-bromo-5-iodo-terephthalic acid,5 2-(2-ethylhexyloxy-phenyl)acetonitrile,6 2,5-dibromo-3,4-dinitrothiophene,7,8 thiophene-3,4-diaminium dichloride,7,8
3,6-dibromo-1,2-phenylenediamine,9
1,2-bis(4-(octyloxyphenyl)ethane-1,2-
dione,10 and 5,10-diethyltetradecane-7,8-dione10 were prepared according to the literature.
Instrumentation 1D (1H,
13
C) and 2D (1H-1H gCOSY, HSQC, HMBC) nuclear magnetic resonance spectra
were recorded on a Bruker Cryomagnet BZH 400 (400 MHz), Bruker AC 300 (300 MHz) and Bruker AC 250 (250 MHz) instrument at 298 K. Chemical shifts are reported in parts per million (ppm, δ scale) relative to the residual signal of the deuterated solvent. Coupling constants are given in Hz. The reaction progress was controlled by GC-MS using a Shimadzu QP2010S. UV-vis absorption and PL emission spectroscopy were recorded on an Analytik Jena SPECORD 250 and Jasco FP-6500 spectrometer, respectively, at 298 K. Absolute photoluminescence quantum yields were evaluated at 298 K on a Hamamatsu Photonic MultiChannel Analyzer C 10027. For these techniques 10-6 M to 10-5 M solutions in chloroform or N,N-dimethylformamide (DMF) were used. Matrix-assisted laser desorption-ionization timeof-flight (MALDI-TOF) mass spectra were obtained from an Ultraflex III TOF/TOF mass 1
Pilgram, K.; Zupan, M.; Skiles, R. J. Heterocycl. Chem. 1970, 7, 629–640. Bangcuyo, C. G.; Evans, U.; Myrick, M. L.; Bunz, U. H. F. Macromolecules 2001, 34, 7592–7594. 3 Bonifacio, M. C.; Robertson, C. R.; Jung, J.-Y.; King, B. T. J. Org. Chem. 2005, 70, 8522–8526. 4 Yao, Y.; Tour, J. M. Macromolecules 1999, 32, 2455–2461. 5 Han, C.-C.; Balasubramanian, A. J. Polym. Sci., Part A: Polym. Chem. 2008, 46, 5483–5498. 6 Ahmed, A. M.; Feast, W. J.; Tsibouklis, J. Polymer 1993, 34, 1297–1302. 7 Kenning, D. D.; Mitchell, K. A.; Calhoun, T. R.; Funfar, M. R.; Sattler, D. J.; Rasmussen, D. C. J. Org. Chem. 2002, 67, 9073–9076. 8 Shahid, M.; Shahid, R. A.; Klemm, E.; Sensfuss, S. Macromolecules 2006, 7844–7853. 9 Huo, L. J.; Tan, Z. A.; Zhou, Y.; Zhou, E. J.; Han, M. F.; Li, Y. F. Macromol. Chem. Phys. 2007, 208, 1294– 1300. 10 Karsten, B. P.; Viani, L.; Gierschner, J.; Cornil, J.; Janssen, R. A. J. J. Phys. Chem. 2008, 112, 10764–10773. 2
2
spectrometer with dithranol as matrix in reflector mode. Elemental analysis was carried out on a CHN-932 Automat Leco instrument.
4’-(4-Ethynyl-phenyl)-[2,2’:6’,2’’]terpyridine (A)
To a solution of 4-ethynylbenzaldehyde (2.05 g, 15.8 mmol) in ethanol (41 mL) was added 2-acetylpyridine (4.10 g, 33.9 mmol) and sodium hydroxide (1.28 g, 32.0 mmol). After stirring (30 min) until complete dissolving of sodium hydroxide, ammonium hydroxide solution (25%, 41 mL) was slowly added. The resulting red suspension was stirred for 24 h at room temperature. Subsequent filtration of the formed precipitate, washing with methanol and water and three times recrystallization from ethanol yielded the desired product as a white powder (2.00 g, 38%). 1
H NMR (CDCl3, 250 MHz, δ): 3.19 (s, 1H, C≡C-H), 7.36 (m, 2H, H5,5’’), 7.65 (d, 3J =
7.9 Hz, 2H, Ha,b), 7.87 (m, 4H, H4,4’’, Ha,b), 8.66 (d, 3J = 8 Hz, 2H, H3,3’’), 8.73 (s, 2H, H3’,5’), 8.74 (m, 2H, H6,6’’). MALDI-TOF MS (dithranol): m/z = 334.11 (100%) [M+H]+. Anal. Calcd. for C23H15N3: C, 82.86%; H, 4.54%; N, 12.60%. Found: C, 82.78%; H, 4.48%; N 12.45%.
3
4,7-Dibromo-[2,1,3]benzothiadiazole (1)
Scheme 1 Schematic representation of the synthesis of 4,7-dibromo-[2,1,3]benzothiadiazole (1).1
Dioctyl 2,5-dibromo-terephthalate (2)
Scheme 2 Schematic representation of the synthesis of dioctyl 2,5-dibromo-terephtalate (2).4 2,5-Dibromo-terephthalic acid4 (2.60 g, 8.0 mmol) was dissolved in thionyl chloride (26 mL, large excess) and stirred at 80 °C for 3 h. The remaining thionyl chloride was removed under reduced pressure (first on a rotary evaporator, later on high vacuum) afterwards. A solution of n-octanol (2.11 g, 16.2 mmol) in CH2Cl2 (25 mL) was slowly dropped to the white solid accompanied by intensive evolution of HCl. The resulting suspension was heated under reflux and the reaction progress was monitored by GC-MS. After 5 h ice water (40 mL) was added in order to terminate the reaction. The organic phase was separated, washed three times with saturated aq. NH4Cl and dried over MgSO4. After evaporation of the solvent, the obtained oil was crystallized from ethanol yielding 2 as a white powder (3.50 g, 79%). 1H NMR (CDCl3, 400 MHz, δ): 0.88 (m, 6H, CH3), 1.22–1.48 (m, 20H, CH2), 1.74–1.81 (m, 4H, OCH2-CH2), 4.34 (mc, 4H, O-CH2), 8.01 (s, 2H, H1). Anal. Calcd. for C24H36Br2O4: C, 52.57%; H, 6.62%. Found: C, 52.48%; H, 6.55%. 4
5,8-Dibromo-2,3-bis(2-ethylhexyl)quinoxaline (3)
Scheme
3
Schematic
representation
of
the
synthesis
of
5,8-dibromo-2,3-bis(2-
ethylhexyl)quinoxaline (3).9,10 3,6-Dibromo-1,2-phenylendiamine9 (1.00 g, 3.8 mmol) and 5,10-diethyltetradecane-7,8dione10 (1.07 g, 3.8 mmol) were dissolved in ethanol (50 mL) and a catalytic amount of glacial acetic acid was added. The resulting mixture was heated under reflux and the reaction progress was monitored by GC-MS. After 19 h the reaction mixture was cooled to room temperature and the solvent was evaporated. Purification of the crude product by column chromatography (silica, n-heptane/CHCl3 3:1) yielded 3 as a yellow oil (1.01 g, 52%). 1
H NMR (CDCl3, 400 MHz, δ): 0.82–0.88 (m, 12H, CH3), 1.22–1.44 (m, 16H, CH2), 2.17
(mc, 2H, tC-H), 2.99 (d, 3J = 6.6 Hz, 4H, N=C-CH2), 7.81 (s, 2H, H1).
13
C NMR (CDCl3,
100 MHz, δ): 10.9 (CH3) , 23.1, 26.0, 28.8, 32.8, 38.0 (CH2), 38.8 (tCH), 118.3 (C-Br), 131.9 (C1-H), 142.9 (Ct,
aryl
), 158.1 (N=C-). Anal. Calcd. for C24H36Br2N2: C 56.26%, H 7.08.
Found: C 56.38%, H 7.23%.
5
2,5-Dibromo-1,4-(phenylene)bis(2-(4-(2-ethylhexyloxy)phenyl)acrylonitrile (4)
Scheme 4 Schematic representation of the synthesis of 2,5-dibromo-1,4-(phenylene)bis(2-(4(2-ethylhexyloxy)phenyl)acrylonitrile (4).6 To a solution of 2,5-dibromo-terephthalaldehyde (100 mg, 0.3 mmol) and 2-(4-(2-ethylhexyloxyphenyl)acetonitrile6 (196 mg, 0.8 mmol) in methanol (10 mL) was added sodium methanolate (25 mg, 0.5 mmol). The resulting solution was degassed with argon for 1 h and afterwards stirred under reflux for 12 h. During the reaction an orange solid precipitated. The precipitate was filtered off and washed intensively with methanol. Finally 4 was obtained as a yellow-orange solid (152 mg, 60%). 1
H NMR (CDCl3, 250 MHz, δ): 0.82–0.92 (m, 12H, CH3), 1.22–1.56 (m, 16H, CH2), 1.77
(mc, 2H, tC-H), 3.92 (d, 3J = 5.8 Hz, 4H, O-CH2), 6.99 (d, 3J = 8.8 Hz, 4H, Ha), 7.63 (d, 3
J = 5.0 Hz, 4H, Hb), 7.68 (s, 2H, H1), 8.34 (s, 2H, =C-H2). 13C NMR (CDCl3, 100 MHz, δ):
11.1, 14.0 (CH3), 23.0, 23.9, 29.1, 30.5 (CH2), 39.4 (tCH), 70.9 (O-CH2), 115.2 (Ca), 116.1 (C-Br), 116.8 (C≡N), 123.9 (NC-C-C), 125.6 (NC-C), 127.8 (Cb), 133.1 (C1-H), 135.8 (=C-C), 136.5 (NC-C=C), 161.2 (O-Caryl). Anal. Calcd. for C40H46Br2N2O2: C, 64.35%; H, 6.21%; N, 3.75%. Found: C, 64.12%; H, 5.88%; N, 3.52%.
6
5,7-Dibromo-2,3-bis(4-(octyloxyphenyl)thieno[3,4-b]pyrazine (5)
Scheme
5
Schematic
representation
of
the
synthesis
of
5,7-dibromo-2,3-bis(4-
(octyloxyphenyl)thieno[3,4-b]pyrazine.7,8,10 2,3-Bis(4-(octyloxyphenyl)thieno[3,4-b]pyrazine: To a suspension of thiophene-3,4-diaminohydrochloride7,8 (490 mg, 2.6 mmol) and 1,2-bis(4(octyloxyphenyl)ethane-1,2-dione10 (1.22 g, 2.6 mmol) in ethanol (40 mL) was slowly dropped triethylamine (556 mg, 5.5 mmol). The mixture was stirred for 48 h at room temperature in the absence of light. Afterwards the solvent was evaporated without heating. The black residue was washed with petrol ether and further purified by column chromatography (silica, CH2Cl2). The desired product was obtained as yellow oil, which crystallizes under cooling and decomposes in the presence of light (571 mg, 40%). 1
H NMR (CDCl3, 300 MHz, δ): 0.89 (mc, 6H, CH3), ), 1.22–1.46 (m, 20H, CH2), 1.66–1.82
(m, 4H, OCH2-CH2), 3.97 (mc, 4H, O-CH2), 6.85 (d, 3J = 8.7 Hz, 4H, Ha), 7.38 (d, 3
J = 8.7 Hz, 4H, Hb), 7.97 (s, 2H, H1). 13C NMR (CDCl3, 75 MHz, δ): 14.1 (CH3), 22.6, 26.0,
29.2, 29.4, 31.8 (CH2), 68.1 (O-CH2), 114.2 (Ca), 116.8 (C1-H), 131.1 (Cb), 131.6 (Ct, 141.6 (Ct,
aryl
),
aryl
), 153.1 (N=C), 159.8 (O-Caryl). Anal. Calcd. could not be obtained due to
decomposing in the presence of light.
5,7-Dibromo-2,3-bis(4-(octyloxyphenyl)thieno[3,4-b]pyrazine (5): A solution of 2,3-bis(4-(octyloxyphenyl)thieno[3,4-b]pyrazine (225 mg, 0.4 mmol) in dry DMF (10 mL) was degassed with argon for 1 h in the absence of light. The solution was cooled with an ice/CaCl2/NaCl mixture. At –15 °C N-bromosuccinimide (NBS, 148 mg, 0.8 mmol) dissolved in dry DMF (3 mL) was slowly added via a syringe. The solution was further 7
stirred in the absence of light for 3 h at –15 °C. Subsequently, the green solution was poured onto ice and extracted three times with diethyl ether. The organic layers were combined, washed with water and dried over MgSO4. Evaporation of the solvent and column chromatography (silica, CH2Cl2:n-hexane 2:1) yielded 5 as green-yellow solid which was highly light sensitive (154 mg, 53%). 1
H NMR (CDCl3, 300 MHz, δ): 0.89 (mc, 6H, CH3), 1.20–1.46 (m, 20H, CH2), 1.66–1.82 (m,
4H, OCH2-CH2), 3.97 (mc, 4H, O-CH2), 6.85 (d, 3J = 8.7 Hz, 4H, Ha), 7.46 (d, 3J = 8.7 Hz, 4H, Hb). 13C NMR (CDCl3, 75 MHz, δ): 14.1 (CH3), 22.6, 26.0, 29.2, 29.4, 31.8 (CH2), 68.1 (O-CH2), 114.2 (Ca), 118.7 (C1-Br), 131.1 (Cb), 131.6 (Ct, aryl), 141.6 (Ct, aryl), 153.1 (N=C), 159.8 (O-Caryl). Anal. Calcd. could not be obtained due to decomposing in the presence of light.
Tetraoctyl 5,5’-([2,1,3]benzothiadiazole-4,7-bis(ethyne-2,1-diyl))bis(2-bromo-terephthalate) (6)
Scheme
6
Schematic
representation
of
the
synthesis
of
tetraoctyl
([2,1,3]benzothiadiazole-4,7-bis(ethyne-2,1-diyl))bis(2-bromo-terephthalate) (6).3-5
8
5,5’-
A solution of dioctyl 2-bromo-5-iodo-terephthalate5 (A, 300 mg, 0.5 mmol) and 4,7diethynyl-[2,1,3]benzothiadiazole2 (B, 42 mg, 0.2 mmol) in THF (30 mL) and diisopropylamine (12 mL) was degassed with argon for 2 h and cooled to 0 °C. Tetrakis(triphenylphosphine)palladium(0) (3 mol%, 8 mg) and copper(I)iodide (3 mol%, 1.3 mg) were added to this solution and stirred 7 h at 0 °C. Afterwards the reaction mixture was allowed to warm up to room temperature and stirred overnight. Thereafter the solution was filtered in order to remove the precipitated ammonia salt and the precipitate was washed intensively with THF. Addition of dichloromethane (10 mL), washing the organic solution with sat. aq. NH4Cl/EDTA solution and evaporation of the solvents yielded the crude product. Finally, 6 was obtained after column chromatography (silica, CH2Cl2:n-hexane 2:1) and precipitation from methanol as intense yellow powder (116 mg, 45%). 1
H NMR (CDCl3, 250 MHz, δ): 0.87 (mc, 12H, CH3), ), 1.13–1.52 (m, 40H, CH2), 1.69–1.87
(m, 8H, OCH2-CH2), 4.32–4.45 (m, 8H, O-CH2), 7.87 (s, 2H, H3), 8.14 (s, 2H, H2) , 8.30 (s, 2H, H1). 13C NMR (CDCl3, 75 MHz, δ): 14.05 (CH3), 22.6, 26.0, 28.5, 28.6, 29.1, 29.1, 29.2, 31.8 (CH2), 66.3, 66.5 (O-CH2), 91.0 (C≡C), 95.1 (C≡C), 114.2 (≡C-C), 117,2 (C-Br), 117.4, 121.5, 122.1, 133.0, 134.9, 135.7, 136.2, 136.6, 140.3 (Caryl), 164.1 (C=O), 165.0 (C=O). Anal. Calcd. for C58H74Br2N2O8S: C 62.25%, H 6.67%, N 2.50% S 2.87%. Found: C 61.87%, H 6.35%, N 2.78%, S 2.49%.
Tetraoctyl 5,5’-(2,5-bis(octyloxy)-1,4-phenylene)bis(ethyne-2,1-diyl)bis(2-bromoterephthalate) (7)
Scheme 7 Schematic representation of the synthesis of tetraoctyl 5,5’-(2,5-bis(octyloxy)-1,4phenylene)bis(ethyne-2,1-diyl)bis(2-bromoterephthalate).4,5
9
A solution of dioctyl 2-bromo-5-iodo-terephthalate5 (A, 500 mg, 0.8 mmol) and 1,4diethynyl-2,5-bis(octyloxy)benzene (150 mg, 0.4 mmol) in THF (30 mL) and diisopropylamine (12 mL) was degassed with argon for 2 h and cooled to 0 °C. Tetrakis(triphenylphosphine)palladium(0) (2 mol%, 10 mg) and copper(I)iodide (2 mol%, 2.2 mg) were added to the solution and stirred 7 h at 0 °C. The reaction mixture was allowed to warm up to room temperature and stirring was continued overnight. Subsequently, the solution was filtered in order to remove the precipitated ammonia salt and the precipitate was washed intensively with THF. Addition of CH2Cl2 (10 mL), washing with sat. aq. NH4Cl/EDTA solution and evaporation of the solvents yielded the crude product. Finally, 7 was obtained after column chromatography (silica, CH2Cl2:n-hexane 1:1) and two times precipitation from methanol as yellow powder (116 mg, 45%). 1
H NMR (CDCl3, 300 MHz, δ): 0.87 (mc, 18H, CH3), 1.17–1.56 (m, 60H, CH2), 1.72–1.91
(m, 12H, OCH2-CH2), 4.03 (mc, 8H, O-CH2), 4.36 (mc, 4H, O-CH2), 7.04 (s, 2H, H3), 8.00 (s, 2H, H2), 8.24 (s, 2H, H1). 13C NMR (CDCl3, 75 MHz, δ): 14.1 (CH3), 22.6, 25.9, 26.0, 26.1, 28.5, 28.6, 29.1, 29.2, 29.2, 29.3, 31.8, 31.8 (CH2), 66.0, 66.4, 69.8 (O-CH2), 92.2 (C≡C), 93.0 (C≡C), 114.2 (≡C-C), 117.1 (C-Br), 120.4, 123.1, 134.5, 135.4, 136.0, 136.4, 153.9 (Caryl), 164.2 (C=O), 165.1 (C=O). Anal. Calcd. for C74H108Br2O10: C 67.46%, H 8.26%, Found: C 67.07%, H 7.88%.
10
General procedure for the synthesis of π-conjugaeted bis-terpyridines by Sonogashira coupling To an argon degassed mixture of 4’-(4-ethynylphenyl)-[2,2’:6’,2’’]terpyridine (A, 0.5 mmol) and an aromatic bromide (1–7, 0.25 mmol) in dry THF (30 mL) and dry triethylamine or diisopropylamine (10 mL) were added tetrakis(triphenylphospine)palladium(0) (10 mol%) and copper(I)iodide (10 mol%) and the reaction mixture was refluxed until TLC indicated complete conversion (5 to 48 h). After cooling to room temperature, the precipitated ammonia salt was filtered off and washed intensively with THF. Dichloromethane was added and the solution was washed with sat. aq. NH4Cl/EDTA solution and dried over MgSO4. After removal of the solvents, the product was precipitated from methanol. Further purification was achieved by column chromatography (aluminum oxide, CH2Cl2 as eluent). When applicable, deviations from this general protocol are given below.
4,7-Bis([2,2’:6’,2’’]terpyridine)-ethynyl-2,1,3-benzothiadiazole (M1)
According to the above mentioned general procedure, M1 was obtained after filtration from the reaction mixture, intensive washing with water and recrystallization (several times) from a large amount of chloroform as orange solid (169 mg, 85%). 1
H and
13
C NMR spectra could not be obtained due to the very low solubility of M1 in
organic solvents. MALDI-TOF MS (dithranol): m/z = 799.25 (100%, [M+H]+). UV-vis (CHCl3) (ε/M-1·cm-1): λmax/nm = 255 (64,350), 282 (81,400), 318 (58,000), 423 (20,700). Emission (CHCl3) (excitation in nm): λPL,max/nm = 503 (423). Anal. Calcd. for C52H30N8S: C, 78.18%; H, 3.78%; N, 14.03%; S, 4.01%. Found: C, 77.98%; H, 4.02%; N, 14.21%; S, 3.76%.
11
Dioctyl 2,5-bis([2,2’:6’,2’’]terpyridine)-ethynyl-terephthalate (M2)
According to the above mentioned general procedure M2 was obtained as a yellow solid (184 mg, 70%). 1
H NMR (CDCl3, 300 MHz, δ): 0.84 (mc, 6H, CH3), 1.19–1.51 (m, 20H, CH2), 1.78–1.88 (m,
4H, OCH2-CH2), 4.44 (mc, 4H, O-CH2), 7.37 (mc, 4H, H5,5’’), 7.73 (d, 3J = 7.5 Hz, 4H, Ha,b), 7.88 (mc, 8H, H4,4’’, Ha,b), 7.95 (d, 3J = 7.5 Hz, 4H, Ha,b), 8.26 (s, 2H, HA), 8.69 (d, 3
J = 7.8 Hz, 4H, H3,3’’), 8.75 (d, 3J = 3.9 Hz, 4H, H6,6’’), 8.76 (s, 4H, H3’,5’). 13C NMR (CDCl3,
75 MHz, δ): 14.1 (CH3), 22.6, 26.1, 28.7, 29.2, 29.3, 31.8 (CH2), 66.1 (O-CH2), 88.9 (C≡C), 96.4 (C≡C), 118.7 (≡C-C), 121.4, 122.9, 123.6, 123.9, 127.3, 132.4, 134.5, 136.1, 136.9, 138.8, 149.2, 149.3, 156.1, 156.1 (Caryl), 165.1 (C=O). MALDI-TOF MS (dithranol): m/z = 1053.51 (100%, [M+H]+). UV-vis (CHCl3) (ε/M-1·cm-1): λmax/nm = 254 (64,400), 279 (65,000), 326 (66,000), 373 (59,300). Emission (CHCl3) (excitation in nm): λPL,max/nm = 424 (373). Anal. Calcd. for C70H64N6O4: C, 79.82%; H, 6.12%; N, 7.98%. Found: C, 79.45%; H, 6.46%; N 7.79%.
5,8-Bis([2,2’:6’,2”]terpyridine)-ethynyl-2,3-bis(2-ethylhexyl)quinoxaline (M3)
According to the above mentioned general procedure M3 was obtained as a yellow-orange solid (164 mg, 65%).
12
1
H NMR (CDCl3, 300 MHz, δ): 0.87 (mc, 6H, CH3), 1.00 (mc, 6H, CH3), 1.23–1.58 (m, 16H,
CH2), 2.31 (mc, 2H, tC-H), 3.05 (d, 3J = 6.9 Hz, 4H, N=C-CH2), 7.38 (mc, 4H, H5,5’’), 7.81 (d, 3
J = 8.4 Hz, 4H, Ha,b), 7.91 (mc, 10H, H4,4’’, Ha,b, HA), 7.98 (d, 3J = 8.4 Hz, 4 H, Ha,b), 8.70 (d,
3
J = 8.1 Hz, 4H, H3,3’’), 8.76 (d, 3J = 4.2 Hz, 4H, H6,6’’), 8.79 (s, 4H, H3’,5’). 13C NMR (CDCl3,
75 MHz, δ): 10.9, 14.1 (CH3), 23.1, 26.0, 28.9, 32.9 (CH2), 38.1 (tCH), 39.1 (N=C-C), 88.5 (C≡C), 96.7 (C≡C), 118.7 (≡C-C), 121.4, 123.1, 123.9, 124.3, 127.3, 131.8, 132.4, 136.9, 138.4, 140.9, 149.2, 149.4, 156.1, 156.2, 157.4 (Caryl). MALDI-TOF MS (dithranol): m/z = 1017.53 (100% [M+H]+). UV-vis (CHCl3) (ε/M-1·cm-1): λmax/nm = 267 (42,600), 284 (39,800), 318 (33,750), 395 (30,000). Emission (CHCl3) (excitation in nm): λPL,max/nm = 443 (395). Anal. Calcd. for C70H64N8: C, 82.64%; H, 6.34%; N, 11.01%. Found: C, 82.85%; H, 5.97%; N, 11.01%.
2,5-Bis([2,2’:6’,2’’]terpyridine)-ethynyl-1,4-(phenylene)bis(2-(4-(2-ethylhexyloxyphenyl)-acrylonitrile (M4)
According to the above mentioned general procedure M4 was obtained as a yellow-orange solid (187 mg, 72%). 1 t
H NMR (CDCl3, 300 MHz, δ): 0.95 (mc, 12H, CH3), 1.22–1.58 (m, 16H, CH2), 1.75 (mc, 2H,
C-H), 3.94 (mc, 4H, O-CH2 E+Z isomer), 6.88–7.06 (d, 3J = 8.4 Hz, 4 H, Ha,b), 7.37 (mc, 8H,
H5,5’’, Ha,b), 7.73 (d, 3J = 5.7 Hz, 4H, Ha,b), 7.90 (mc, 8H, H4,4’’, Ha,b), 8.06 (s, 2H, HA), 8.46– 8.54 (s, 2H, C=C-HB E+Z isomer), 8.69 (d, 3J = 8.4 Hz, 4H, H3,3’’), 8.77 (mc, 8H, H6,6’’, H3’,5’). 13
C NMR (CDCl3, 75 MHz, δ): 11.1, 14.1 (CH3), 23.0, 23.8, 29.1, 30.5 (CH2), 39.4 (tCH),
70.8 (O-CH2), 87.9 (C≡C), 97.9 (C≡C), 114.2 (≡C-C), 115.1, 115.0, 117.5, 118.7, 118.8, 121.4, 123.1, 123.9, 126.3, 127.5, 127.6, 131.0, 132.1, 132.3, 132.5, 135.7, 136.3, 136.9, 139.0, 149.1, 156.1 (Caryl), 160.9 (O-C=). MALDI-TOF MS (dithranol): m/z = 1251.69 (100%, [M+H]+). UV-vis (CHCl3) (ε/M-1·cm-1): λmax/nm = 253 (72,700), 283 (84,750), 318 (33,750), 354 (88,100). Emission (CHCl3) (excitation in nm): λPL,max/nm = 484 (395), 510 (395). Anal. Calcd. for C86H74N8O2: C, 82.53%; H, 5.96%; N, 8.95%. Found: C, 82.18%; H, 5.58%; N 8.56%. 13
5,7-Bis([2,2’:6’,2’’]terpyridine)-ethynyl-2,3-bis(4-(octyloxy)phenyl)thieno[3,4-b]pyrazine (M5)
According to the above mentioned general procedure M5 was obtained as a red solid (225 mg, 75%). 1
H NMR (CDCl3, 300 MHz, δ): 0.90 (mc, 6H, CH3), 1.23–1.31 (m, 20H, CH2), 1.78–1.88 (m,
4H, OCH2-CH2), 4.00 (mc, 4H, O-CH2), 6.88 (d, 3J = 9.0 Hz, 4 H, Ha,b) 7.40 (mc, 4H, H5,5’’), 7.56 (d, 3J = 8.7 Hz, 4H, Ha,b), 7.78 (d, 3J = 8.4 Hz, 4H, Ha,b), 7.90 (mc, 4H, H4,4’’), 7.97 (d, 3
J = 8.4 Hz, 4H, Ha,b), 8.70 (d, 3J = 7.8 Hz, 4H, H3,3’’), 8.77 (mc, 8H, H6,6’’, H3’,5’). 13C NMR
(CDCl3, 75 MHz, δ): 14.1 (CH3), 22.7, 26.0, 29.2, 29.4, 29.5, 31.8 (CH2), 68.1 (O-CH2), 88.9 (C≡C), 96.5 (C≡C), 114.2, 115.2, 118.7, 121.4, 123.6, 123.9, 127.3, 131.2, 131.6, 132.3, 136.9, 138.6, 142.8, 149.2, 149.3, 156.1, 156.1 (Caryl), 160.3 (C=O). MALDI-TOF MS (dithranol): m/z = 1207.61 (100%, [M+H]+). UV-vis (CHCl3) (ε/M-1·cm-1): λmax/nm = 255 (76,400), 283 (93,500), 346 (61,250), 436 (20,400), 498 (20,200). Emission (CHCl3) (excitation in nm): λPL,max/nm = 587 (498). Anal. Calcd. for C80H70N8O2S: C, 79.57%; H, 5.84%; N, 9.28%; S, 2.66%. Found: C, 79.41%; H, 5.99%; N, 9.08%; S, 2.92%.
14
Tetraoctyl
5,5’-(2,1,3-benzothiadiazole-4,7-diylbis(ethyne-2,1-diyl))bis(2-((4-
([2,2’:6’,2’’]terpyridine-4’-yl)phenyl)ethynyl)terephthalate) (M6)
According to the above mentioned general procedure M6 was obtained after two times column chromatographic purification and three times precipitation from methanol as an orange solid (121 mg, 30%). 1
H NMR (CDCl3, 300 MHz, δ): 0.86 (mc, 12H, CH3), 1.19–1.52 (m, 40H, CH2), 1.77–1.89
(m, 8H, OCH2-CH2), 4.40–4.49 (m, 8H, O-CH2), 7.38 (mc, 4H, H5,5’’), 7.56 (d, 3J = 8.7 Hz, 4H, Ha,b), 7.75 (d, 3J = 8.4 Hz, 4H, Ha,b), 7.95 (mc, 6H, H4,4’’, HC), 7.97 (d, 3J = 9.0 Hz, 4H, Ha,b), 8.32 (s, 2H, HB), 8.40 (s, 2H, HA), 8.70 (d, 3J = 7.8 Hz, 4H, H3,3’’), 8.76 (mc, 4H, H6,6’’), 8.78 (s, 4H, H3’,5’).
13
C NMR (CDCl3, 75 MHz, δ): 14.1 (CH3), 22.6, 26.1, 28.6, 29.1, 29.2,
29.2, 31.8 (CH2), 66.2 (O-CH2), 88.9 (C≡C), 95.1 (C≡C), 116.0, 118.7, 118.7, 121.4, 123.2, 124.0, 127.3, 127.4, 132.4, 139.0, 139.3, 142.2, 146.90, 149.2, 154.3, (Caryl), 156.0, 156.1 (C=O). MALDI-TOF MS (dithranol): m/z = 1623.85 (100%, [M+H]+). UV-vis (CHCl3) (ε/M-1·cm-1): λmax/nm = 255 (55,500), 276 (64,450), 316 (48,300), 359 (30,300), 433 (32,300). Emission (CHCl3) (excitation in nm): λPL,max/nm = 498 (433). Anal. Calcd. for C104H102N8O8S: C, 76.91%; H, 6.33%; N, 6.90%; S, 1.97%. Found: C, 76.65%; H, 5.98%; N, 6.61%; S 1.80%.
15
Tetraoctyl
5,5’-(2,5-bis(octyloxy)-1,4-phenylene)bis(ethyne-2,1-diyl)bis(2-((4-
([2,2’:6’,2’’]terpyridine-4’-yl)phenyl)ethynyl)terephthalate) (M7)
According to the above mentioned general procedure M7 was obtained after two times column chromatographic purification and three times precipitation from methanol as an orange solid (141 mg, 31%). 1
H NMR (CDCl3, 300 MHz, δ): 0.82–1.00 (m, 18H, CH3), 1.21–1.65 (m, 60H, CH2), 1.76–
1.93 (m, 12H, OCH2-CH2), 3.99–4.09 (m, 4H, O-CH2), 4.34–4.54 (m, 8H, O-CH2), 7.05 (s, 2H, HC), 7.39 (mc, 4H, H5,5’’), 7.74 (d, 3J = 8.1 Hz, 4H, Ha,b), 7.94 (mc, 6H, H4,4’’, Ha,b), 8.25 (s, 2H, HB), 8.26 (s, 2H, HA), 8.70 (d, 3J = 7.8 Hz, 4H, H3,3’’), 8.76 (mc, 4H, H6,6’’), 8.78 (s, 4H, H3’,5’). 13C NMR (CDCl3, 75 MHz, δ): 14.1 (CH3), 22.6, 26.1, 28.6, 29.1, 29.2, 29.3, 31.8 (CH2), 66.2 (O-CH2), 88.9 (C≡C), 95.1 (C≡C), 116.0, 118.7, 118.7, 121.4, 123.2, 124.0, 127.3, 127.4, 132.4, 139.0, 139.3, 142.2, 147.0, 149.2, 154.3, (Caryl), 156.0, 156.1 (C=O). MALDI-TOF MS (dithranol): m/z = 1822.32 (100%, [M+H]+). UV-vis (CHCl3) (ε/M-1·cm-1): λmax/nm = 283 (34,450), 327 (34,000), 427 (23,900). Emission (CHCl3) (excitation in nm): λPL,max/nm = 490 (427). Anal. Calcd. for C120H136N6O10: C, 79.09%; H, 7.52%; N, 4.61%. Found: C, 78.71%; H, 7.58%; N, 4.32%.
16
General procedure for the metallo-polymerization To the bis-terpyridine monomers M1–M7 (0.025 mmol) in N-methylpyrrolidone (NMP, 5 mL), zinc(II) acetate (0.025 mmol) in NMP (1 mL) was added. The resulting solution was stirred at 105 °C under argon atmosphere for 24 h. An excess of NH4PF6 (50 mg) was added to the hot solution and stirring was continued for 1 h. The solution was poured into methanol (50 mL), and the resulting metallo-polymer was filtered off and washed with methanol (10 mL). Further purification was achieved by repeated dissolving of the metallo-polymer in NMP (2 mL) and precipitation from diethyl ether. Finally, the products were dried under vacuum at 40 °C for 24 h.
Metallo-homo polymer P1: {[Zn(M1)](PF6)2}n.
According to the above mentioned procedure, homo polymer P1 was obtained as a yellow solid (22 mg, 84%). 1
H NMR (DMSO-d6, 300 MHz, δ): 7.50 (mc, H5,5’’), 7.98 (mc, H6,6’’), 8.32 (mc, Haryl), 8.56
(mc, H4,4’’), 8.76 (mc, Haryl), 9.17 (mc, H3,3’’), 9.46 (mc, H3’,5’). Anal. Calcd. for C52H30F12N8P2SZn: C 54.11%, H 2.62%, N 9.71%, S 2.78%. Found: C 54.61%, H 2.34%, N 8.98%, S 2.12%.
Metallo-homo polymer P2: {[Zn(M2)](PF6)2}n.
According to the above mentioned procedure, homo polymer P2 was obtained as yellow solid (29 mg, 82%). 17
1
H NMR (DMSO-d6, 300 MHz, δ): 0.72 (mc, CH3), 1.09–1.22 (m, CH2), 4.44 (mc, O-CH2),
7.52 (mc, H5,5’’), 7.97 (mc, H6,6’’), 8.30 (mc, Haryl), 8.58 (mc, H4,4’’), 8.78 (mc, Haryl), 9.18 (mc, H3,3’’), 9.46 (mc, H3’,5’). Anal. Calcd. for C70H64F12N6O4P2Zn: C 59.69%, H 4.58%, N 5.97%. Found: C 58.91%, H 4.23%, N 4.98%.
Metallo-homo polymer P3: {[Zn(M3)](PF6)2}n.
According to the above mentioned procedure, homo polymer P3 was obtained as yellow solid (27 mg, 78%). 1
H NMR (DMSO-d6, 300 MHz, δ): 0.82 (mc, CH3), 1.01 (mc, CH3), 1.18–1.58 (mc, CH2),
3.09 (mc, N=C-CH2), 7.54 (mc, H5,5’’), 7.99 (mc, H6,6’’), 8.32 (mc, Haryl), 8.60 (mc, H4,4’’), 8.79 (mc, Haryl), 9.18 (mc, H3,3’’), 9.48 (mc, H3’,5’). Anal. Calcd. for C70H64F12N8P2Zn: C 61.25%, H 4.70%, N 8.16%. Found: C 60.71%, H 4.13%, N 7.58%.
Metallo-homo polymer P4: {[Zn(M4)](PF6)2}n.
According to the above mentioned procedure, homo polymer P4 was obtained after three times precipitation as yellow solid (8 mg, 20%).1H NMR (DMSO-d6, 300 MHz, δ): 0.85 (mc, CH3), 1.04–1.54 (m, CH2), 3.08 (mc, O-CH2), 7.05 (mc, Haryl), 7.52 (mc, H5,5’’), 7.93 (mc, H6,6’’), 8.30 (mc, Haryl), 8.60 (mc, H4,4’’), 8.79 (mc, Haryl), 9.13 (mc, H3,3’’), 9.34 (mc, H3’,5’). Anal. Calcd. for C86H74F12N8O2P2Zn: C 64.28%, H 4.64%, N 6.97%. Found: C 63.78%, H 4.04%, N 6.77%.
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Metallo-homo polymer P5: {[Zn(M5)](PF6)2}n.
According to the above mentioned procedure, homo polymer P5 was obtained as orange solid (21 mg, 54%). 1
H NMR (DMSO-d6, 300 MHz, δ): 0.84 (mc, CH3), 0.99–1.47 (m, CH2), 3.99 (mc, O-CH2),
7.07 (mc, Haryl), 7.52 (mc, H5,5’’), 7.97 (mc, H6,6’’), 8.03 (mc, Haryl), 8.30 (mc, H4,4’’), 8.76 (mc, Haryl), 9.19 (mc, H3,3’’), 9.48 (mc, H3’,5’). Anal. Calcd. for C80H70F12N8O2P2SZn: C 61.48%, H 4.51%, N 7.17%, S 2.05%. Found: C 60.63%, H 3.58%, N 6.64%, S 1.65%.
Metallo-homo polymer P6: {[Zn(M6)](PF6)2}n.
According to the above mentioned procedure, homo polymer P6 was obtained after three times precipitation as yellow solid (23 mg, 48%). 1
H NMR (DMSO-d6, 300 MHz, δ): 0.75 (mc, CH3), 0.98–1.48 (m, CH2), 4.40 (mc, O-CH2),
7.52 (mc, H5,5’’), 8.06 (mc, H6,6’’), 8.08 (mc, Haryl), 8.30 (mc, H4,4’’), 8.68 (mc, Haryl), 8.77 (mc, Haryl), 9.15 (mc, H3,3’’), 9.41 (mc, H3’,5’). Anal. Calcd. for C104H102F12N8O8P2SZn: C 63.11%, H 5.19%, N 5.66%, S 1.62%. Found: C 62.47%, H 4.78%, N 5.37%, S 1.22%.
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Metallo-homo polymer P7: {[Zn(7)](PF6)2}n.
According to the above mentioned procedure, homo polymer P7 was obtained as yellow solid (44 mg, 82%). 1H NMR (DMSO-d6, 300 MHz, δ): 0.76 (mc, CH3), 0.97–1.53 (m, CH2), 4.18 (mc, O-CH2), 4.40 (mc, O-CH2), 7.55 (mc, H5,5’’), 8.04 (mc, H6,6’’), 8.08 (mc, Haryl), 8.31 (mc, H4,4’’), 8.69 (mc, Haryl), 8.77 (mc, Haryl), 9.16 (mc, H3,3’’), 9.45 (mc, H3’,5’). Anal. Calcd. for C120H136F12N6O10P2Zn: C 66.18%, H 6.29%, N 3.86%. Found: C 65.35%, H 4.23%, N 3.37%.
Metallo-random copolymer R1: {[Zn(M1)](PF6)2}n{[Zn(MD1)](PF6)2}m According to the above mentioned procedure, random copolymer R1 was obtained as yellow solid (46 mg, 75%). 1
H NMR (DMSO-d6, 300 MHz, δ): 0.80 (mc, CH3), 0.94–1.57 (m, CH2), 3.14 (mc, O-CH2),
7.54 (mc, H5,5’’), 7.66 (mc, Haryl), 7.78 (mc, Haryl), 7.99 (mc, H6,6’’), 8.06 (mc, Haryl), 8.31 (mc, H4,4’’), 8.58 (mc, Haryl), 8.69 (mc, Haryl), 8.77 (mc, Haryl), 9.18 (mc, H3,3’’), 9.47 (mc, H3’,5’). Metallo-random copolymer R2: {[Zn(M3)](PF6)2}n{[Zn(MD2)](PF6)2}m According to the above mentioned procedure, random copolymer R2 was obtained as greenyellow solid (48 mg, 70%). 1
H NMR (DMSO-d6, 300 MHz, δ): 0.80 (mc, CH3), 0.94–1.57 (mc, CH2), 3.14 (mc, O-CH2),
7.54 (mc, H5,5’’), 7.66 (mc, Haryl), 7.78 (mc, Haryl), 7.99 (mc, H6,6’’), 8.06 (mc, Haryl), 8.31 (mc, H4,4’’), 8.58 (mc, Haryl), 8.69 (mc, Haryl), 8.77 (mc, Haryl), 9.18 (mc, H3,3’’), 9.47 (mc, H3’,5’).
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1
H NMR spectra of the aromatic dibromides (2–7)
For all displayed spectra: CDCl3, 300 MHz (1H NMR), respectively 75 MHz (13C NMR), 25 °C
Figure 1 1H NMR of 2.
Figure 2 1H NMR of 3. 21
Figure 3 1H NMR of 4.
Figure 4 1H NMR of 5.
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Figure 5 1H NMR of 6.
Figure 6 1H NMR of 7. 23
1
H NMR spectra of the bis-terpyridine monomers M2-7
For all displayed spectra: CDCl3, 300 MHz (1H NMR), respectively 75 MHz (13C NMR), 25 °C
Figure 7 1H NMR (top) and 13C NMR (bottom) of M2.
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Figure 8 1H NMR (top) and 13C NMR (bottom) of M3.
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Figure 9 1H NMR (top) and 13C NMR (bottom) of M4
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Figure 10 1H NMR (top) and 13C NMR (bottom) of M5.
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Figure 11 1H NMR (top) and 13C NMR (bottom) of M6.
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Figure 12 1H NMR (top) and 13C NMR (bottom) of M7.
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Representative 1H NMR spectra of metallo-homo polymer P1 and metallo-random polymers R1 and R2 For all displayed spectra: 300 MHz, DMSO-d6, 25 °C
Figure 13 1H NMR of P1.
Figure 14 1H NMR of R1. 30
Figure 15 1H NMR of R2.
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MALDI-TOF mass spectra of bis-terpyridine monomers M1–M7 For all displayed spectra: dithranol as matrix
Figure 16 MALDI-TOF mass spectra of M1.
Figure 17 MALDI-TOF mass spectra of M2.
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Figure 18 MALDI-TOF mass spectra of M3.
Figure 19 MALDI-TOF mass spectra of M4.
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Figure 20 MALDI-TOF mass spectra of M5.
Figure 21 MALDI-TOF mass spectra of M6.
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Figure 22 MALDI-TOF mass spectra of M7.
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