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Supplementary Material (ESI) for Organic Chemistry FrontiersThis journal is The Royal Society of Chemistry 2012○C
S1
One-step rapid synthesis of π-conjugated large oligomers via C–H activation couplingShi-Yong Liu,*ab Di-Gang Wang,b Ai-Guo Zhongb and He-Rui Wen*a
aSchool of Metallurgical and Chemical Engineering, Jiangxi University of Science and Technology, Ganzhou 341000, P. R. Chinab Department of Pharmacy & Chemistry, Taizhou University, Taizhou 317000, P. R. China
Contents
1. Figs. S1 .......................................................................................................................................S2
2. Scheme S1...................................................................................................................................S2
3. Fig. S2 and 3..............................................................................................................................S3
4. Fig. S4 ........................................................................................................................................S4
5. Fig. S5..........................................................................................................................................S5
6. Fig. S6..........................................................................................................................................S6
7. Fig. S7 .........................................................................................................................................S7
8. 1H and 13C NMR, and Maldi-TOF MS spectra.......................................................................S8-22
Electronic Supplementary Material (ESI) for Organic Chemistry Frontiers.This journal is © the Partner Organisations 2017
Supplementary Material (ESI) for Organic Chemistry FrontiersThis journal is The Royal Society of Chemistry 2012○C
S2
PAr2
Pd
Ar2P
Pd
O O
CH3
CH3
OO
Ar = o-CH3(C6H4)
Herrmann-Beller catalyst
O
PdPdPd2(dba)3
3
P
PCy3
P
OCH3
OCH3
H3CO
P(o-MeOPh)3
Fig. S1 The molecular structures of Herr Pd, Pd2(dba)3, PCy3 and P(o-MeOPh)3.
[Pd0]
[PdII]Ar'
X
H, basebase HX
Ar'Ar
[PdII]Ar
Ar'
Ar'X
PdIIB2H2
2 HBPdAr Ar
Ar
Transmetallation+
Reductive elimination
ArH Ar'X+ Ar Ar'PdIIB2
-HX
B = Cl, -OAc, etc
Ar
Ar
Ar
Overall reaction
Transformation of PdII pre-catalyst to Pd0 catalyticspecies
C-H/C-H homo-coupling side product
C-H activaion
Oxidative additionReductive
elimination
Pd
O
Ar'
L
O
R
H -RCOOHAr'Pd(L)ArO
O
HAr
Pd
R
L
Ar
The Palladation ofC-H bond via CMDpathway
Ar
Scheme S1 The Pd-catalyzed DA reaction, the reduction of PdII pre-catalyst to Pd0 catalytic species, the catalytic cycle of the DA coupling, and the palladation of C-H bond.
Supplementary Material (ESI) for Organic Chemistry FrontiersThis journal is The Royal Society of Chemistry 2012○C
S3
LigandNon- ligand
Starting DPP
p- B (DPP)2
Non- ligand Ligand
Fig. S2 The reaction between DPP and p-dibromobenzene with and without ligand P(o-MeOPh)3 using toluene as reaction medium (entries 10 and 11 in Table 1). Digital photos of (a) The reaction mixtures after reacting for 12 h and cooling to room temperature. (b) The TLC analysis of both reaction mixtures, using CH2Cl2 : hexane (2:1, v/v) as eluent, and the spots marked with green and red frame are the reactant DPP and target product p-B(DPP)2, respectively.
Starting DPP
p- B- (DPP)2
Fig. S3 The TLC analysis of the reactions between DPP and p-dibromobenzene (left) or p-diiodobenzene (right). (see Entries 12 and 13 in Table 1). The spots marked with green and red frame are the reactant DPP and target product p-B(DPP)2, respectively.
Supplementary Material (ESI) for Organic Chemistry FrontiersThis journal is The Royal Society of Chemistry 2012○C
S4
p- B- (DPP)2 m- B- (DPP)2
di- Br- Ph- DPP
DPP- DPP- DPPo- B- (DPP)2 TB- (DPP)3 Py- (DPP)4 TBE- (DPP)4 SF- (DPP)4
Fig. S4 Digital photos of TLC analysis of the synthetic reactions for the eight oligomers. From left to right are respectively p-B-(DPP)2, m-B-(DPP)2, o-B-(DPP)2, DPP-DPP-DPP, TB-(DPP)3, Py-(DPP)4, TBE-(DPP)4 and SF-(DPP)4. For all the TLC plates, the spots on the left are the starting DPP, and the spots marked with red dotted frames are the target oligomers.
Supplementary Material (ESI) for Organic Chemistry FrontiersThis journal is The Royal Society of Chemistry 2012○C
S5
Max = 567 nm
S
N
N
O
O
R
R
SS
R
R
O
O
N
N
S
Max = 577 nm
S
R
R
O
O
N
N
SS
N
N
O
O
R
R
S
Max = 579nm
S
N
N
O
O
R
R
S
S
NN
O
O
RR
S
S N
N
O
O
R
RS
Max = 596 nm
S
R
R
O
O
N
N
SS
N
N
O
O
R
R
S
R =C6H13
C8H17
< =.
<
Fig. S5 The shortest pathways of π-electron delocalization (marked with blue color) of the phenyl-cored DPP-based oligomers o-B-(DPP)2, m-B-(DPP)2, p-B-(DPP)2 and TB-(DPP)3, and the corresponding normalized Uv-vis spectra (below).
Supplementary Material (ESI) for Organic Chemistry FrontiersThis journal is The Royal Society of Chemistry 2012○C
S6
o- B- (DPP)2 m- B- (DPP)2
TB- (DPP)3p- B- (DPP)2
Fig. S6 DFT optimized geometries of phenyl-cored DPP-based oligomers, o-B-(DPP)2, m-B-(DPP)2, p-B-(DPP)2 and TB-(DPP)3 (the alkyl chains replaced by methyl groups).
Supplementary Material (ESI) for Organic Chemistry FrontiersThis journal is The Royal Society of Chemistry 2012○C
S7
S
N
N
O
O
R
R
S
S
R
R
O
O
N
N
S
S
N
N
O
O
R
R
S
S
R
R
O
O
N
N
S
Max = 570nmN
S
R
R
O
O
N
NN
S
N
N
O
O
R
RS
O
O
R
R
S
S
S
SS
R
R
O
O
N
N
twisted
Max = 584nm
S
N
N
O
O
R
R
S
SN
N
O
O
R
S
SN
N
O
O
R
R
S
S
N
N
O R
R
S
O
R
Max = 596nm
< <
Fig. S7 The shortest pathways of π-electron delocalization (marked with blue color) of the Py-, TBE- and SF-(DPP)4 oligomers, and the corresponding normalized Uv-vis spectra (below).
Supplementary Material (ESI) for Organic Chemistry FrontiersThis journal is The Royal Society of Chemistry 2012○C
S8
Fig. S8 The Uv-vis spectra of the starting DPP, oligomers o-B-(DPP)2, m-B-(DPP)2, TB-(DPP)3, p-B-(DPP)2, Py-(DPP)4, TBE-(DPP)4 and SF-(DPP)4 in CHCl3 at concentrations of 4.54, 2.54, 2.03, 1.55, 2.16, 1.89, 1.07, 1.69 and 1.27 ×10-5 mol/L.
Table S1 The extinction coefficients of the DPP materials at λmaxs (×104 M-1 cm-1).
DPP o-B-(DPP)2 m-B-(DPP)2 p-B-(DPP)2 TB-(DPP)3 DPP-DPP-DPP
Py-(DPP)4
TBE-(DPP)4
SF-(DPP)4
2.02 4.47 5.82 4.38 6.94 7.12 12.61 12.74 14.08
Supplementary Material (ESI) for Organic Chemistry FrontiersThis journal is The Royal Society of Chemistry 2012○C
S9
Fig. S8 The 1H and 13C NMR spectra of p-B-(DPP)2 in CDCl3.
Supplementary Material (ESI) for Organic Chemistry FrontiersThis journal is The Royal Society of Chemistry 2012○C
S10
Fig. S9 The 1H and 13C NMR spectra of m-B-(DPP)2 in CD2Cl2.
Supplementary Material (ESI) for Organic Chemistry FrontiersThis journal is The Royal Society of Chemistry 2012○C
S11
Fig. S10 The 1H and 13C NMR spectra of o-B-(DPP)2 in CD2Cl2.
Supplementary Material (ESI) for Organic Chemistry FrontiersThis journal is The Royal Society of Chemistry 2012○C
S12
Fig. S11 The 1H and 13C NMR spectra of DPP-DPP-DPP in CDCl3.
Supplementary Material (ESI) for Organic Chemistry FrontiersThis journal is The Royal Society of Chemistry 2012○C
S13
Fig. S12 The 1H and 13C NMR spectra of TB-(DPP)3 in CDCl3.
Supplementary Material (ESI) for Organic Chemistry FrontiersThis journal is The Royal Society of Chemistry 2012○C
S14
Fig. S13 The 1H and 13C NMR spectra of Py-(DPP)4 in CD2Cl2.
Supplementary Material (ESI) for Organic Chemistry FrontiersThis journal is The Royal Society of Chemistry 2012○C
S15
Fig. S14 The 1H and 13C NMR spectra of TBE-(DPP)4 in CD2Cl2 and in CDCl3, respectively.
Supplementary Material (ESI) for Organic Chemistry FrontiersThis journal is The Royal Society of Chemistry 2012○C
S16
Fig. S15 The 1H and 13C NMR spectra of SF-(DPP)4 in CD2Cl2.
Supplementary Material (ESI) for Organic Chemistry FrontiersThis journal is The Royal Society of Chemistry 2012○C
S17
1572.433
881.4691678.507
0
1000
2000
3000
4000
Inte
ns. [
a.u.
]
1000 1500 2000 2500 3000 3500m/z
Fig. S16 The MALDI-TOF MS spectrum of p-B-(DPP)2, calcd. 1572.51, found 1572.43.
Supplementary Material (ESI) for Organic Chemistry FrontiersThis journal is The Royal Society of Chemistry 2012○C
S18
1572.311
0
100
200
300
400
500
Inte
ns. [
a.u.
]
1000 1200 1400 1600 1800 2000 2200m/z
Fig. S17 The MALDI-TOF MS spectrum of m-B-(DPP)2, calcd. 1572.51, found 1572.31.
1572.639
0
1000
2000
3000
4000
5000Inte
ns. [
a.u.
]
1000 1200 1400 1600 1800 2000 2200m/z
Fig. S18 The MALDI-TOF MS spectrum of o-B-(DPP)2, calcd. 1572.51, found 1572.64.
Supplementary Material (ESI) for Organic Chemistry FrontiersThis journal is The Royal Society of Chemistry 2012○C
S19
Fig. S19 The MALDI-TOF MS spectrum of DPP-DPP-DPP, calcd. 2007.13, found 2007.82.
Supplementary Material (ESI) for Organic Chemistry FrontiersThis journal is The Royal Society of Chemistry 2012○C
S20
Fig. S20 The MALDI-TOF MS spectrum of TB-(DPP)3, calcd. 2319.71, found 2319.77.
Supplementary Material (ESI) for Organic Chemistry FrontiersThis journal is The Royal Society of Chemistry 2012○C
S21
Fig. S21 The MALDI-TOF MS spectrum of Py-(DPP)4, calcd. 3191.05, found 3191.63.
Supplementary Material (ESI) for Organic Chemistry FrontiersThis journal is The Royal Society of Chemistry 2012○C
S22
Fig. S22 The MALDI-TOF MS spectrum of TBE-(DPP)4, calcd. 3321.34, found 3321.30.
Supplementary Material (ESI) for Organic Chemistry FrontiersThis journal is The Royal Society of Chemistry 2012○C
S23
Fig. S23 The MALDI-TOF MS spectrum of SF-(DPP)4, calcd. 3305.20, found 3305.50.