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ELECTRONIC SUPPLEMENTARY MATERIAL
Bisaminoferrocenyl Triazine Derivatives:
Effects of the ThirdSubstituent on the Extent
of Interaction Between the Ferrocene
Centers
Wei Wang,a Dongmei Xu,b Daniel Gesua,a Burjor Captain,a and Angel E. Kaifer*,a
a
Center for Supramolecular Science and Department of Chemistry, University of Miami, Coral Gables,
Florida 33124-0431, U.S.A. and bKey Laboratory of Organic Synthesis of Jiangsu Province, College of
Chemistry, Chemical Engineering and Materials Science, Suzhou University, Suzhou 215123, Jiangsu,
China.
[email protected]
TABLE OF CONTENTS
Synthetic details
Pages S2-S4.
Scheme S1 (New compound structures)
Page S5
FAB-MS, 1H-NMR, 13C-NMR spectra
Pages S5-S12
Near IR spectra
Pages S13-S14
Crystallographic data
Pages S14-S16
References
Page S17
ESM: Wang, Xu, Gesua, Captain, and Kaifer
Page S1
Experimental section
Starting materials were purchased from Aldrich and Acros and were used as received.
THF was freshly distilled before use. Column chromatography was performed using
Scientific Adsorbents silica gel (63200 m). Aminoferrocene was prepared according to
literature procedures.1 The synthesis of 3,5-diferrocenylamino-1-phenoltriazine (2,
F0TFc2) was reported recently in another paper.2 1H-NMR and
13
C-NMR spectra were
recorded on a Bruker Avance 400 MHz spectrometer. FAB-MS spectra were obtained
using a VG Trio 2000 (Manchester, UK). All compound structures are shown in Scheme
S1.
3,5-Di(ferrocenylamino)-1-chlorotriazine (1)
To a solution (kept in an ice-water bath) of 24.5 mg (0.13 mmol) cyanuric chloride in 25
mL THF was added dropwise a mixture of 80 mg (0.40 mmol) aminoferrocene and 0.2
mL of diisopropylethylamine (DIPEA) in 15 mL THF. The reaction mixture was stirred
at 0 °C for 4 hrs, then warmed up to RT overnight. The solvent was removed under
reduced pressure and the residue was purified by column chromatography (silica gel,
chloroform). The product was collected as a yellow solid, 41 mg (yield = 60.1 %). 1HNMR (400 MHz, DMSO-d6, 70 °C):  9.20 (br, 2H), 4.75 (s, 4H), 4.16 (s, 10H), 4.04 (s,
4H). 13C-NMR (100 MHz, DMSO-d6, 70 °C):  163.80, 94.96, 68.34, 63.64, 61.58. FABMS: m/z 515 (MH+, M calc. 514). Anal. Calc for (C23H20N5Fe2Cl): C: 53.79%, H: 3.93,%
N: 13.64%. Found: C: 54.41%, H: 4.20%, N: 13.29%.
3,5-Di(ferrocenylamino)-1-phenylaminotriazine (3)
i) To an ice-bath cooled solution of 885 mg (4.8 mmol) cyanuric chloride in 100 mL THF
was added dropwise a mixture of 0.366 mL aniline and 1.0 mL DIPEA in 20 mL THF.
The reaction mixture was stirred at 0 °C for 4 hrs and then warmed up to RT overnight.
After removing the solvent, the residue was purified by column chromatography (silica
gel, 1:2 Hexanes:CHCl3). The product (5-phenylamino-1,3-dichlorotriazine) is a white
solid, 816 mg (yield = 85%). FAB-MS found: 241 (M+, calc for 241). ii) A sample of 80
mg (0.33 mmol) of 5-phenylamino-1,3-dichlorotriazine was dissolved in 10 mL THF
(solution A). Another solution of 133 mg aminoferrocene (0.66 mmol) and 0.2 mL
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Page S2
DIPEA in 5 mL THF was separately prepared (solution B). Solution B was added
dropwise to solution A at RT. This reaction mixture was stirred at RT for 4 hrs. An
additional 66 mg (0.33 mmol) aminoferrocene was added and the reaction mixture was
transferred to an autoclave. This autoclave was sealed and placed in an oil bath and
heated at 85-90 °C overnight. The reaction mixture was cooled down to RT. After
removing the solvent with a rotary evaporator, the residue was subjected to column
chromatography (silica gel, CHCl3). The product was a yellow solid, 86 mg (yield =
45.5 %). 1H-NMR (400 MHz, DMSO-d6, 70 °C):  8.76 (s, 1H), 8.18 (d, 2H), 7.82 (d,
2H), 7.30 (s, 2H), 7.00 (s, 1H), 4.84 (s, 4H), 4.13 (s, 10H), 3.97 (s, 4H).
13
C-NMR (100
MHz, DMSO-d6, 70 °C):  164.09, 163.78, 139.77, 127.72, 121.35, 120.06, 97.11, 68.11,
62.99, 60.95. FAB-MS: m/z 571 (MH+, M calc. 570). Anal. Calc for (C29H26N6Fe2): C:
61.08%, H: 4.60%, N: 14.74%. Found: C: 61.54%, H: 4.84%, N: 14.40%.
3,5-Di(ferrocenylamino)-1-(4’-nitrophenol)triazine (4)
i) To an ice-water bath cooled solution of 2.0 g (10.8 mmol) cyanuric chloride in 40 mL
THF was added dropwise a solution of 1.0 g (7.2 mmol) 4-nitrophenol and 2.0 mL
DIPEA in 20 mL THF. The mixture was stirred at 0 °C for 4 hrs, then warmed up to RT
overnight. After removal of the solvent by rotovap, the residue was subjected to a column
(silica gel, CHCl3). The product [5-(4’-nitrophenol)-1,3-dichlorotriazine] was a white
solid (1.16 g, 56.3%). GC-MS: m/z 286 (M-H+, calcd. 287). ii) A sample of 144 mg (0.5
mmol) of the above prepared 5-(4’-nitrophenol)-1,3-dichlorotriazine was dissolved in 30
mL THF (solution A). Another solution of 201 mg aminoferrocene (1.0 mmol) and 0.5
mL DIPEA in 20 mL THF was separately prepared (solution B). Solution B was added
dropwise to solution A at RT. This reaction mixture was stirred overnight and then heated
under reflux overnight. An additional sample of aminoferrocene (100 mg) was added and
the reaction mixture was kept under reflux for 2 days. The reaction mixture was then
cooled down to RT. After removing the solvent by rotary evaporator, the residue was
subjected to column chromatography (silica gel, CHCl3). The product was a brownish
solid, 219 mg (yield = 70.6 %). 1H-NMR (400 MHz, DMSO-d6, 90 °C):  8.75 (s, 2H),
8.33 (d, J = 8 Hz, 2H), 7.77 (d, J = 8 Hz, 2H), 4.68 (s, 4H), 4.12 (s, 10H), 3.96 (s, 4H).
C-NMR (100 MHz, DMSO-d6, 90 °C):  165.07, 157.28, 144.13, 124.43, 122.43, 95.66,
13
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Page S3
68.08, 63.18, 61.12. FAB-MS: m/z 618 (M+, M calc. 618). Anal. Calc for
(C29H24N6Fe2O3): C: 56.52%, H: 3.93%, N: 13.64%. Found: C: 56.27%, H: 4.05%, N:
13.48%.
3,5-Di(ferrocenylamino)-1-(2’,4’-dinitrophenol)triazine (5)
A mixture of 160 mg (0.87 mmol) cyanuric chloride, 160 mg (0.87 mmol) 2,4dinitrophenol and 0.3 mL DIPEA was dissolved in 30 mL THF. The reaction mixture was
stirred under N2 overnight. Without isolation of the product, 437 mg (2.15 mmol)
aminoferrocene was added and the reaction mixture was heated up to reflux overnight.
The reaction mixture was cooled down to RT. After removal of the solvent by rotary
evaporator, the residue was subjected to column chromatography (silica gel, 10:1
Hexanes:Ethylacetate). The product was a brownish solid, 108 mg (yield = 18.8 %). 1HNMR (400 MHz, DMSO-d6, 90 °C):  8.93 (s, 1H), 8.92 (s, 2H), 8.65 (m, 1H), 7.93 (d, J
= 8 Hz, 1H), 4.65 (s, 4H), 4.12 (s, 10 H), 3.97 (s, 4H). 13C-NMR (100 MHz, DMSO-d6,
90 °C):  164.79, 149.12, 143.85, 141.41, 128.47, 127.91, 126.53, 120.36, 95.28, 68.16,
63.23, 61.16. FAB-MS: m/z 662 (MH+, M calc. 661). Anal. Calc for (C29H23N7Fe2O5 ·1/3
toluene): C: 54.36%, H: 3.79%, N: 14.16%. Found: C: 54.38%, H: 3.75%, N: 13.94%.
1,3,5-Triferrocenylaminotriazine (6)
To an ice-water bath cooled solution of 24.5 mg (0.13 mmol) cyanuric chloride in 5 mL
THF was added dropwise a solution of 100 mg (0.5 mmol) aminoferrocene and 0.2 mL
DIPEA in 5 mL THF. The reaction mixture was stirred for 30 min at 0°C and then
warmed up to RT for 2 hrs. The reaction mixture was then transferred to an autoclave
(equipped with a magnetic stirring bar) and an additional 80 mg (0.40 mmol)
aminoferrocene was added. The autoclave was sealed and placed in an oil bath, which
was heated to 85-90°C overnight. The reaction mixture was cooled down to RT. After
removal of the solvent under reduced pressure, the residue was subjected to column
chromatography (silica gel, 3:3:1 Hexanes : Chloroform : Ethylacetate). The product was
a yellow solid, 12.5 mg (yield = 13.9 %). 1H-NMR (400 MHz, DMSO-d6, 50 °C):  8.24
(s, br, 3H), 4.87 (s, 6H), 4.12 (s, 15H), 3.98 (s, 6H).
13
C-NMR (100 MHz, DMSO-d6,
50 °C):  164.19, 97.56, 68.36, 63.19, 61.07. FAB-MS: m/z 679 (MH+, M calc. 678).
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Page S4
Anal. Calc for (C33H30N6Fe3 · ½ HCl · ½ H2O): C: 56.19%, H: 4.50%, N: 11.91%.
Found: C: 56.14%, H: 4.44%, N: 11.75%.
Scheme S1. Structures of the compounds investigated in this work
Figure S1. FAB mass spectrum of 1
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Page S5
Figure S2. Variable temperature 1H-NMR (400 MHz, DMSO-d6) spectrum of 1.
Figure S3. 13C-NMR spectrum (100 MHz, DMSO-d6, 70 °C) of 1
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Page S6
Figure S4. FAB mass spectrum of 3.
Figure S5. 1H-NMR spectra (400 MHz, DMSO-d6) of 3.
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Page S7
Figure S6. 13C-NMR spectrum (100 MHz, DMSO-d6, 70 ْC) of 3.
Figure S7. FAB mass spectrum of 4
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Page S8
Figure S8. 1H-NMR spectra (400 MHz, DMSO-d6) of 4.
Figure S9. 13C-NMR spectrum (100 MHz, DMSO-d6, 90 ْC) of 4.
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Page S9
Figure S10. FAB mass spectrum of 5.
Figure S11. 1H-NMR spectra (400 MHz, DMSO-d6) of 5.
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Page S10
Figure S12. 13C-NMR spectrum (100 MHz, DMSO-d6, 90 ْ C) of 5.
Figure S13. FAB mass spectrum of 6.
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Page S11
Figure S14. 1H-NMR spectra (400 MHz, DMSO-d6) of 6.
Figure S15. 13C-NMR spectrum (100 MHz, DMSO-d6, 50 ْC) of 6.
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Page S12
Preparation of the mixed valence compounds and the observation of their near IR
absorbance,
1) Oxidation: A solution of 25.7 mg 1 (ClTFc2, 50 μmol) in 10 mL methylene chloride
was added dropwise to a solution of 31.75 mg iodine (125 μmol) in 3 mL toluene at room
temperature. The reaction mixture was stirred 20 minutes at room temperature. A dark
brown precipitate formed at the bottom of the reaction vial. The precipitate was collected,
rinsed several times with methylene chloride and dried under vacuum to afford 48 mg of
a dark brown solid (yield = 83.6%). 2) Ion exchange: 2.67 mg (2.32 μmol) of the above
prepared solid was suspended in 2.32 mL methylene chloride, to which 3.5 mg
KB(C6F5)4 was added as a solid. The mixture was sonicated for several minutes and the
turbid mixture gradually turned to a reddish clear solution accompanied by the formation
of a white precipitation at the bottom. This solution was filtered and the resulting solution
was used for the subsequent near IR analysis.
Figure S16. UV to near IR absorbance for the mixed valence
Cations, 1.0 mM in methylene chloride.
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Page S13
Table S1. Wavelength of maximum absorbance for the mixed valence cations.
Cation
Wavelength
(nm)
5+
1+
6+
4+
2+
3+
767
769
772
775
787
803
Crystallographic Analyses: Orange single crystals of 4 suitable for x-ray diffraction
analyses were obtained by evaporation of methylene chloride solvent at 25 °C. Red
single crystals of 5 suitable for x-ray diffraction analyses were obtained by evaporation of
toluene solvent at 25 °C. Each data crystal was glued onto the end of a thin glass fiber.
X-ray intensity data were measured by using a Bruker SMART APEX2 CCD-based
diffractometer using Mo K radiation ( = 0.71073 Å).1 The raw data frames were
integrated with the SAINT+ program by using a narrow-frame integration algorithm.3
Corrections for Lorentz and polarization effects were also applied with SAINT+. An
empirical absorption correction based on the multiple measurement of equivalent
reflections was applied using the program SADABS. All structures were solved by a
combination of direct methods and difference Fourier syntheses, and refined by fullmatrix least-squares on F2, by using the SHELXTL software package.3 Hydrogen atoms
were placed in geometrically idealized positions and included as standard riding atoms
during the least-squares refinements. Crystal data, data collection parameters, and results
of the analyses are listed in Table 1.
Compound 4 crystallized in the orthorhombic crystal system. The unique space
group Pbca was identified based on the systematic absences in the intensity data. All
non-hydrogen atoms were refined with anisotropic thermal parameters. Compound 5
crystallized in the triclinic crystal system. The space group P1 was assumed and
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Page S14
confirmed by the successful refinement and solution of the structure. The asymmetric
crystal unit of 5 contains four independent formula equivalents of the molecule. All four
molecules were located and refined with anisotropic thermal parameters for the
nonhydrogen atoms. One and a half molecules of toluene from the crystallization solvent
also cocrystallized with the complex. Six geometric restraints were used in modeling the
three toluene molecules, which were disordered about an inversion center. For each
disordered toluene component, the benzene rings were refined as a rigid hexagon with
d(C-C) = 1.39 Ǻ, and the methyl group was restrained to be in a chemically reasonable
position (SHELX: AFIX, DFIX, SADI instructions). The carbon atoms of each group
were refined with a 50% occupancy factor and a common isotropic thermal parameter.
Due to the large number of parameters (1576), the final stages of the structural
refinement was performed using the XH program part of the SHELXTL software
package.4
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Page S15
Table 1. Crystallographic Data for Compounds 4 and 5.
4
5
Empirical formula
Fe2O3N6C29H24
Fe8O20N28C116H92•3/2 C7H8
Formula weight
616.24
2783.18
Crystal system
Orthorhombic
Triclinic
a (Å)
9.8210(4)
15.3887(2)
b (Å)
14.5100(6)
19.9371(3)
c (Å)
35.4641(15)
22.4511(3)
 (deg)
90
73.891(1)
 (deg)
90
70.914(1)
 (deg)
90
71.244(1)
V (Å3)
5053.7(4)
6048.32(14)
Space group
Pbca (# 61)
P1 (# 2)
Z value
8
2
calc (g / cm3)
1.620
1.528
 (Mo K) (mm-1)
1.194
1.013
Temperature (K)
296(2)
296(2)
2max (°)
54.00
56.56
No. Obs. ( I > 2(I))
4491
17775
No. Parameters
361
1576
Goodness of fit
1.133
1.010
Max. shift in cycle
0.002
0.002
Residuals*:R1; wR2
Absorption Correction,
Max/min
Largest peak in Final
Diff. Map (e- / Å3)
0.0463; 0.0573
Multi-scan
0.9765/0.7012
0.0518; 0.1437
Multi-scan
1.000/0.851
0.639
1.061
Lattice parameters
*R = hkl(Fobs-Fcalc)/hklFobs; Rw = [hklw(Fobs-Fcalc)2/hklwFobs2]1/2,
w = 1/2(Fobs); GOF = [hklw(Fobs-Fcalc)2/(ndata – nvari)]1/2.
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Page S16
References:
1. Van Leusen D, Hessen B (2001) Organometallics 20:224.
2. Xu D, Wang W, Gesua D, Kaifer AE (2008) Org Lett 10:4517.
3. Apex2 Version 2.2-0 and SAINT+ Version 7.46A; Bruker Analytical X-ray
System, Inc., Madison, Wisconsin, USA, 2007.
4. Sheldrick, G. M. SHELXTL Version 6.1; Bruker Analytical X-ray Systems, Inc.,
Madison, Wisconsin, USA, 2000.
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Page S17
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