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1P: Yield ca. 90%; H NMR (500 MHz, CDCl3, 298 K, TMS): d=2.91
with vigorous stirring. The progress of the reaction was monitored
by taking small aliquots and treating them with H2O. The appear-
ance of a red color indicated the presence of unreacted K2PtCl4.
After 2 days, the starting PtII salt was completely consumed and
the mixture was allowed to cool to 08C. The resulting bright
yellow crystalline complex was filtered off and washed with H2O
and Et2O to give 1.35 g of the crude PtII complex as a bright yellow
solid mass. The crude product was then purified by column
chromatography using silica gel with 100% DCM as eluent.
(s, 12H), 2.93 (s, 6H), 3.05–3.07 (m, 8H), 3.08–3.10 (m, 4H), 3.24–
3.26 (m, 8H), 3.27–3.29 (m, 5H), 3.46–3.48 (m, 8H), 3.49–3.51 (m,
4H), 3.59–3.61 (m, 8H), 3.62–3.64 (m, 4H), 3.80–3.82 (m, 8H), 3.83–
3.85 (m, 4H), 4.22–4.23 (m, 8H), 4.24–4.26 (m, 4H), 6.86 (t, J=
2.2 Hz, 2H), 6.89 (t, J=2.2 Hz, 1H), 7.40–7.41 (m, 6H), 7.86 (d, J=
8.1 Hz, 2H), 8.17 (d, J=8.2 Hz, 2H), 8.86 (d, J=4.6 Hz, 2H), 8.96 (s,
4H), 8.98 ppm (d, J=4.6 Hz, 2H); 13C NMR spectra (125 MHz, CDCl3,
298 K, TMS): d=58.5, 67.7, 69.7, 69.8, 70.0, 70.1, 70.3, 70.4, 70.6,
70.7, 71.3, 71.4, 78.1, 83.7, 101.2, 114.7, 119.6, 120.6, 121.1, 130.2,
131.4, 131.8, 131.9, 134.3, 143.7, 144.7, 149.6, 149.7, 149.8, 149.9,
157.7 ppm; MALDI-TOF-MS: m/z calcd for C88H112N4O24Zn: 1675.2;
found: 1675.9 (100%).
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Yield ca. 78%; H NMR (500 MHz, CDCl3, 298 K, TMS): d=0.98 (t, J=
7.4 Hz, 3H), 1.99 (sextet, J=7.3 Hz, 2H), 4.59 (t, J=7.2 Hz, 2H), 6.64
(d, J=2.6 Hz, 1H), 7.05 (td, J=7.5 Hz, J=1.2 Hz, 1H), 7.18 (td, J=
7.5 Hz, J=1.4 Hz, 1H), 7.23 (dd, J=7.8 Hz, J=1.0 Hz, 1H), 7.27 (dd,
J=7.6 Hz, J=1.4 Hz, 1H), 7.34 (d, J=8.2 Hz, J=1.0 Hz, 1H), 7.53 (d,
J=2.6 Hz, 1H), 7.71 (t, J=7.9 Hz, 1H), 7.79 ppm (dd, J=7.7 Hz, J=
0.9 Hz, 1H); 13C NMR spectra (125 MHz, CDCl3, 298 K, TMS): d=
10.9, 24.3, 54.4, 105.0, 115.8, 116.3, 124.0, 124.1,130.7, 132.4, 133.9,
138.4, 138.8, 145.8, 150.7, 152.6, 166.5 ppm; ESI-MS: m/z calcd for
C17H16N3ClPt: 492.9; found: 498.1 (M-Cl+MeCN)+ (100%) and
(M-Cl)+(25%).
F) Synthesis of the Ph·Pt complex: All of the final PtII complexes
were synthesized by following the methods reported earlier, where
the corresponding acetylides were prepared by deprotonation
with 5% NaOMe solution in MeOH followed by the addition of
cyclometallated PtII(C^N^NNPr)Cl complex precursor.
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2P: Yield ca. 87%; H NMR (500 MHz, CDCl3, 298 K, TMS): d=2.85
(s, 12H), 3.02 (t, J=4.6 Hz, 8H), 3.22 (t, J=4.4 Hz, 8H), 3.29 (s, 2H),
3.50 (t, J=4.7 Hz, 8H), 3.63 (t, J=4.4 Hz, 8H), 3.84 (t, J=4.4 Hz,
8H), 4.25 (t, J=4.3 Hz, 8H), 6.88 (s, 2H), 7.43 (s, 4H), 7.87 (d, J=
7.5 Hz, 4H), 8.16 (d, J=7.5 Hz, 4H), 8.87 (d, J=4.4 Hz, 4H),
8.99 ppm (d, J=4.4 Hz, 4H); 13C NMR spectra (125 MHz, CDCl3,
298 K, TMS): d=58.6, 67.9, 69.9, 70.1, 70.5, 70.8, 71.4, 78.1, 83.8,
101.6, 114.8, 120.0, 120.9, 121.3, 130.3, 131.6, 132.2, 134.4, 143.6,
144.5, 149.8, 149.9, 157.8 ppm; MALDI-TOF-MS: m/z calcd for
C76H84N4O16Zn: 1374.9; found: 1374.7 (100%).
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3P: Yield ca. 88%; H NMR (500 MHz, CDCl3, 298 K, TMS): d=2.64
(s, 6H), 2.78 (t, J=5.0 Hz, 4H), 3.00 (t, J=4.7 Hz, 4H), 3.27 (s, 1H),
3.28 (s, 2H), 3.32 (t, J=5.0 Hz, 4H), 3.48 (t, J=5.0 Hz, 4H), 3.71 (t,
J=4.7 Hz, 4H), 4.16 (t, J=4.5 Hz, 4H), 6.82 (t, J=2.2 Hz, 1H), 7.41
(d, J=1.9 Hz, 2H), 7.85–7.87 (m, 6H), 8.17(d, J=7.8 Hz, 6H), 8.89 (d,
J=4.6 Hz, 2H), 8.91 (s, 4H), 9.01 ppm (d, J=4.6 Hz, 2H); 13C NMR
spectra (125 MHz, CDCl3, 298 K, TMS): d=58.3, 67.8, 69.7, 69.8,
70.3, 70.6, 71.0, 78.1, 83.7, 101.5, 114.8, 120.1, 121.1, 121.3, 130.3,
131.7, 131.8, 132.3, 134.3, 143.5, 144.4, 149.7, 149.8, 149.9,
150.0,157.8 ppm; MALDI-TOF-MS: m/z calcd for C64H56N4O8Zn:
1074.5; found: 1074.3 (100%).
In a 250 mL round-bottomed flask, phenyl acetylene (0.022 mL,
0.2 mmol) was added under an argon atmosphere. Anhydrous
methanol (30 mL) was added to this. NaOMe (0.5m, 3 mL) was
added to this solution and stirred for 3 h at room temperature
under inert atmosphere. PtII(C^N^N)Cl complex (0.1182 g,
0.24 mmol) dissolved in CHCl3 (20 mL) was added to the phenyl
acetylide solution and the solution was stirred for 1 day at 608C in
the dark. After removing the solvent under reduced pressure and
aqueous extraction with 250 mL DCM, the crude mixture was puri-
fied by column chromatography on SiO2 using dichloromethane as
eluent.
Ph·Pt: Yield ca. 45%; 1H NMR (500 MHz, CDCl3, 298 K, TMS): d=
0.89 (t, J=7.3 Hz, 3H), 1.99 (sextet, J=7.3 Hz, 2H), 4.59 (t, J=
7.2 Hz, 2H), 6.54 (d, J=2.6 Hz, 1H), 6.99 (td, J=7.4 Hz, J=1.2 Hz,
1H), 7.09–7.15 (m, 2H), 7.18 (dd, J=7.7 Hz, J=0.7 Hz, 1H), 7.23–
7.29 (m, 3H), 7.33 (d, J=8.1 Hz, 1H), 7.40 (d, J=2.6 Hz, 1H), 7.46
(dd, J=8.2 Hz, J=1.2 Hz, 2H), 7.60 (t, J=7.9 Hz, 1H), 8.04 ppm (dd,
J=7.6 Hz, J=0.8 Hz, 1H); 13C NMR spectra (125 MHz, CDCl3, 298 K,
TMS): d=10.9, 24.3, 54.4, 105.0, 115.8, 116.3, 124.0, 124.1,130.7,
132.4, 133.9, 138.4, 138.8, 145.8, 150.7, 152.6, 166.5 ppm; ESI-MS:
m/z calcd for C25H21N3Pt: 558.5; found: 559.1 (M+H)+ (100%) and
279.2 (M)2+(45%).
G) Synthesis of the porphyrin–PtII conjugate, P·Pt1: In a 250 mL
round-bottomed flask, 1P (0.0419 g, 0.025 mmol) was added. This
was evaculated and back-filled with argon several times. Anhy-
drous methanol (10 mL) was added to this. NaOMe (0.5m, 1 mL)
was added to this and stirred for 3 h at room temperature under
inert atmosphere. PtII(C^N^N)Cl (0.0148 g, 0.03 mmol) dissolved in
CHCl3 (20 mL) and MeOH (10 mL) was added to the porphyrin ace-
tylide solution and the solution was stirred for 1 day at 608C in
dark. After removing the solvent under reduced pressure and
aqueous extraction with DCM (150 mL) the crude mixture was puri-
fied by column chromatography on SiO2 using dichloromethane–
methanol (95:5 v/v) as eluent. A second chromatography using
silica gel is necessary for further purification.
D) Synthesis of the C^N^NNPr ligand: The C^N^NNH ligand was
prepared by following the previously reported method.[25] Then the
C^N^NNPr ligand was prepared by the standard substitution
method.[12d] 2-Phenyl-6-(1H-pyrazol-3-yl)pyridine (1.1 g, 5 mmol)
and NaH (60% by weight dispersed in mineral oil), (0.24 g, 6 mmol)
was taken in a 250 mL two-necked round-bottomed flask, which
was evacuated and back-filled with Ar several times. Anhydrous
THF (100 mL) was added to this and stirred for 1 h at RT. Propyl
bromide (0.91 mL, 10 mmol) was injected slowly to this reaction
mixture and heated at 708C with constant stirring for overnight.
White solids were filtered off under vacuum. The brown solvent
mixture was evaporated under reduced pressure and the crude
product was purified by silica gel column chromatography using
hexane/diethyl ether (2:1) as the eluent to give 1.4 g of the
colorless semisolid materials.
C^N^NNPr: Yield ca. 87%; 1H NMR (400 MHz, CDCl3, 298 K, TMS):
d=0.98 (t, J=7.4 Hz, 3H), 1.97 (sextet, J=7.3 Hz, 2H), 4.17 (t, J=
7.2 Hz, 2H), 7.10 (d, J=2.3 Hz, 1H), 7.45–7.47 (m, 2H), 7.52 (t, J=
7.6 Hz, 2H), 7.67 (dd, J=7.8 Hz, J=0.8 Hz, 1H), 7.79 (t, J=7.8 Hz,
1H), 7.97 (dd, J=7.8 Hz, J=0.8 Hz, 1H), 8.16 ppm (dd, J=7.1 Hz,
J=1.4 Hz, 2H); 13C NMR spectra (100 MHz, CDCl3, 298 K, TMS): d=
11.2, 23.9, 54.2, 104.5, 118.2, 118.8, 127.0, 128.6, 128.9, 130.5, 137.2,
139.5, 152.0, 152.3, 156.6 ppm; ESI-MS: m/z calcd for C17H17N3:
263.3; found: 264.2 (100%).
E) Synthesis of the Pt(C^N^N)Cl complex: In a 100 mL two-
necked clean and dry round-bottomed flask, C^N^NNPr ligand
(0.5267 g, 2 mmol) and K2PtCl4 (0.7887 g, 1.9 mmol) was added
under an argon atmosphere. Then degassed HOAc (50 mL) was
added to this reaction mixture and heated at 110–1158C for 2 days
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P·Pt1: Yield ca. 60%; H NMR (500 MHz, CDCl3, 298 K, TMS): d=1.12
(t, J=7.3 Hz, 3H), 2.23 (sextet, J=7.3 Hz, 2H), 2.94–2.96 (m, 18H),
Chem. Eur. J. 2016, 22, 4164 – 4174
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