Hexakis Porphyrinato Cyclotriphosphazene Systems
FULL PAPER
2-[Hydroxy(4-hydroxyphenyl)methyl]-5-[hydroxy
(p-tolyl)methyl]thio-
2: M.p.>3008C; 1H NMR (400 MHz, CDCl3): d=À2.77 (s, 6H), 2.70 (s,
54H), 6.73 (d, J=7.6 Hz, 12H), 6.85 (d, J=7.6 Hz, 12H), 7.41 (d, J=
7.6 Hz, 12H), 7.44 (d, J=7.6 Hz, 12H), 7.52 (d, J=7.6 Hz, 12H), 8.03 (d,
J=7.6 Hz, 12H), 8.13 (d, J=7.6 Hz, 6H), 8.27 (d, J=8.2 Hz, 12H), 8.42
(d, J=4.5 Hz, 6H), 8.48 (d, J=8.2 Hz, 12H), 8.51 (d, J=4.5 Hz, 6H),
8.66 (d, J=4.5 Hz, 6H), 8.70 (m, 6H), 8.85 (m, 6H), 9.26 (d, J=4.5 Hz,
6H), 9.68 ppm (d, J=4.5 Hz, 6H); 31P{1H} NMR (161.8 MHz, CDCl3):
d=7.57 ppm (s); MALDI-TOF MS: m/z: calcd (C282H204N21O6S6P3):
4267.7; found: 4268.4 [M+1]+; UV/Vis (in toluene): lmax (log e)=430
(5.9), 515 (4.9), 551 (4.4), 619 (4.0), 680 nm (4.3 molÀ1 dm3 cmÀ1).
phene (5): 2-(p-tolylhydroxymethyl)thiophene (1 g, 4.9 mmol) was placed
in a two-necked round-bottomed flask equipped with a nitrogen bubbler
and a rubber septum. Dry diethyl ether (30 mL) and TMEDA (1.48 mL,
9.79 mmol) were added, and this was followed by careful addition of
nBuLi (6.12 mL of an approximately 15% solution in hexane) at 08C.
The resultant mixture was stirred at 08C for 1 h. An ice-cold dry THF so-
lution of 4-hydroxybenzaldehyde (0.72 g, 5.87 mmol) was added, and the
mixture was stirred for 6 h at room temperature. The reaction was
quenched by adding saturated aqueous ammonium chloride solution and
extracted with dichloromethane (3ꢁ50 mL). The organic layers were
combined, washed with saturated brine, and dried over Na2SO4. The
crude product was concentrated in vacuo and purified by silica gel
column chromatography with petroleum ether/ethyl acetate (70:30) as
the eluent to give a yellowish oily compound (0.51 g, 30%): 1H NMR
(400 MHz, CDCl3): d=2.25 (s, 3H), 3.00 (s, 2H), 5.82–5.85 (m, 2H),
6.62–6.65 (m, 2H), 7.16 (d, J=8.2 Hz, 2H), 7.27 (d, J=7.8 Hz, 2H), 7.78
(d, J=7.8 Hz, 2H), 8.42 ppm (d, J=8.2 Hz, 2H); 13C NMR (100 MHz,
CDCl3): d=22.53, 70.51, 71.55, 120.12, 124.33, 124.54, 128.17, 129.30,
134.57, 136.00, 139.45, 140.22, 143.73, 145.36, 146.07, 156.92 ppm; ESMS:
m/z: calcd (C19H18O3S): 326.4; found: 309.3 [MÀ17]+; IR (neat): n˜ =3380,
3058, 2850, 1486, 1436, 1050, 810, 750, 690 cmÀ1; elemental analysis:
calcd: C 58.62, H 4.40, S 8.24; found C 70.01, H 5.41, S 9.62.
Zn61: A solution of 1 (10 mg, 0.0024 mmol) and an excess of ZnACHTUNGTRENNUNG(OAc)2
in dichloromethane/methanol (3:1, 30 mL) was heated to reflux for 4 h.
The crude compound was purified by neutral alumina column chroma-
tography with dichloromethane as the eluent, and Zn61 was collected as
a violet solid (10 mg, 90%). M.p.>3008C; 1H NMR (400 MHz, CDCl3):
d=2.70 (s, 54H), 6.92 (d, J=7.3 Hz, 24H), 7.51 (m, 36H), 7.97 (d, J=
7.6 Hz, 12H), 8.16 (d, J=7.9 Hz, 12H), 8.36 (d, J=8.2 Hz, 12H), 8.51 (d,
J=4.5 Hz 12H), 8.64 (d, J=4.5 Hz, 12H), 8.75 (d, J=4.5 Hz, 12H),
8.91 ppm (d, J=4.5 Hz, 12H); 31P{1H} NMR (161.8 MHz, CDCl3): d=
8.02 ppm (s); MALDI-TOF MS: m/z: calcd (C282H198N27O6P3Zn6): 4546.9;
found: 4547.5 [M+1]+; UV/Vis (in toluene): lmax (log e): 423 (6.4), 512
(4.2), 550 (5.1), 590 nm (4.4 molÀ1 dm3 cmÀ1).
Cu61: A solution of 1 (10 mg, 0.0024 mmol) and an excess of CuCl2 in di-
chloromethane/methanol (3:1, 30 mL) was heated to reflux for 4 h. The
crude compound was purified by neutral alumina column chromatogra-
phy with petroleum ether/dichloromethane (3:1) as the eluent, and Cu61
was collected as a violet solid (10 mg, 91%). M.p.>3008C; MALDI-TOF
MS: m/z: calcd (C282H198Cu6N27O6P3): 4534.9; found: 4535.7 [M+1]+;
UV/Vis (in toluene): lmax (log e): 417 (6.9), 539 nm (5.5 molÀ1 dm3 cmÀ1).
5-(4-Hydroxyphenyl)-10,15,20-trisACTHNUTRGNE(UNG p-tolyl)-21-thiaporphyrin (4): Unsym-
metrical thiophene diol 5 (0.5 g, 1.53 mmol), p-tolualdehyde (0.36 mL,
3.06 mmol), and freshly distilled pyrrole (0.32 mL, 4.60 mmol) were dis-
solved in warm propionic acid (200 mL), and the temperature was in-
creased slowly to the reflux temperature. The reaction mixture was
heated at reflux for 3 h. The propionic acid was distilled off under re-
duced pressure, and the crude residue was washed thoroughly with water
to remove any traces of the propionic acid. A dark powdered slurry was
then prepared by dissolving the crude solid in dichloromethane; the
slurry was loaded onto a silica gel column with dichloromethane as the
solvent. The desired compound was collected as the second band in di-
chloromethane, and removal of the solvent afforded 4 as a purple solid
(35 mg, 3%). M.p.>3008C; 1H NMR (400 MHz, CDCl3): d=À2.69 (s,
1H), 2.73 (s, 9H), 7.28 (m, 2H), 7.55 (d, J=7.9 Hz, 4H), 7.62 (d, J=
8.2 Hz, 6H), 8.00–8.10 (m, 8H), 8.61 (m, 2H), 8.69 (m, 2H), 8.93 (s, 2H),
9.75 ppm (s, 2H); ESMS: m/z: calcd (C47H35N3OS): 689.87; found: 689.97
[M]+.
Acknowledgements
M.R. thanks DST, CSIR, and DAE for financial support. G.N.N. thanks
DST for a Swarnajayanthi fellowship. M.R.R. thanks the CNIR for a fel-
lowship. A.K. thanks C. P. Rao for guidance and encouragement. We all
thank IIT-Bombay for the use of its instrumentation facilities.
General synthetic method for the preparation of hexakis porphyrinato
cyclotriphosphazenes (1 and 2): The appropriate meso-phenylhydroxypor-
phyrin building block (3 or 4; 0.034 mmol) and cesium carbonate
Mark, H. R. Allcock, R. West, Inorganic polymers, 2nd ed., Oxford
University Press, New York, 2005, p. 62.
[2] a) V. Chandrasekhar, Inorganic and Organometallic Polymers,
Springer, Heidelberg, 2005; b) J. E. Mark, H. R. Allcock, Inorganic
polymers, Prentice Hall, New Jersey, 1992; c) H. R. Allcock, Chemis-
try and Application of Polyphosphazenes, Wiley, New York, 2003.
[3] a) E. W. Ainscough, A. M. Brodie, C. V. Depree, J. Chem. Soc.
C. V. Depree, B. Moubaraki, K. S. Murray, C. A. Otter, Dalton
7327; d) E. W. Ainscough, A. M. Brodie, C. V. Depree, C. A. Otter,
[4] a) P. I. Richards, A. Steiner, Inorg. Chem. 2004, 43, 2801–2817; b) F.
Rivals, A. Steiner, Eur. J. Inorg. Chem. 2003, 18, 3309–3313; c) G. T.
Lawson, F. Rivals, M. Tascher, C. Jacob, J. F. Bickley, A. Steiner,
642–650; f) R. Boomishankar, J. Ledger, J.-B. Guilbaud, N. L.
Campbell, J. Bacsa, R. Bonar-Law, Y. Z. Khimyak, A. Steiner,
Turrin, L. Vendier, C. Duhayon, A.-M. Caminade, J.-P. Majoral, J.
(0.068 mmol)
were
added
to
hexachlorocyclotriphosphazene
(0.0057 mmol) in THF at 08C. The reaction mixture was brought to room
temperature and stirred for 6 h at 408C. The progress of the reaction was
monitored with TLC analysis at regular intervals. The reaction was stop-
ped after the spot corresponding to the initial porphyrin building block
(3 or 4) had almost completely disappeared and a new spot correspond-
ing to the required compound (1 or 2) had appeared, as judged by TLC
analysis. The reaction mixture was concentrated with a rotary evaporator
under reduced pressure, and the resulting crude compound was subjected
to silica gel column chromatography. The desired compound was collect-
ed as the first band by using petroleum ether/dichloromethane (1:1), and
the solvent was removed under reduced pressure to afford the hexakis
porphyrinato tricyclophosphazene (1 or 2) in 80–85% yield as a purple
solid.
1
1: M.p.>3008C; H NMR (400 MHz, CDCl3): d=À2.88 (s, 12H), 2.70 (s,
54H), 6.74 (d, J=7.6 Hz, 24H), 7.43 (d, J=7.6 Hz, 24H), 7.53 (d, J=
7.6 Hz, 12H), 8.05 (d, J=7.6 Hz, 12H), 8.23 (d, J=8.2 Hz, 12H), 8.40 (d,
J=4.5 Hz, 12H), 8.44 (d, J=8.2 Hz, 12H), 8.60 (d, J=4.5 Hz 12H), 8.76
(d, J=4.5 Hz, 12H), 8.85 ppm (d, J=4.2 Hz, 12H); 31P{1H} NMR
(161.8 MHz, CDCl3): d=7.52 ppm (s); 13C NMR (100 MHz, CDCl3): d=
139.9, 139.5, 138.8, 138.6, 138.4, 138.1, 137.4, 136.8, 136.1, 134.6, 134.1,
133.5, 133.1, 132.6, 132.2, 127.7, 127.5, 127.0, 120.1, 119.8, 118.3, 31.7,
29.8 ppm; MALDI-TOF MS: m/z: calcd (C282H210N27O6P3): 4165.7;
found: 4166.9 [M+H]+; UV/Vis (in toluene): lmax (log e)=421 (6.1), 516
(4.8), 551 (4.5), 593 (4.3), 648 nm (4.2 molÀ1 dm3 cmÀ1).
Chem. Eur. J. 2009, 15, 3488 – 3496
ꢀ 2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
3495