Dalton Transactions
Laboratory of the Ruhr-Universität Bochum. H and P NMR 3H, Ar-dipp), 4.39 (s, 3H, CH
Paper
1
31
+
3
3
-N ), 3.6 (septet, 2H,
J
HH
31
=
P
i
3
i
spectra were recorded using a Bruker Advance DPX-250 6.9 Hz, Pr-CH), 1.1 (d, 12H, J
= 6.7 Hz, Pr-CH ) ppm.
HH
3
spectrometer. The peaks which are not labeled are always NMR (DMSO-d , 100 MHz): δ −5.24 (s, 1P, dipp), −144 (septet,
6
1
19
solvent peaks and methylbipyridinium protons are labeled as 1P, JPF = 710 Hz, PF
6 6
) ppm. F NMR (DMSO-d , 250 MHz):
a, b, c and d (see ESI†). Thermogravimetric analysis was δ −68.8, −71.8 ppm.
carried out with a Perkin Elmer Pyris thermal analysis system,
Synthesis of [Zn(dipp)(L)] [ClO
4
4 4 3 2
] ·(CH OH) (3). To a solu-
under a stream of nitrogen gas at the heating rate of 10 °C tion of [Zn(dipp){(CH
3
)
2
SO}] (0.041 g, 0.025 mmol) in metha-
4
−
1
min . The film morphologies of the hybrid materials were nol (20 mL), 1-methyl-4,4′-bipyridinium perchlorate (0.027 g,
investigated by using a LEO1530 Gemini Scanning Electron 0.1 mmol) in methanol (15 mL) was added. The reaction
Microscope. Prior to the measurements being recorded, the mixture was stirred for overnight while the product precipi-
samples were coated with a thin carbon film.
The starting materials and the products described in this washed with methanol and dried under vacuum. Yield: 0.016 g
study were found to be stable towards moisture and air, and (26%). M.p: >275 °C. Anal. Calcd for C94 Zn : C,
tated as a white solid. The precipitate was filtered, thoroughly
H
120Cl
4
N
8
O
34
P
4
4
1
hence no specific precautions were taken to rigorously exclude 46.40; H, 4.97; N, 4.60. Found: C, 46.25; H, 4.69; N, 4.50. H
3
air. Commercial grade solvents were purified by employing NMR (DMSO-d6, 250 MHz): δ 9.1 (d, 2H, JHH = 7.1 Hz, Ar-d),
3
3
conventional procedures. The chemicals such as 2,6-di-iso-pro- 8.8 (d, 2H, JHH = 6.0 Hz, Ar-a), 8.6 (d, 2H, JHH = 6.7 Hz, Ar-c),
3
pylphenol, 4-aminopyridine, 4,4′-bipyridine, ammonium hexa- 8.0 (d, 2H,
fluorophosphate (NH PF ), sodium perchlorate (NaClO ), (s, 3H, CH -N ), 3.6 (septet, 2H, JHH = 6.9 Hz, Pr-CH), and 1.1
methyl iodide (MeI), and zinc acetate dihydrate (S.d. Fine- (d, 12H,
Chem.) were used as received. 1-methyl-4,4′-bipyridinium salts 100 MHz): δ −5.2 ppm.
and 2,6-di-iso-propylphenyl dihydrogenphosphate (dippH Synthesis of [Zn (dipp)(L)]
[Zn(dipp)(L)] [PF (0.53 g, 0.21 mmol) in acetonitrile (15 mL),
Zn(dipp){(CH ) SO}] was also synthesized as white crystals by a solution of [(TBA) (Mo O )] (0.43 g, 0.20 mmol) in aceto-
J
= 6.3 Hz, Ar-b), 7.0 (m, 3H, Ar-dipp), 4.38
HH
+
3
i
4
6
4
3
3
i
31
3 6
JHH = 6.7 Hz, Pr-CH ) ppm. P NMR (DMSO-d ,
2
)
4 8
·[Mo O26] (4). To a solution of
1
3,14
were prepared according to literature reported methods.
4
6 4
]
[
3
2
4
4
8 26
1
5
employing a protocol developed in our laboratory earlier.
Synthesis of [Zn(dipp)(4-ampyr] ·[CH OH] (1). To a clear four hours while the desired product precipitated as a white
solution of [Zn(dipp){(CH ) SO}] (0.399 g, 0.25 mmol) in solid. The precipitate was filtered and thoroughly washed with
nitrile (15 mL) was added. The reaction mixture was stirred for
4
3
3
3
2
4
methanol (20 mL), a methanolic solution of 4-amino pyridine methanol (30 mL) and acetonitrile (30 mL). The compound
0.094 g, 1 mmol) was added. The resulting clear solution was was dried under vacuum. Yield: 0.50 g (60%). M.p: >275 °C.
kept on the bench-top for crystallization. After one day, the Anal. Calcd for C H Mo N O P Zn : C, 35.02; H, 3.58; N,
(
9
2
112
8
8
42
4
4
−
1
product crystallizes as colourless crystals. The product was 3.55. Found: C, 34.66; H, 3.93; N, 3.46. FT-IR (neat, cm ):
thoroughly washed with cold methanol and dried under 2962(br), 1619(s), 1422(w), 1332(w), 1256(w), 1174(vs), 1079(w),
vacuum. Yield: 0.31 g (64%). M.p: >275 °C. Anal. Calcd for 1046(w), 1019(vs), 912(vs), 843(s), 811(s), 779(vs), 714(s), 665(s).
1
3
C
71
H
92
N
8
O
20
P
4
Zn
4
: C, 48.28; H, 6.08; N, 6.26. Found: C, 48.04;
H NMR (DMSO-d6, 250 MHz): δ 9.2 (d, 2H, JHH = 6.6 Hz,
−1
3
3
H, 5.91; N, 6.31. FT-IR (KBr, cm ): 3476(br), 3353(br), Ar-d), 8.9 (d, 2H, JHH = 6.1 Hz, Ar-a), 8.7 (d, 2H, JHH = 6.6 Hz,
225(br), 2964(vs), 2867(vs), 1639(vs), 1619(w), 1561(w), Ar-c), 8.1 (d, 2H, J = 6.1 Hz, Ar-b), 7.1 (m, 3H, Ar-dipp), 4.4
HH
522(vs), 1460(w), 1440(w), 1382(w), 1361(w), 1338(w), 1256(w), (s, 3H, CH -N ), 3.7 (septet, 2H, JHH = 6.7 Hz, Pr-CH), and 1.2
3
177(vs), 1063(vs), 1026(vs), 1015(w), 915(vs), 771(vs), 554(s) (d, 12H,
3
3
1
1
+
3
i
3
i
31
3 6
JHH = 6.9 Hz, Pr-CH ) ppm. P NMR (DMSO-d ,
1
and 527(vs). H NMR (DMSO-d 400 MHz): δ 7.39 (br, 2H, Ar), 100 MHz): δ −5.2 ppm.
6
,
3
6
.90 (m, 3H, Ar-dipp), 6.68 (br, 2H, NH
2
), 6.4 (d, 2H, JHH
=
Synthesis of [Zn(dipp)(L)] ·[PMo11VO40] 12H
4
2
O (5). To a
3
i
6
.59 Hz, Ar), 3.6 (septet, 2H,
J
HH = 6.9 Hz, Pr-CH), 0.9 solution of [Zn(dipp)(L)]
d, 12H, JHH = 6.7 Hz, Pr-CH ) ppm. P NMR (DMSO-d6, nitrile (5 mL), a solution of [(TBA) (PMo VO )] (0.06 g,
3 4 11 40
4
[PF ] (0.07 g, 0.02 mmol) in aceto-
6 4
3
i
31
(
1
60 MHz): δ −4.5 ppm.
Synthesis of [Zn(dipp)(L)]
0.02 mmol) in acetonitrile (5 mL) was added. The reaction
mixture was stirred for four hours while the product precipi-
4
6 4 3 2 3 2 2
[PF ] ·(CH OH) ·[(CH ) SO]
(
2). To a stirred solution of [Zn(dipp){(CH ) SO}] (0.16 g, tated as a yellowish solid. The precipitate was filtered and
3 2 4
0
.10 mmol) in methanol (20 mL), 1-methyl-4,4′-bipyridinium thoroughly washed with acetonitrile (40 mL) and dried under
hexafluorophosphate (0.12 g, 0.40 mmol) in methanol (15 mL) vacuum. Yield: 0.08 g (77%). M.p: >275 °C. Anal. Calcd for
was added. The reaction mixture was stirred for 3 hours while C H Mo N O P VZn : C, 29.48; H, 3.01; N, 2.99. Found: C,
9
2
136
11
8
68
5
4
−
1
the product precipitated as white solid. The precipitate was 27.87; H, 3.46; N, 2.83. FT-IR (neat, cm ): 2992(br), 1620(s),
thoroughly washed with methanol and dried under vacuum. 1464(w), 1330(w), 1176(br), 1074(s), 1055(s), 1019(vs), 945(vs),
1
Yield: 0.14
g
(50%). M.p: >275 °C. Anal. Calcd for 872(s), 789(vs). H NMR (DMSO-d , 250 MHz): δ 9.1 (d,
6
3
3
C
98
H
132
F
24
N
8
O
20
P
8
S
2
Zn
4
: C, 42.47; H, 4.80; N, 4.04. Found: C, 2H, JHH = 7.1 Hz, Ar-d), 8.8 (d, 2H, JHH = 6.0 Hz, Ar-a), 8.6 (d,
1.98; H, 4.71; N, 3.88. FT-IR (neat, cm ): 2966(br), 1619(s), 2H, JHH = 6.9 Hz, Ar-c), 8.0 (d, 2H, JHH = 6.1 Hz, Ar-b), 7.0 (m,
421(w), 1335(w), 1174(vs), 1077(w), 1020(vs), 917(s), 832(vs), 3H, Ar-dipp), 4.4 (s, 3H, CH -N ), 3.7 (septet, 2H, J = 6.7 Hz,
−
1
3
3
4
1
7
9
+
3
3
HH
1
i
3
i
76(s), 750(s), 731(w), 668(w). H NMR (DMSO-d
6
, 250 MHz): δ Pr-CH), and 1.1 (d, 12H,
3
JHH = 6.9 Hz, Pr-CH ) ppm.
3
3
31
.1 (d, 2H, JHH = 6.9 Hz, Ar), 8.8 (d, 2H, JHH = 6.0 Hz, Ar), 8.5
P NMR (DMSO-d
6
, 100 MHz): δ −4.5 (POM), −5.2 (zinc
3
3
(d, 2H, J = 6.7 Hz, Ar), 8.0 (d, 2H, J = 6.1 Hz, Ar), 6.9 (m, cubane) ppm.
HH HH
This journal is © The Royal Society of Chemistry 2013
Dalton Trans., 2013, 42, 9755–9763 | 9761