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New Journal of Chemistry
Page 6 of 8
DOI: 10.1039/C5NJ02246K
ARTICLE
Journal Name
Luminescence Quantum Yield Measurement System (Hamamatsu
Photonics, C9920-03), which comprised an excitation Xenon light
source (the excitation wavelength was set at 380 nm), an
(m), 1106 (s), 992 (m), 865 (m), 831 (m), 757 (w), 700 (w), 654 (m),
404 (w) cm–1. ESI-MS (MeCN, m/z): 1209.7 [{Mo6I8}(OC6H4NO2)6]2–
(1H NMR (C3D6O, 25°C): δ = 0.96 (t, 3JH,H = 7.33 Hz, 24 H), δ = 1.41
(sextet, 3JH,H = 7.32 Hz, 16 H), δ = 1.79 (p, 3JH,H = 7.80 Hz, 16 H), δ =
integrating sphere, and
a
red-sensitive multichannel
3
photodetector (Hamamatsu Photonics, PMA-12).
3.40 (m, 16 H), δ = 6.67 (d, JH,H = 9.15 Hz, 12 H, 2-H and 6-H), δ =
8.02 (d, 3JH,H = 9.15 Hz, 12 H, 3-H and 5-H) ppm (Figure 1S). UV/Vis
Table 3. Selected crystallographic data for 1·CH3CN·H2O and
2·3THF.
(MeCN):
(Bu4N)2[{Mo6I8}(OC6H3-2,4-(NO2)2)6]·3THF (
λ
max [nm] (ε [L·mol–1·cm–1]) = 392 (143380).
2
·3THF). The complex
1·CH3CN·H2O
C70H101I8Mo6N9O19
2963.44
2·3THF
C80H114I8Mo6N14O33
3390.69
was obtained in a similar way from (Bu4N)2[{Mo6I8}I6] (0.162 g,
0.057 mmol) and [AgOC6H3-2,4-(NO2)2] (0.10 g, 0.34 mmol). Single
crystals suitable for X-ray analysis were obtained by slow diffusion
of hexane into THF solution. Yield: 112 mg (0.035 mmol, 62 %).
Mo6I8O30N14C68H90 (3174.38): calcd. C 25.73, H 1.30 N 6.17; found
C 25.50, H 1.30, N 6.12. IR (KBr): ν˜ = 3098 (w), 2961 (m), 2874
(w), 1593 (s), 1522 (s), 1474 (s), 1317 (s), 1132 (s), 1058 (m), 1329
(s), 925 (m), 848 (w), 827 (m), 748 (w), 719 (m), 689 (m), 640 (m),
513 (w), 474 (w), 418 (w) cm–1. ESI-MS (MeCN, m/z): 1344.5
Formula
Mr
Crystal system, space group Triclinic, P¯1
Monoclinic, C2/c
100
Temperature (K)
100
a, b, c (Å)
10.2810(6), 18.6929(13),
24.7011(16)
40.500(5), 10.2557(13),
32.799(5)
α, β, γ (°)
V (Å3)
90.145(2), 99.641(2),
104.611(2)
90, 123.367(7), 90
4523.7(5)
11378(3)
1
([{Mo6I8}(OC6H3-2,4-(NO2)2)6]2–, 1344.7). H NMR (CD3CN, 25 °C): δ
Z, Dx (g·cm–3
)
2, 2.176
4, 1.979
= 0.97 (t, 3JH,H = 7.33 Hz, 24 H), δ = 1.35 (sextet, 3JH,H = 7.39 Hz, 16
μ (mm–1
)
3.60
2.89
3
Crystal size (mm)
0.30 × 0.12 × 0.06
0.641, 0.745
21341, 16798, 9728
0.30 × 0.11 × 0.03
0.178, 0.263
18809, 9686, 6292
H), δ = 1.60 (p, JH,H = 7.97 Hz, 16 H), δ = 3.07 (m, 16 H), δ = 6.87
3
3
4
Tmin, Tmax
(d, JH,H = 9.37 Hz, 6 H, 6-H), δ = 8.20 (d-d, JH,H = 9.37 Hz, JH,H
=
2.95 Hz 6 H, 5-H), δ = 8.53 (d, 4JH,H = 2.95 Hz, 6H, 3-H) ppm (Figure
2S). UV/Vis (MeCN): λ
max [nm] (ε [L·mol–1·cm–1]) = 368 (151050).
Number of measured,
independent and observed
[I > 2σ(I)] reflections
Rint
0.043
0.053
Acknowledgements
θmax (°)
25.73
25
R[F2 > 2s(F2)], wR(F2), S
0.055, 0.128, 0.97
16798
0.062, 0.162, 1.09
9686
No. of reflections
K.A. Brylev thanks the Japan Society for the Promotion of Science
(JSPS) for a Post Doctoral Fellowship for Foreign Researchers and
Prof. N. Kitamura (Hokkaido University) for the opportunity to
study the luminescence properties. We thank Ms. Darya Brazhnik
for experimental help.
Δρmax, Δρmin (e Å–3
)
1.48, –1.11
2.58, –1.08
Preparations
[AgOC6H4-p-(NO2)]. To a solution of p-nitrophenol (120 mg, 863
mmol) in 10 mL of CH2Cl2, 100 mg (432 mmol) of Ag2O was added.
The flask was wrapped in aluminum foil to isolate the reaction
mixture from light, and the mixture was stirred overnight. The
orange solid was collected by filtration and washed with diethyl
ether. Yield: 163 mg (77%). AgH4C6NO3 (245.97): calcd. C 29.30, H
1.64, N 5.69; found C 28.95, H 1.30, N 6.00. IR (KBr): ν˜ = 3370
(m), 1639 (w), 1586 (s), 1556 (m), 1502 (s), 1459 (w), 1423 (m),
1390 (m), 1295 (s), 1170 (s), 1118 (s), 858 (m), 760 (w), 710 (w),
References
1 N. Prokopuk, D. F. Shriver, Adv. Inorg. Chem. 1999, 46, 1-49.
2 a) J. A. Jackson, R. D. Mussell, D. G. Nocera, Inorg. Chem. 1993,
32, 4643-4645; b) M. Amela-Cortes, A. Garreau, S. Cordier, E.
Faulques, J.-L. Duvail, Y. Molard, J. Inorg. Organomet. Polymers
and Materials 2015, 25, 189-204; c) M. Prévôt, M. Amela-Cortes,
S.K. Manna, R. Lefort, S. Cordier, H. Folliot, L. Dupont, Y. Molard,
Advanced Functional Materials, 2015, 25, 4966-4975; d) M.
Prévôt, M. Amela-Cortes, S. K. Manna, S. Cordier, T. Roisnel, H.
Folliot, L. Dupont, Y. Molard. J. Mater. Chem. C. 2015, 3, 5152-
5161.
3 J. A. Jackson, C. Turro, M. D. Newsham, D. G. Nocera, J. Phys.
Chem. 1990, 94, 4500-4507.
4 J. Elistratova, M. Mikhailov, V. Burilov, V. Babaev, I. Rizvanov, A.
Mustafina, P. Abramov, M. Sokolov, A. Konovalov, V. Fedin, RSC
Advances 2014, 4, 27922-27930.
5 a) D. H. Johnston, D. C. Gaswick, M. C. Lonergan, C. L. Stern, D.
F. Shriver, Inorg. Chem. 1992, 31, 1869-1873; b) K. Harder, W.
Preetz, Z. Anorg. Allg. Chem. 1992, 612, 97-100; c) P. Braack, M.
K. Simsek, W. Preetz, Z. Anorg. Allg. Chem. 1998, 624, 375-380;
d) K. Kirakci, P. Kubat, M. Dusek, K. Fejfarova, V. Sicha, J.
Mosinger, K. Lang, Eur. J. Inorg. Chem. 2012, 3107-3111; e) M.
N. Sokolov, M. A. Mikhailov, P. A. Abramov, V. P. Fedin, J. Struct.
Chem. 2012, 53, 197-201; f) G. M. Ehrlich, C. J. Warren, R. C.
Haushalter, F. J. DiSalvo, Inorg. Chem. 1995, 34, 4284-4286; g)
M. K. Simsek, W. Preetz, Z. Anorg. Allg. Chem. 1997, 623, 515-
523; h) M. K. Simsek, D. Bublitz, W. Preetz, Z. Anorg. Allg. Chem.
1997, 623, 1885-1891; i) D. Bublitz, W. Preetz, M. K. Simsek, Z.
Anorg. Allg. Chem. 1997, 623, 1-7; j) G. Pilet, S. Cordier, S.
Golhen, C. Perrin, L. Ouahab, A. Perrin, Solid State Sci. 2003, 5,
1263-1270; k) D. Mery, L. Plault, S. Nlate, D. Astruc, S. Cordier,
649 (m), 492 (w), 462 (w) cm–1
.
[AgOC6H3-2,4-(NO2)2]. The silver salt was obtained in a similar way
from 2,4-dinitrophenol (239 mg, 1.30 mmol) and Ag2O (150 mg,
646 mmol). Yield: 307 mg, (1.05 mmol, 81%). AgH3C6N2O5
(290.97): calcd. C 24.77, H 1.04, N 9.63; found C 25.20, H 1.40, N
9.85. IR (KBr): ν˜ = 3468 (m), 3101 (w), 1949 (w), 1605 (s), 1565
(s), 1534 (m), 1469 (m), 1434 (m), 1380 (m), 1329 (s), 1264 (s),
1135 (s), 1053 (w), 925 (w), 838 (m), 750 (w), 715 (w), 633 (w),
529 (w) cm–1
(Bu4N)2[{Mo6I8}(OC6H4-p-(NO2))6]·CH3CN·H2O (
.
1
·CH3CN·H2O). To a
solution of (Bu4N)2[{Mo6I8}I6] (0.15 g, 0.052 mmol) in 10 mL of
CH2Cl2 a 12-fold excess of solid [AgOC6H4-p-(NO2)] (0.156 g, 0.634
mmol) was added. The mixture was stirred for one day. Then the
resulting fine suspension was filtered through a thick filter paper
and the filtrate was rotary evaporated, leaving a red oil. The oil
was dissolved in CH3CN. Single crystals suitable for X-ray analysis
were obtained by slow diffusion of diethyl ether into the CH3CN
solution. Yield: 0.08 g (0.028 mmol, 52 %). Analysis for desolvated
Mo6I8O18N8C68H96 (2904.04): calcd. C 28.12, H 3.33 N 3.86; found C
28.40, H 3.50, N 3.91. IR (KBr): ν˜ = 3065 (w), 2959 (m), 2872 (w),
2571 (w), 2389 (w), 1974 (w), 1576 (s), 1485 (s), 1284 (s), 1158
6 | J. Name., 2012, 00, 1-3
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