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619(s). 1HNMR (300 MHz, DMSO, 25 1C, TMS, ppm): 8.69–8.70
(d, J = 3.0 Hz, 4H –C5H4N), 8.45 (s, 2H, –C6H4), 8.11–8.13 (d, J = 6.0 Hz,
2H, –C6H4), 7.96–7.99 (d, J = 9.0 Hz, 2H, –C6H4), 7.81–7.82 (d, J = 3.0 Hz,
4H, –C5H4N), 7.70–7.75 (t, J = 15.0 Hz, 2H, –C6H4), 6.87 (s, 1.6H, –C6H4O),
6.55 (s, 0.1H, –C6H6O), 6.47 (s, 2H, –NH2), 4.32–4.35 (t, J = 9.0 Hz, 0.6H,
–OH), 3.41–3.48 (m, J = 21.0 Hz, 1.3H, –CH2–), 1.02–1.07 (t, J = 15.0 Hz,
1.9H, –CH3). Elemental analysis (%): calcd for C56H46CdCl2N12O11: C
53.97, H 3.72, N 13.49; found: C 54.15, H 3.57, N 13.53. Synthesis of 4
([CdL2(ClO4)2]ꢂ0.4(C6H4O2)ꢂ0.6(C6H6O2)). Compound 3 was exposed to
simulated solar light for 24 h to generate 4. IR (KBr pellet cmꢁ1): 3348(w),
3071(w), 1652(w), 1605(s), 1521(ms), 1480(ms), 1402(ms), 1085(vs),
1008(ms), 882(ms), 796(s), 689(ms), 620(s). 1H NMR (300 MHz, DMSO,
25 1C, TMS, ppm): 8.69–8.70 (d, J = 3.0 Hz, 4H –C5H4N), 8.69 (s, 0.5H,
–OH), 8.45 (s, 2H, –C6H4), 8.11–8.13 (d, J = 6.0 Hz, 2H, –C6H4), 7.96–7.99
(d, J = 9.0 Hz, 2H, –C6H4), 7.81–7.82 (d, J = 3.0 Hz, 4H, –C5H4N), 7.70–7.75
(t, J = 15.0 Hz, 2H, –C6H4), 6.86 (s, 0.6H, –C6H4O), 6.54 (s, 1.0H, –C6H6O),
6.46 (s, 2H, –NH2), 4.32–4.35 (t, J = 9.0 Hz, 0.17H, –OH), 3.41–3.48 (m, J =
21.0 Hz, 0.25H, –CH2–), 1.02–1.07 (t, J = 15.0 Hz, 0.5H, –CH3). Elemental
analysis (%): calcd for C54H41.2CdCl2N12O10: C 53.98, H 3.46, N 13.99;
found: C 53.73, H 3.57, N 13.86.
Fig. 7 Left: 1H NMR spectra (DMSO-d6) recorded on the samples which
were obtained by immersing 1 in the EtOH solutions of Q/QH2 with the
molar ratios at 1 :1 and 1: 2, respectively. The proton peaks of the encapsu-
lated Q and QH2 are marked. Right: LC measurement. The standard sample
was prepared by mixing equimolar amounts of Q and QH2 in MeOH. The
MeOH extractions of Q/QH2CCdL2 obtained from the EtOH solution of Q/
QH2 at molar ratios of 1: 1 and 1: 2, respectively.
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shows that Q is the preferred guest for the CdL2 host in both
cases. The selectivity of 1 is further supported by the liquid
chromatographic (LC) measurement. The above Q/QH2 loaded
crystals were extracted by MeOH, and the MeOH-extractions
were used for the LC analysis. As shown in Fig. 7, chromato-
graphic measurements on the MeOH extracts of CdL2 immersed
in a EtOH solution of Q/QH2 (molar ratio, 1 : 1 and 1 : 2)
indicated that the ratios of Q/QH2 are 4.6 : 1 and 3.2 : 1, respec-
tively. So the porous CdL2 framework can effectively separate Q
and QH2 under ambient conditions.
In conclusion, we have reported Q adsorption/separation,
sensing, and photoinduced transformation based on a porous
Cd(II)-MOF framework in a SC–SC fashion. Notabtly, Q exists in
the pores as a radical species in solar light, which makes the
CdL2 framework become a very sensitive luminescent sensor for
probing Q under ambient conditions. Furthermore, the porous
CdL2 framework can be a specific molecular flask to successively
upload different substrates, and moreover, facilitate the sunlight
induced Q transformation in the solid state. These results are in
sharp contrast to those of common molecular adsorption and
sensing behaviors based on MOFs, and reported photoinduced
chemical transformations in aqueous and organic media.
We are grateful for financial support from NSFC (Grant No.
21271120, 21475078 and 21101100), 973 Program (Grant No.
2012CB821705 and 2013CB933800) and the Taishan scholar’s
construction project.
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Notes and references
‡ Synthesis of 2. Compound 1 was sealed in a small vial full of Q vapour
at 70 1C for 48 h in the dark to generate 2 ([CdL2(ClO4)2]ꢂC6H4O2).
IR(KBr pellet cmꢁ1): 3348(w), 1650(ms), 1604(s), 1523(ms), 1480(ms),
1
1402(ms), 1071(vs), 1010(ms), 881(ms), 795(s), 689(ms), 619(s). HNMR
(300 MHz, DMSO, 25 1C, TMS, ppm): 8.69–8.70 (d, J = 3.0 Hz, 4H,
–C5H4N), 8.45 (s, 2H, –C6H4), 8.11–8.13 (d, J = 6.0 Hz, 2H, –C6H4), 7.96–
7.99 (d, J = 9.0 Hz, 2H, –C6H4), 7.81–7.82 (d, J = 3.0Hz, 4H, –C5H4N),
7.70–7.75 (t, J = 15.0 Hz, 2H, –C6H4), 6.86 (s, 1.6H, –C6H4O), 6.55
(s, 0.1H, –C6H6O), 6.45 (s, 2H, –NH2). Elemental analysis (%): calcd for
C54H40CdCl2N12O10: C 54.04, H 3.36, N 14.00; found: C 54.17, H 3.28,
N 14.05. Synthesis of 3. Compound 2 was immersed in EtOH vapour for
2 days in the dark to generate 3 ([CdL2(ClO4)2]ꢂ(C6H4O2)ꢂ(C2H5OH)).
IR(KBr pellet cmꢁ1): 3348(w), 3069(w), 1651(ms), 1604(s), 1521(ms),
1480(ms), 1402(ms), 1085(vs), 1008(ms), 881(ms), 796(s), 689(ms),
Chem. Commun.
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