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synchronized sampling of the indirect dimension. Phase cycling in-
volved the States method for acquisition of pure absorption line
shapes and a 48 step phase cycle for coherence transfer pathway
selection. The SOQE parameters and isotropic chemical shift values
were determined by momenta analyses[39,40] from the extracted
rows of the sheared MQMAS spectrum. The 13C MAS NMR spectra
were obtained with a ramped 13C{1H} cross-polarization experiment
at contact time of 5 ms and a sample spinning frequency of
10 kHz.
ferent fluorescence emission spectra could be observed due to
isolated chromophores at low concentration and chromo-
phores in close proximity at higher concentrations.
At this point it shall be highlighted that the method that we
used to incorporate a fluorescent dye inside a MOF scaffold
can be transferred to any other fluorescent dye that possesses
the right thermostability and solubility for the MOF synthesis.
The concentration of the dye can easily be lowered to prevent
any self-quenching. Because the fluorescence can be switched-
on by the covalent attachment of an electron acceptor to the
amino group, this step could be used to incorporate the recep-
tor. Hence, this promising strategy could be used in the future
for the fabrication of a selective recognition MOF chemosen-
sor.
Solid-state fluorescence: The experiments were run on a Varian
Cary Eclipse (detector Hamamatsu R3896, excitation slit 5.0 nm,
emission slit 5.0 nm, data interval 0.20 nm, averaging time 0.10 s,
detector voltage 590 mV, scan rate 120 nmminÀ1) equipped with
a solid sample holder. About 1 mg of the corresponding sample
were spread between two glass slides and fixed on the sample
holder.
Sample preparation
Experimental Section
Materials
2-[9-(1-Hexylheptyl)-1,3,8,10-tetraoxo-3,8,9,10-tetrahydro-1H-
anthra[2,1,9-def;6,5,10-d’e’f’]diisoquinolin-2-yl]terephthalic acid
Acetic anhydride (p.A.), acetic acid (in-house chemical supply), alu-
minium(III) chloride hexahydrate (99.9%, Aldrich), 2-amino tereph-
thalic acid (99%, Aldrich), N,N-dimethylformamide (99.8%, Aldrich),
hydrochloric acid (in-house chemical supply), formanilde (99%, Al-
drich), caesium fluoride (ꢀ98.0%, Aldrich), chloroform (in-house
chemical supply), deuterium oxide (99.9%, Eurisotop),
[D6]dimethylsulfoxide (99.8%, Eurisotop), ethanol (for analysis, in-
house chemical supply), imidazole (99%, Aldrich), perylene mono
imide mono anhydride 1.[37]
(2): 9-(1-Hexylheptyl)-2-benzopyrano[6’,5’,4’:10,5,6]anthra[2,1,9-def]-
isoquinoline-1,3,8,10-tetraone (200 mg, 0.35 mmol)[37] and 2-amino-
terephthalic acid (190 mg, 1.1 mmol) were dissolved in molten imi-
dazole (1.5 g) at 1408C and stirred for 2 h. The mixture was dis-
solved in CHCl3 and washed with aqueous HCl (2m, 2100 mL).
The organic phase was collected, washed with distilled water, dried
with Na2SO4, and evaporated in vacuo. The residue was purified by
using column separation (silica gel 80044 mm, chloroform/acetic
acid 20:1). The residue was dissolved in a minimum amount of
a mixture of CHCl3 and acetic acid, an excess of distilled water was
added and the CHCl3 was removed completely in vacuo. The solid
was collected by vacuum filtration (D4 glass filter) and dried at
110 8C. Yield: 170 mg (64%), red solid, M.p. >2508C. Rf value (silica
gel, chloroform/acetic acid 20:1): 0.30. 1H NMR (600 MHz, CDCl3/
(CD3)2SO (10:1), 258C): d=0.77 (t, 3J(H,H)=6.9 Hz, 6H, 2CH3),
1.23–1.32 (m, 16H, 8CH2), 1.77–1.84 (m, 2H, b-CH2), 2.15–2.23 (m,
Characterization
Nitrogen sorption: Nitrogen sorption measurements were per-
formed on a Quantachrome NOVA 4000e station at 77 K. Outgas-
sing of 20–30 mg sample was performed for 12 h at 423 K. Scientif-
ic evaluation of sorption data was carried out with the software
suite NovaWin, Version 10.0 (Quantachrome Instruments 2007). BET
surface areas for all samples were calculated employing the linear-
ized form of the BET equation with 6 data points (p/p0 =0.050,
0.075, 0.100, 0.125, 0.150, and 0.200) in the range from p/p0 0.05 to
0.2. For all samples the correlation coefficient was higher than
0.999.
X-ray Diffraction (XRD): Powder X-ray diffraction (PXRD) measure-
ments were performed by using a Bruker D8 diffractometer
(CuKa1 =1.5406 ; CuKa2 =1.5444 ) in q–q geometry equipped with
a Lynx-Eye detector. The powder samples were measured between
2 and 208 2q, with a step-size of 0.058 2q.
4
2H, b-CH2), 5.10–5.16 (m, 1H, N-CH), 8.00 (d, J(H,H)=1.7 Hz, 1H,
CHaryl), 8.18 (dd, 3J(H,H)=8.2, 4J(H,H)=1.7 Hz, 1H, CHaryl), 8.28 (d,
3J(H,H)=8.2 Hz, 1H, CHaryl), 8.56–8.64 ppm (m, 8H, 8CHperylene);
13C NMR (100 MHz, CDCl3/(CD3)2SO (10:1), 258C): d=14.0, 22.5,
26.9, 31.7, 32.3, 54.7, 123.0, 123.2, 123.4, 126.4, 126.7, 129.5, 130.0,
130.2, 131.6, 131.9, 132.2, 132.5, 134.9, 135.6, 135.9, 163.5, 165.8,
166.8 ppm; IR (ATR): n˜ =2952.5 (w), 2924.2 (m), 2855.5 (w), 1711.4
(w), 1695.0 (s), 1652.1 (m), 1592.1 (s), 1575.8 (m), 1504.7 (w), 1456.0
(w), 1432.5 (m), 1432.5 (m), 1341.4 (s), 1303.0 (w), 1252.7 (m),
1199.8 (w), 1175.6 (w), 1124.9 (w), 1108.1 (w), 966.5 (m), 854.0 (m),
808.5 (s), 743.3 (s), 658.6 cmÀ1 (m); UV/Vis (CHCl3): lmax (Erel)=459.8
NMR spectroscopy: Analyses were performed on
AMX 600 (Varian Vnmrs 600) or JEOL ECX-400. For the deuterium
lock chloroform and [D6]DMSO were used as an internal reference.
a Bruker
Solid-state nuclear magnetic resonance: The NMR experiments
were carried out on
a BRUKER Avance III 500 spectrometer
equipped with a commercial 4 mm MAS NMR probe. The magnetic
field strength was 11.75 T corresponding to 13C and 27Al resonance
frequencies of 125.8 and 130.5 MHz, respectively. The deshielding
values reported for 13C and 27Al refer to 1% Si(CH3)4 in CDCl3 and
(0.22), 490.2 (0.62), 527.0 nm (1.00); Fluorescence (CHCl3, lexc
=
490 nm): lmax (Irel)=534.6 (1.00), 576.0 (0.53), 626.4 nm (0.12); Fluo-
rescence quantum yield (CHCl3, lexc =490 nm, E490 nm/1 cm =0.0152,
reference 2,9-bis-(1-hexylheptyl)anthra[2,1,9-def;6,5,10-d’e’f’]diiso-
quinoline-1,3,8,10(2H,9H)-tetraone RN110590-84-6 with F=1.00):
0.90; MS (FAB+): m/z (%): 737.5 (22) [M++H], 719.4 (41), 555.3
(100), 537.3 (68), 509.3 (57), 391.2 (40); HRMS: m/z calcd (%) for
a solution of Al(NO3)3 1.1 mol kgÀ1 in D2O. The H resonance of 1%
1
Si(CH3)4 in CDCl3 served as an external secondary reference using
the X value for 27Al as reported by IUPAC.[37] Saturation combs
were applied prior to all repetition delays. A triple-quantum 27Al
MQMAS 2D spectrum was acquired using a three-pulse sequence
with a zero-quantum filter,[39] a repetition delay of 10 s and rotor-
Chem. Eur. J. 2015, 21, 10714 – 10720
10718
ꢀ 2015 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim