Molecules 2013, 18. S12. Table S1a. IR data for the δC-H ip bands for pyrene and Copo C6-H/Pyr materials. á¿¡ (cmâ1. ) Îá¿¡ á¿¡ (cm. â1. ) Îá¿¡. Pyrene (guest).
Supporting Information Content I.
CCNPyr guest molecule ................................................................................................. S2 I.1. NMR spectra ............................................................................................................ S2 I.2. Photoluminescence data .......................................................................................... S5
II. "Host-guest" materials Copo C6-H/CCNPyr............................................................... S7 II.1. X-Ray data .............................................................................................................. S7 II.2. FT-IR spectra.......................................................................................................... S8 II.3. 31P-NMR spectra .................................................................................................... S9 III. "Host-guest" materials Copo C6-H/Pyr ..................................................................... S10 III.1. X-Ray data........................................................................................................... S10 III.2. FT-IR spectra ...................................................................................................... S11 III.3. Photoluminescence data ..................................................................................... S13 IV. "Host-guest" materials Copo C6-H/NPyrMal ........................................................... S14 IV.1. X-Ray data ........................................................................................................... S14 IV.2. FT-IR spectra ...................................................................................................... S14 V.
"Host-guest" materials PEG-5000/CCNPyr .............................................................. S17 V.1. X-Ray data ............................................................................................................ S17
Molecules 2013, 18 I.
S2
CCNPyr Guest Molecule I.1. NMR Spectra 1
H-NMR spectrum
O
O P
OEtO N O
Figure S1. 1H-NMR spectrum of CCNPyr (CDCl3, room temperature).
Molecules 2013, 18
S3 13
C-NMR spectrum
O
O P
OEtO N O
100000000
200000000
300000000
0
0
16.333 16.378 16.422 16.472 22.286 24.011 33.745 33.971 34.879 35.168 38.961 39.005
400000000
500000000
Figure S2. 13C-NMR spectrum of CCNPyr (CDCl3, room temperature).
41.179 41.203 41.646 41.670 62.001 62.057 62.365 62.422
50
40.243 40.329
63.371 63.423 63.488 63.540 121.374 122.414
150
124.420 124.552 125.132 125.371 125.606 125.781 125.835 125.904 126.004 126.346 126.366 127.133 127.176 127.584
100
123.507 123.581
132.080 176.121 176.395 178.700 179.026
ppm (t1)
130.548 130.638 130.757 130.834 130.916 131.018
200
128.410 128.489 128.683 128.885
Molecules 2013, 18
S4 31
P-NMR spectrum
O
O P
OEtO N O
0
-50
-100
-150
0
10000000
20000000
30000000
40000000
Figure S3. 31P-NMR spectrum of CCNPyr (CDCl3, room temperature, 85 % H3PO4 external probe).
ppm (t1)
150
100
50
25.597 25.872
Molecules 2013, 18
S5
I.2. Photoluminescence Data Figure S4. Absorption spectra of CCNPyr at various concentrations in two solvents (cyclohexane [CCNPyr] from 5.03.10−6 M to 2.45.10−9 M or acetonitrile [CCNPyr] from 4.41.10−6 M to 2.15.10−9 M).
Figure S5. (A) Photoluminescence spectra (emission mode, excitation at 317 nm) of CCNPyr at various concentrations in cyclohexane ([CCNPyr] from 1.26.10−6 M to 1.23.10−9 M) and acetonitrile ([CCNPyr] from 2.21.10−6 M to 2.15.10−9 M); (B) Photoluminescence spectra (emission mode, excitation at 317 nm) of CCNPyr at almost-similar concentration in both solvents.
(A)
(B)
Molecules 2013, 18
S6
Figure S6. Beer-Lambert graph for solutions of CCNPyr at various concentrations in cyclohexane and acetonitrile. Acetonitrile
Cyclohexane
-0,6
log(A(S0->Sn))
-0,8 -1,0
0,0 S0->Sn transitions S0->S4 S0->S3 S0->S2
-0,5 log(A(S0->Sn))
-0,4
-1,2 -1,4 -1,6 -1,8
S0->Sn transitions S0->S4 S0->S3 S0->S2
-1,0
-1,5
-2,0
-2,0
-2,2
-6,4
-7,0 -6,8 -6,6 -6,4 -6,2 -6,0 -5,8 -5,6 -5,4
-6,2
-6,0
-5,8
-5,6
-5,4
log([CCNPyr])
log([CCNPyr])
Figure S7. (a) Absorption spectrum of CCNpyr in the solid state; (b) Photoluminescence spectrum (emission mode, excitation at 317 nm) of CCNPyr in the solid state.
(a)
(b)
Molecules 2013, 18 II. "Host-guest" materials Copo C6-H/CCNPyr II.1. X-Ray data Figure S8. X-Ray diffractograms of "host-guest" materials Copo C6-H/CCNPyr. For sake of clarity, each diffractogram with a positive CCNPyr loading was shifted of + 100 cps one of the other.
S7
Molecules 2013, 18
S8
II.2. FT-IR spectra Figure S9. (a) IR spectra of CCNPyr (guest) and Copo C6-H matrix (host); (b) IR spectra of "host-guest" materials Copo C6-H/CCNPyr.
(a)
(b)
Molecules 2013, 18
S9
II.3. 31P-NMR spectra Figure S10. 31P-NMR spectra of Copo C6-H/CCNPyr redissolved in CDCl3. CCNPyr (0.00 equiv) by Copo C6-H monomer unit VEmCopoC6NNNPhA std_31P MeOD {D:\Bruker\TOPSPIN} ORGJ 1
H3PO4 5
VEmCopoC6NCCNpyrB std_31P MeOD {D:\Bruker\TOPSPIN} ORGJ 1
CCNPyr (0.05 equiv) by Copo C6-H monomer unit 4
VEmCopoC6NaCCNpyrC std_31P MeOD {D:\Bruker\TOPSPIN} ORGJ 1
CCNPyr (0.10 equiv) by Copo C6-H monomer unit 3
VEmCopoC6NaCCNpyrD std_31P MeOD {D:\Bruker\TOPSPIN} ORGJ 1
CCNPyr (0.25 equiv) by Copo C6-H monomer unit 2
VEmCopoC6NaCCNpyrE std_31P MeOD {D:\Bruker\TOPSPIN} ORGJ 1
CCNPyr (0.50 equiv) by Copo C6-H monomer unit 1
65
60
55
50
45
40
35
30
25
20
15
10
5
0 -5 f1 (ppm)
-10
-15
-20
-25
-30
-35
-40
-45
-50
-55
-60
-65
Molecules 2013, 18
S10
III. "Host-guest" materials Copo C6-H/Pyr III.1. X-Ray data Figure S11. Experimental X-Ray diffractogram of pyrene.
Figure S12. Theoretical X-Ray diffractogram of pyrene. (calculated with the X-Ray data described in "R.Allmann Z.Kristallogr.,Kristallgeom.,Kristallphys., Kristallchem. 1970, 132, 129").
Figure S13. X-Ray diffractograms of "host-guest" materials Copo C6-H/Pyr. For sake of clarity, each diffractogram with a positive Pyr loading was shifted of + 300 cps one of the other.
Molecules 2013, 18
S11
III.2. FT-IR spectra Figure S14. (a) IR spectra of Pyr (guest) and Copo C6-H matrix (host); (b) IR spectra of "host-guest" materials Copo C6-H/Pyr.
(a)
(b)
Molecules 2013, 18
S12
Table S1a. IR data for the δC-H ip bands for pyrene and Copo C6-H/Pyr materials. Pyrene (guest) Materials (Pyr equiv) 0.05 0.1 0.12 0.25 0.51
ῡ (cm−1) Δῡ ῡ (cm−1) Δῡ 1239 / 1182 / 1224 -15 1188 +6 1224 -15 1185 +3 / / 1186 +4 1241 +2[a] 1184 +2 1240 +1 1183 +1 [a]
[a] Not significant shift (Resolution = 0.8 cm−1).
Table S1b. IR data for the δC-H oop bands for pyrene and Copo C6-H/Pyr materials. Pyrene (guest) Materials (Pyr equiv) 0.05 0.1 0.12 0.25 0.51
ῡ (cm−1) Δῡ ῡ (cm−1) Δῡ ῡ (cm−1) 839 / 748 / 707 851 +12 757 +9 715 851 +12 757 +9 715 851 +12 757 +9 715 846 +7 752 +4 712 [a] 839 0 749 +1 709
[a] Not significant shift (Resolution = 0.8 cm−1).
Δῡ / +8 +8 +8 +5 +2
Molecules 2013, 18 III.3. Photoluminescence data Figure S15. Photoluminescence spectra (emission mode, excitation at 317 nm) of “guesthost” materials Copo C6-H/Pyr. in the solid state.
Figure S16. Comparison of Ix/Iy emission intensity ratios with the values of pyrene (from the litterature: Kalyanasundaram, K.; Thomas, J.K. J. Am. Chem. Soc. 1977, 99, 2039–2044).
S13
Molecules 2013, 18
S14
IV. "Host-guest" materials Copo C6-H/NPyrMal IV.1. X-Ray data Figure S17. X-Ray diffractogram of N-pyrenyl maleimide.
Figure S18. X-Ray diffractograms of "host-guest" materials Copo C6-H/NPyrMal for sake of clarity, each diffractogram with a positive NPyrMal loading was shifted of + 400 cps one of the other.
IV.2. FT-IR spectra
Molecules 2013, 18
S15
Figure S19. (a) IR spectra of NPyrMal (guest) and Copo C6-H matrix (host); (b) IR spectra of "host-guest" materials Copo C6-H/NPyrMal.
(a)
(b) Table S2a. IR data for the νC=O band of carboxylic acid of the host for the Copo C6-H/and Copo C6-H/NPyrMal materials. ῡ (cm−1) Δῡ
Molecules 2013, 18
S16 Copo C6-H (host) Materials (NPyrMal equiv) 0.05 0.08 0.1 0.25 0.50
1717 1714 1714 1712 1712 1712
/ -3 -3 -5 -5 -5
Table S2b. IR data for the νC=O band of imide group of the guest for the Npyrenylmaleimide and Copo C6-H/NPyrMal materials. NPyrMal (guest) Materials (NPyrMal equiv) 0.05 0.08 0.1 0.25 0.50
ῡ (cm−1) Δῡ 1702 / [a] / / [a] 1705 +3 1714 +2 1702 0 1701 +1 [b]
[a] νC=O (COOH, host) band superimposed with νC=O (imide, guest).[b] Not significant shift (Resolution = 0.8 cm−1).
Molecules 2013, 18
S17
V. "Host-guest" materials PEG-5000/CCNPyr V.1. X-Ray data Figure S20. X-Ray difractogramms of “guest-host” materials PEG 5000/CCNPyr. For sake of clarity, each diffractogram with a positive CCNPyr loading was shifted of + 1500 cps one of the other.
Figure S21. Schematic representation of the postulated non covalent interactions, in the solid state, (A) between pyrene and the Copo C6-H matrix; (B) between N-pyrenylmaleimide and the Copo C6-H matrix.
(A)
(B)
