SUPPORTING INFORMATION
Effects of temperature and CO2 pressure on the emission of N,N’dialkylated perylene diimides in poly(alkyl methacrylate) films.
Are guest-host alkyl group interactions important?
KIZHMURI P DIVYA a,b, MICHAEL J BERTOCCHI a and RICHARD G WEISS *,a
a
Department of Chemistry, Georgetown University, Washington, DC 20057-1227, USA
b
PSMO College, Tirurangadi, Malappuram, Kerala 676 306, India
e-mail: weissr@georgetown.edu
Table of Contents:
Page
1. Syntheses
1a. N,N′-dibutylperylene-3,4,9,10-tetracarboxylic diimide (PERBUT)
4
1b. N,N′-dicyclohexylperylene-3,4,9,10-tetracarboxylic diimide (PERCYA)
4
Table S1. Densities, and average molecular weights of the PAMAs employed
in this study (data from suppliers).
5
Table S2. Energies of conformations from single point and optimized geometry
calculations of twisted N,N’-dimethyl bisperylene diimide using M06/6-31(d) in butyl acetate, as
modeled by the PCM function. Excited state calculations were made on the vertically-excited,
optimized ground state geometry.
5
Table S3. Excited singlet-state lifetimes (τ) of ~10-6 mol perylenes/kg PAMA in films at 295
K (λex = 480, λem = 530 nm).
6
Figure S1. Optimized ground-state geometry of N,N’-dimethyl bisperylene diimide. The angle
between the two aromatic groups is 90˚ as measured about the C25-N30-N59-C53 bonds. 6
Figure S2. Energies of conformations from single point and optimized geometry calculations of
twisted N,N’-dimethyl bisperylene diimide using M06/6-31(d) in butyl acetate, as modeled by
the PCM function. Excited state calculations were made on the vertically-excited, optimized
ground state geometry.
6
Figure S3. Emission intensities at the emission maxima of (a) PERCYA( ), PERBUT(),
PERPDA ( )and (b)TP ( ) in butyl acetate versus temperature (ex = 480 nm; conc.  10-6 M).
6
1
Figure S4. Normalized emission spectra (ex= 480 nm) of  10-6 mol/kg(a) PERBUT and (b)
PERCYA in PIBMA (), PEMA (----), PBMA (….), PHDMA (---) and PCHMA (--) at 295
K.
8
Figure S5. Normalized emission spectra (ex= 480 nm) of  10-6 mol/kg (a) PERPDA and (b) TP
in PAMA films at 295 K.
8
Figure S6. Emission intensities at 530 nm of ~ 10-6 mol/kg (a) PERBUT and (b) PERCYA in
PBMA versus temperature during heating () and cooling (). Tg (290 K) of PBMA is indicated
by the vertical dashed line (ex= 480 nm).
9
Figure S7. Emission maxima of ~ 10-6 mol/kg (a) PERPDA and (b) TP in PBMA versus
temperature during heating () and cooling (). Tg (290 K) of PBMA is indicated by the vertical
dashed line (ex= 480 nm).
9
Figure S8. Emission intensities at 530 nm of ~ 10-6 mol/kg (a) PERBUT and (b) PERCYA in
PEMA versus temperature during heating () and cooling () cycles. Tg (342 K) of PEMA is
indicated by the vertical dashed line (ex= 480 nm).
10
Figure S9. Emission maxima of ~ 10-6 mol/kg (a) PERPDA and (b) TP in PEMA versus
temperature during heating () and cooling () cycles. Tg (342 K) of PEMA is indicated by the
vertical dashed line (ex= 480 nm).
10
Figure S10. Emission intensities at 530 nm of ~ 10-6 mol/kg (a) PERBUT and (b) PERCYA in
PIBMA versus temperature during heating () and cooling () cycles. Tg (322 K) of PIBMA is
indicated by the vertical dashed line (ex= 480 nm).
11
Figure S11. Emission maxima of ~ 10-6 mol/kg(a) PERPDA and (b) TP in PIBMA versus
temperature during heating () and cooling () cycles. Tg (322 K) of PIBMA is indicated by the
vertical dashed line (ex= 480 nm).
11
Figure S12. Emission intensities at 530 nm of ~ 10-6 mol/kg (a) PERBUT and (b) PERCYA in
PCHMA versus temperature during heating () and cooling () cycles. Tg (368 K) of PCHMA is
indicated by the vertical dashed line (ex= 480 nm).
12
Figure S13. Emission maxima of ~ 10-6 mol/kg (a) PERPDA and (b) TP in PCHMA versus
temperature during heating () and cooling () cycles. Tg (368 K) of PCHMA is indicated by the
vertical dashed line (ex= 480 nm).
12
Figure S14. Emission intensities at 530 nm of ~ 10-6 mol/kg (a) PERBUT and (b) PERCYA in
PHDMA versus temperature during heating () and cooling () cycles. Tm (281 K) is indicated
by the vertical dashed line (ex= 480 nm).
13
2
Figure S15. Emission maxima of ~ 10-6 mol/kg (a) PERPDA and (b) TP in PHDMA versus
temperature during heating () and cooling () cycles. Tm (281 K) of PHDMA is indicated by the
vertical dashed line (ex= 480 nm).
13
Figure S16. Effect of CO2 pressure on the emission intensity of ~ 10-6 mol PERCYA/kg PAMA
at 295 K: PBMA ( ), PIBMA (), and PEMA ( ) (ex= 480 nm).
14
Figure S17. Effect of CO2 () and N2 () pressure on emission intensity of ~ 10-6 mol
PERCYA/kg PBMA at 295 K (ex= 480 nm; Tg = 290 K).
14
Figure S18. Decay profiles of perylene diimide guest molecules ~10-6 M in butyl acetate at 295 K
(λex = 480, λem = 530 nm).
15
Figure S19. Decay profiles of ~10-6 mol/kg (a) PERCYA and (b) PERPDA in PAMA films at 295 K
(λex = 480, λem = 530 nm).
15
Figure S20. Decay profiles of ~10-6 mol/kg (a) PERBUT and (b) TP in PAMA films at 295 K (λ ex =
480, λem = 530 nm).
16
1.
Syntheses: PERBUT and PERCYA were synthesized by a slight modification of the
condensation procedure developed by Langhals.1
1a.N,N′-dibutylperylene-3,4,9,10-tetracarboxylic diimide (PERBUT).
Perylene-3,4,9,10-tetracarboxylic dianhydride 250 mg (0.64 mmol) and n-butylamine (467 mg,
6.40 mmol) in toluene (10 mL) were heated with stirring at 116-118°C for 12 h under a N2
atmosphere. The reaction mixture was then cooled to room temperature and toluene was
removed under reduced pressure. The crude product was purified by column chromatography on
silica gel (mesh 60-200) with CHCl3/MeOH (99.5/0.5) as eluent. The product was dried at 60 C
under vacuum (200 mmHg) for 24 h to yield a dark red solid (yield: 95 mg, 30%).
N,N′-dibutylperylene-3,4,9,10-tetracarboxylic diimide (PERBUT) (>99 pure by HPLC). Mp
>300 C. 1H NMR (CF3CO2D, 400 MHz), δ 9.02-8.60 (m, 8H, perylene), 4.59-4.55 (t, 4H, -NCH2-), 2.10-2.03 (m, 4H, -N-CH2-CH2-), 1.83-1.74 (m, 4H, -N-CH2-CH2-CH2-), 1.31-1.27 (t,
6H, -CH3). Elemental analysis: calcd for C33H28N2O4: C, 76.73; H, 5.46; N, 5.42. Found C,
76.48; H, 5.21; N, 5.57.
1b.N,N′-dicyclohexylperylene-3,4,9,10-tetracarboxylic diimide (PERCYA).
A similar procedure as that for the synthesis of PERBUT, except with cyclohexylamine (1.26 g,
12.7 mmol) instead of n-butylamine, was used. The crude product was purified by column
3
chromatography on silica gel (mesh: 60-200) with CHCl3 as the eluent. Yield 200 mg (30).
PERCYA obtained was dried at room temperature under vacuum (200 mm/Hg) for 24 h.
N,N′-dicyclohexylperylene-3,4,9,10-tetracarboxylic diimide (PERCYA) (>99 pure by HPLC).
Mp >300 C. 1H NMR (CDCl3, TMS, 400 MHz), δ 8.68-8.60 (m, 8H, perylene), 5.09-5.02 (m,
2H, -N-CH-), 2.62-2.56 (m, 4H), 1.94 (m, 4H,), 1.76-1.73 (m, 6H), 1.43 (m, 6H); Elemental
analysis: calcd for C36H32N2O4: C, 77.68; H, 5.79; N, 5.03. Found; C, 77.51; H, 5.67;
N, 5.17. Syntheses of TP and PERPDA are reported elsewhere (2). They were >99 pure
according to HPLC analyses.
Table S1: Densities, and average molecular weights of the PAMAs employed in this study (data
from suppliers).
Polymer
density
mol wt
(g cc-1)
(Mw)
PHDMA
0.87
200 000
PBMA
1.07
180 000
PIBMA
1.05
70 000
PEMA
1.10
350 000
PCHMA
1.10
65 000
Table S2. Energies of conformations from single point and optimized geometry calculations of
twisted N,N’-dimethyl bisperylene diimide using M06/6-31(d) in butyl acetate, as modeled by
the PCM function. Excited state calculations were made on the vertically-excited, optimized
ground state geometry.
Dihedral
Angle (˚)
Ground
StateEnergy
(kcal/mol)
Energy
(kcal/mol)
90
85
80
75
70
0
0.14
0.67
1.5
2.4
0
0.14
0.67
1.5
2.4
1S
4
65
60
55
50
45
40
35
30
25
20
15
10
5
0
4.3
7.3
12.5
20.8
34.4
55.6
87.6
132.7
190.3
254.3
311.6
340.4
358
364.6
4.2
7
11.7
19.3
31.9
51
79.5
113.4
157.7
-----------
Table S3. Excited singlet-state lifetimes (τ) of ~10-6 molperylenes/kg PAMA in films at 295 K
(λex = 480, λem = 530 nm).
PAMAa
PIBMA(g)
PEMA(g)
PERBUT PBMA(r)
PCHMA(g)
PHDMA(r)
PIBMA(g)
PEMA(g)
PERCYA PBMA(r)
PCHMA(g)
PHDMA(r)
PIBMA(g)
PEMA(g)
PERPDA PBMA(r)
PCHMA(g)
PHDMA(r)
PIBMA(g)
PEMA(g)
TP
PBMA(r)
PCHMA(g)
PHDMA(r)
a
g = glassy state; r = rubbery state.
Perylene
5
 (ns)
4.0
4.1
4.1
4.0
4.0
4.0
4.0
4.0
4.0
4.0
4.1
4.1
3.9
4.0
4.0
2.8
2.8
2.9
2.9
2.8
2
1.0
1.1
1.2
1.0
1.2
1.0
1.1
1.1
1.0
1.1
1.3
1.0
1.0
1.2
1.0
1.3
1.0
1.0
1.2
1.0
Figure S1. Optimized ground-state geometry of N,N’-dimethyl bisperylene diimide. The angle
between the two aromatic groups is 90˚ as measured about the C25-N30-N59-C53 bonds.
Figure S2. Normalized (a) absorption and (b) emission spectra (ex= 480 nm) of  10-6
MPERPDA (), PERCYA () PERBUT (---) and TP (----) in butyl acetate.
6
Figure S3. Emission intensities at the emission maxima of (a) PERCYA( ), PERBUT(),
PERPDA ( )and (b)TP ( ) in butyl acetate versus temperature (ex = 480 nm; conc.  10-6 M).
Figure S4. Normalized emission spectra(ex= 480 nm) of  10-6mol/kg(a) PERBUT and (b)
PERCYA in PIBMA (), PEMA (----), PBMA (….), PHDMA (---) and PCHMA (--)at 295
K.
Figure S5. Normalized emission spectra (ex= 480 nm) of  10-6mol/kg (a) PERPDA and (b) TP
in PAMA films at 295 K.
7
Figure S6. Emission intensities at 530 nm of ~ 10-6 mol/kg (a) PERBUT and (b) PERCYA in
PBMA versus temperature during heating () and cooling (). Tg (290 K) of PBMA is indicated
by the vertical dashed line (ex= 480 nm).
Figure S7. Emission maxima of ~ 10-6 mol/kg (a) PERPDA and (b) TP in PBMA versus
temperature during heating () and cooling (). Tg (290 K) of PBMA is indicated by the vertical
dashed line (ex= 480 nm).
8
Figure S8. Emission intensities at 530 nm of~ 10-6 mol/kg (a) PERBUT and (b) PERCYA in
PEMA versus temperature during heating () and cooling () cycles. Tg (342 K) of PEMA is
indicated by the vertical dashed line (ex= 480 nm)
Figure S9. Emission maxima of ~ 10-6 mol/kg (a) PERPDA and (b) TP in PEMA versus
temperature during heating () and cooling () cycles. Tg (342 K) of PEMA is indicated by the
vertical dashed line (ex= 480 nm)
9
Figure S10. Emission intensities at 530 nm of ~ 10-6 mol/kg (a) PERBUT and (b) PERCYA in
PIBMA versus temperature during heating () and cooling () cycles. Tg (322 K) of PIBMA is
indicated by the vertical dashed line (ex= 480 nm).
Figure S11. Emission maxima of ~ 10-6 mol/kg(a) PERPDA and (b) TP in PIBMA versus
temperature during heating () and cooling () cycles. Tg (322 K) of PIBMA is indicated by the
vertical dashed line (ex= 480 nm).
10
Figure S12. Emission intensities at 530 nm of ~ 10-6 mol/kg (a) PERBUT and (b) PERCYA in
PCHMA versustemperature during heating () and cooling () cycles. Tg (368 K) of PCHMA is
indicated by the vertical dashed line (ex= 480 nm)
Figure S13. Emission maxima of ~ 10-6 mol/kg (a) PERPDA and (b) TP in PCHMA versus
temperature during heating () and cooling () cycles. Tg (368 K) of PCHMA is indicated by the
vertical dashed line (ex= 480 nm).
11
Figure S14. Emission intensities at 530 nm of ~ 10-6 mol/kg (a) PERBUT and (b) PERCYA in
PHDMA versus temperature during heating () and cooling () cycles. Tm (281 K) is indicated
by the vertical dashed line (ex= 480 nm).
Figure S15. Emission maxima of ~ 10-6 mol/kg (a) PERPDA and (b) TP in PHDMA versus
temperature during heating () and cooling () cycles. Tm (281 K) of PHDMA is indicated by the
vertical dashed line (ex= 480 nm).
12
Figure S16. Effect of CO2 pressure on the emission intensity of ~ 10-6 mol PERCYA/kg PAMA
at 295 K: PBMA ( ), PIBMA (), and PEMA ( ) (ex= 480 nm).
Figure S17. Effect of CO2 () and N2 () pressure on emission intensity of ~ 10-6 mol
PERCYA/kg PBMA at 295 K (ex= 480 nm; Tg = 290 K).
13
10000
Lamp profile
PERPDA
PERCYA
PERBUT
TP
1000
Counts
100
10
1
0
50
Time (ns)
100
Figure S18. Decay profiles of perylene diimide guest molecules~10-6Min butyl acetate at 295 K
(λex = 480, λem = 530 nm).
Lamp profile
PBMA
PIBMA
PEMA
PCHMA
PHDMA
a)
Counts
1000
100
10
10000
Lamp profile
PBMA
PIBMA
PEMA
PCHMA
PHDMA
b)
1000
Counts
10000
100
1
10
1
0
50
100
0
Time (ns)
50
100
Time (ns)
Figure S19. Decay profiles of ~10-6 mol/kg (a) PERCYA and (b) PERPDA in PAMA films at 295 K
(λex = 480, λem = 530 nm).
14
a)
Lamp profile
PBMA
PIBMA
PEMA
PCHMA
PHDMA
Counts
1000
100
10
10000
b)
1000
Counts
10000
100
Lamp profile
PBMA
PIBMA
PEMA
PCHMA
PHDMA
10
1
1
0
50
100
0
Time (ns)
50
100
Time (ns)
Figure S20. Decay profiles of ~10-6 mol/kg (a) PERBUT and (b) TP in PAMA films at 295 K (λex =
480, λem = 530 nm).
1. Langhals H 1995 Heterocycles 40 477.
2. Rajaram S, Shivanna R, Kandappa S K and Narayan K S 2012 J. Phys. Chem. Lett. 3
2405
15