solid state emissive bodipy dyes with bulky substituents
TRANSCRIPT
S1
SUPPORTING INFORMATION
Solid state emissive BODIPY dyes with bulky substituents as spacers
Tugba Ozdemir,† Serdar Atilgan,‡,§ Ilker Kutuk,‡ Leyla T. Yildirim,¶ Abdullah Tulek†, Mehmet Bayindir†,αααα and Engin U. Akkaya†,β*
UNAM-Institute of Materials Science and Nanotechnology, Bilkent
University, 06800 Ankara, Turkey. Fax: 90 312 266 4068; Tel: 90 312 290
3570; Department of Chemistry, Middle East Technical University, 06531,
Ankara, Turkey. Department of Chemistry, Suleyman DemirelUniversity,
Isparta, 32260, Turkey; Department of Engineering Physics, Hacettepe
University, Beytepe, 06800, Ankara, Turkey. Department of Physics,
Bilkent University, 06800 Ankara, Turkey. Department of Chemistry,
Bilkent University, 06800 Ankara, Turkey.
EXPERIMENTAL PROCEDURES
General
All chemicals and solvents purchased from Aldrich were used without further purification. 1H
NMR and 13C NMR spectra were recorded using a Bruker DPX-400 in CDCl3 or DMSO-d6
with TMS as internal reference. Absorption spectrometry was performed using a Varian
spectrophotometer. Steady state fluorescence measurements were conducted using a Varian
Eclipse spectrofluorometer. Column chromatography of all products was performed using
Merck Silica Gel 60 (particle size: 0.040–0.063 mm, 230–400 mesh ASTM). Reactions were
monitored by thin layer chromatography using fluorescent coated aluminum sheets. Solvents
used for spectroscopy experiments were spectrophotometric grade. Mass spectrometry
measurements were done at the Ohio State University Mass Spectrometry and Proteomics
Facility, Columbus, Ohio, U.S.A.
S2
Synthesis (Numbering of the compunds is different for the SI)
4,4-difluoro-8-(3,5-di-tert-butyl)phenyl-1,3,5,7-tetramethyl-4-bora-3a,4a-diaza-s-
indacene (3).
3,5-di-tert-butylbenzaldehyde (1) (1.83 mmol, 400 mg) and 2,4-dimethylpyrrole (2)
(3.67 mmol, 348 mg) were dissolved in CH2Cl2 (350 mL) purged with argon in a 100 mL
flask. 1 drop of TFA was added and the mixture was stirred at room temperature for 3 hrs.
When TLC showed consumption of the aldehyde was complete, a solution of 295 mg (1.83
mmol) of DDQ (2,3-Dichloro-5,6-dicyano-p-benzoquinone) in CH2Cl2 was added. After 3 h,
Et3N (4 ml) and BF3.OEt2 (4 ml) were added. Immediately after the addition of BF3.OEt2
bright green fluorescence was observed. Crude product was washed three times with water,
dried over Na2SO4 and concentrated in vacuo. Then crude product purified by silica gel
column chromatography using CHCl3. The pale orange fraction which has bright green
fluorescence was collected. Orange solid (0.476 mmol, 207 mg, 26 %). 1H NMR (400 MHz, CDCl3) δ 7.41 (s, 2H), 7.02 (s, 1H), 5.93 (s, 2H), 2.54 (s, 6H), 1.33 (s,
6H), 1.22 (s, 18H) 13C NMR (100 MHz, CDCl3) δ 155.1, 152.0, 143.3, 143.2, 134.0, 131.5, 122.1, 121.9, 121.0,
35.0, 31.4, 14.5, 14.1.
ESI-HRMS calcd for M+Na 458.2795, found 458.2780, ∆= 3.3 ppm
S3
4,4-difluoro-8-(4-tert-butyl)phenyl-2,6-diethyl-1,3,5,7-tetramethyl-4-bora-3a,4a-diaza-s-
indacene (6).
4-tert-butylbenzaldehyde (4) (3.10 mmol, 500 mg) and 2,4-dimethyl-3-diethyl pyrrole (5) (6.2
mmol, 761.26 mg) were dissolved in CH2Cl2 (400 mL) purged with argon in a 100 mL flask.
1 drop of TFA was added and the mixture was stirred at room temperature for 3 hrs. When
TLC showed consumption of the aldehyde was complete, a solution of 500 mg (3.10 mmol)
of DDQ (2,3-Dichloro-5,6-dicyano-p-benzoquinone) in CH2Cl2 was added. After 3 h, Et3N (3
ml) and BF3.OEt2 (3 ml) were added. Immediately after the addition of BF3.OEt2 bright
yellow fluorescence was observed. Crude product was washed three times with water, dried
over Na2SO4 and concentrated in vacuo. Then crude product purified by silica gel column
chromatography using CH2Cl2. The orange fraction which has bright yellow fluorescence was
collected. Orange solid (0.147 mmol, 608 mg, 45 %). 1H NMR (400 MHz, CDCl3) δ 7.42 (d, 2H J=8.1 Hz), 7.15 (d, 2H J=8.1 Hz), 2.51 (s, 6H),
2.25-2.18 (q, 4H J=7.5Hz), 1.29 (s, 9H), 1.2 (s, 6H), 0.93-0.96 (t, 6H, J=7.5 Hz) 13C NMR (100 MHz, CDCl3) δ 152.9, 151.7, 140.2, 138.0, 132.2, 132.1, 130.5, 127.4, 125.3,
34.3, 30.9, 16.6, 14.1, 12.0, 11.0. Elemental analysis, calcd for C27H35BF2N2 C: 74.31, H:
8.08, N: 6.42. Found C: 74.21, H: 8.10, N: 6.39.
S4
Quantum yield calculations: (The numbering of the compounds from this point on is the same as the article.) Compound 1 was excited at 489 nm excitation and emission slits was both 5 nm. Fluorescein
was used as the reference compound for the quantum yield calculations of compound 1. The
quantum yield for fluorescein is 0.95 in 0.1 M NaOH solution. (see: R. Lakowicz, Principles
of Fluorescence Spectroscopy, 2nd Ed., Kluwer Academic/Plenum Publishers, New York,
London, Moscow, Dordrecht, 1999.) Compound 2 was excited at 480 nm and excitation,
emission slits were both 5 nm. Rhodamine 6G was used for quantum yield calculation of the
Mono-tert BODIPY. Rhodamine 6G quantum yield is 0.95 in ethanol. (see: H. Du, R. A. Fuh,
J. Li, A. Corkan, J. S. Lindsey, "PhotochemCAD: A computer-aided design and research tool
in photochemistry," Photochemistry and Photobiology, 68, 141-142, 1998)
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ppm (t1)
1.02.03.04.05.06.07.0
0
100000000
200000000
300000000
400000000
500000000
600000000
ppm (t1)050100150200
0
100000000
200000000
300000000
400000000
500000000
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Mass Spectrometry Data for 1: ESI-HRMS
S7
ppm (t1)
0.01.02.03.04.05.06.07.08.0
0
100000000
200000000
300000000
400000000
500000000
ppm (t1)050100150
0
100000000
200000000
300000000
400000000
S8
X-ray Diffraction Structure Analysis:
X-ray diffraction data were obtained on an Enraf-Nonius CAD4 (κ-geometry) diffractometer
operating in ω/2θ scan mode using graphite-monochromated MoKα radiation (λ = 0.71073 Å)
at room temperature. The lattice parameters and their estimated standard deviations were
determined by using CAD4 Express1. Three standard reflections were measured every 100
reflections and their intensities showed a good stability. Data reduction was carried out using
XCAD42. The structures were solved by direct methods and refined by the full-matrix least-
squares refinement on F2 using the programs SHELXS97 and SHELXL973, respectively, in
the WinGX package4. Atomic scattering factors were taken from the International Tables for
X-ray Crystallography5. The data collection details, crystals data and refinement parameters
are summarized in Table S1. Positional parameters of non-hydrogen atoms are given in Table
S2.
Perspective view of molecules is given in Figure S1. Selected bond lengths and angles are
given in Table S3. The molecules are held together by weak van der Waals interactions.
Hydrogen bond and molecular packing geometry of the molecules were calculated with
PLATON6 and hydrogen bonding geometry is summarized in Table S4. Packing figures (Fig
S2-S5) are prepared by MERCURY7 program.
S9
Table S1. Crystal data and experimental details of the title compounds Compound 1 Compound 2
Empirical formula C27 H35 B F2 N2 C27 H35 B F2 N2
Formula weight 436.38 436.38 Crystal system Monoclinic Triclinic Space group P 2/c 1P Crystal shape /color Prism/orange Prism/red Unit cell dimensions a (Å) 6.7325(10) 8.2514(10) b (Å) 12.196(2) 11.4775(10) c (Å) 15.301(2) 13.7766(10) α (º) 90 73.867(8)
β (º) 101.739(10) 79.099(7) γ (º) 90 89.638(8)
Volume (Å3) 1230.1(3) 1229.2(2) Z 2 2 Dcalc (Mg/m3) 1.283 1.179 Absorbtion coefficient (mm-1) 0.078 0.078 F(000) 468 468 h, k, l ranges -8→ 0, -15 →0, -18 →19 -10→ 10, -14 →0, 0 →-17 Refinement on F2 [ ]22
02 (0.0893P)Fσ1w += ,
)/32F(FP 2c
20 +=
[ ]220
2 (0.089P)Fσ1w += ,
)/32F(FP 2c
20 +=
Reflections collected/unique 2635/2433 [Rint=0.1121] 5194/4929 [Rint=0.0467] Parameters 151 309 Goodness of fit on F2 0.883 0.951 R indices [I>2σ(I)] R1=0.0737, wR2=0.1497 R1=0.0615, wR2=0.1427 R indices [all data] R1=0.3316, wR2=0.2156 R1=0.2240, wR2=0.1922 (∆/σ)max 0.000 0.000 Largest difference peak and hole (e/Å3) 0.219 and -0.261 0.199 and -0.221
Additional material available from Cambridge Crystallographic Data Center as deposition numbers: CCDC 712038, 712037.
Table S2.a: Atomic coordinates and equivalent isotropic displacement parameters for non-hydrogen atoms of compound 1. .
jii j jiijeq aaaaUU ∑∑= **3
1 )(
Atom x y z Ueq (Å2)
B 0.5 0.1545(7) 0.25 0.052(2)
F 0.4398(5) 0.0887(2) 0.3133(2) 0.0977(13)
N 0.3248(6) 0.2285(3) 0.2057(2) 0.0431(11)
C1 0.1418(8) 0.1957(4) 0.1596(3) 0.0493(14)
C2 0.0227(7) 0.2876(5) 0.1317(3) 0.0588(15)
C3 0.1349(8) 0.3797(4) 0.1592(3) 0.0479(14)
C4 0.3265(7) 0.3429(4) 0.2068(3) 0.0394(12)
C5 0.0834(8) 0.0778(4) 0.1425(4) 0.0724(17)
C6 0.0593(7) 0.4943(4) 0.1384(3) 0.0644(16)
C7 0.5 0.3973(5) 0.25 0.0383(17)
C8 0.5 0.5194(5) 0.25 0.0373(17)
C9 0.4690(6) 0.5778(4) 0.3242(3) 0.0415(13)
C10 0.4677(7) 0.6916(4) 0.3260(3) 0.0422(12)
C11 0.5 0.7453(6) 0.25 0.045(2)
C12 0.4308(8) 0.7556(4) 0.4067(3) 0.0525(15)
C13 0.4325(9) 0.6833(4) 0.4877(3) 0.0674(17)
C14 0.2234(9) 0.8116(5) 0.3822(4) 0.097(2)
C15 0.5966(10) 0.8423(4) 0.4322(4) 0.086(2)
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Table S2.b: Atomic coordinates and equivalent isotropic displacement parameters
for non-hydrogen atoms of compound 2. .
Atom x y z Ueq (Å2)
B 0.4775(5) 0.7252(4) 0.3338(3) 0.0442(10)
F1 0.4107(3) 0.6282(2) 0.41692(14) 0.0755(7)
F2 0.5378(2) 0.8137(2) 0.36973(15) 0.0710(7)
N1 0.6164(3) 0.6831(2) 0.26225(18) 0.0408(7)
N2 0.3441(3) 0.7761(2) 0.27113(19) 0.0416(7)
C1 0.7543(4) 0.6295(3) 0.2872(2) 0.0452(9)
C2 0.8543(4) 0.6062(3) 0.2003(3) 0.0462(9)
C3 0.7728(4) 0.6465(3) 0.1188(2) 0.0426(8)
C4 0.6223(4) 0.6954(3) 0.1573(2) 0.0385(8)
C5 0.7878(7) 0.6001(5) 0.3939(3) 0.0627(12)
C6 1.0161(5) 0.5462(3) 0.2004(3) 0.0629(11)
C7 0.9967(6) 0.4082(4) 0.2334(3) 0.0887(15)
C8 0.8378(4) 0.6395(3) 0.0112(2) 0.0570(10)
C9 0.4928(4) 0.7479(3) 0.1105(2) 0.0374(8)
C10 0.3556(4) 0.7886(3) 0.1661(2) 0.0392(8)
C11 0.2091(4) 0.8413(3) 0.1385(3) 0.0446(9)
C12 0.1123(4) 0.8607(3) 0.2259(3) 0.0477(9)
C13 0.1990(4) 0.8192(3) 0.3062(3) 0.0479(9)
C14 0.1597(4) 0.8720(3) 0.0343(2) 0.0599(11)
C15 -0.0509(4) 0.9190(3) 0.2332(3) 0.0623(11)
C16 -0.0317(5) 1.0561(4) 0.2069(3) 0.0844(14)
C17 0.1446(5) 0.8170(4) 0.4173(3) 0.0654(11)
C18 0.4988(4) 0.7571(3) -0.0001(2) 0.0388(8)
C19 0.4483(4) 0.6595(3) -0.0283(2) 0.0472(9)
C20 0.4597(4) 0.6642(3) -0.1311(2) 0.0513(10)
C21 0.5223(4) 0.7673(3) -0.2102(2) 0.0464(9)
C22 0.5666(5) 0.8656(3) -0.1794(3) 0.0565(10)
C23 0.5569(5) 0.8618(3) -0.0775(3) 0.0528(10)
C24 0.5374(5) 0.7736(3) -0.3243(3) 0.0554(10)
C25 0.5161(7) 0.6496(4) -0.3401(3) 0.0985(17)
C26 0.7059(5) 0.8304(4) -0.3862(3) 0.0917(15)
C27 0.4068(6) 0.8561(5) -0.3683(3) 0.0994(17)
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(a) (b)
Fig. S1 ORTEP [18] drawing of the molecular structure of the title compounds with the atomic numbering scheme. a) Compound 1, b) Compound 2.
Table S3. Selected bond lengths (Å) and bond angles (°). Compound 1 Compound 2
B – F 1.381(5) B – F1 1.384(4) F2 – B 1.380(4) N – C1 1.350(5) N1 – C1 1.346(4) N – C4 1.395(5) N1 – C4 1.405(3) B – N 1.530(6) N1 – B 1.533(4) N2 – B 1.538(5) N2 – C13 1.349(4) N2 – C10 1.398(4) F – B – Fi 108.9(7) F2 – B – F1 108.9(3) F – B – Ni 110.0(2) F2 – B – N1 110.3(3) F – B – N 110.11(19) F1 – B – N1 110.0(3) F1 – B – N2 109.8(3) F2 – B – N2 110.3(3) Ni – B – N 107.7(6) N1 – B – N2 107.6(3) B – N – C1 126.6(5) B – N1 – C1 126.9(3) B – N – C4 125.5(5) B – N1 – C4 125.4(3) B – N2 – C10 125.3(3) B – N2 – C13 126.6(3)
Symmetry code i: 1-x, y, 1/2-z
Table S4. Structural parameters of hydrogen bonds between donor (D), acceptor (A) and hydrogen (H).
Compound D −−−− H ⋅⋅⋅⋅⋅⋅⋅⋅⋅⋅⋅⋅ A D−−−−H (Å) A⋅⋅⋅⋅⋅⋅⋅⋅⋅⋅⋅⋅H (Å) D⋅⋅⋅⋅⋅⋅⋅⋅⋅⋅⋅⋅A (Å) D−−−−H⋅⋅⋅⋅⋅⋅⋅⋅⋅⋅⋅⋅H (°°°°)
1 C5 – H5C⋅⋅⋅F 1.01(5) 2.55(6) 3.173(8) 120(4)
2 C5 – H5C⋅⋅⋅F1a 0.98(5) 2.35(5) 3.315(4) 166(4)
Symmetry codes [a: 1-x, 1-y, 1-z]
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Fig. S2 Two different views of the packing diagram of the title compound 1. Planes A, B and C are the closest near parallel π-surfaces defined as the boradiazaindacene framework. Table S5. The distance between the closest near parallel π-surfaces for compound 1.
Table S6. The distance between the closest near parallel π-surfaces for compound 2.
S13
Fig. S3 Packing diagram of the title compound 2. Planes A, B and C are the closest near parallel π-surfaces defined as the boradiazaindacene framework.
Fig. S4 View of the plane defined by the bodipy π-surfaces (A) and 8-phenyl substituent (P), dihedral angle between the A and P is 79.56 and 84.35° for compound 1 and 2 respectively.
S14
Fig. S5 Packing diagram of the of the bodipy dye with no meso substituent studied in reference 8. Dihedral angle between the A and B group planes is 17.90°. Table S7. The distance between the closest near parallel π-surfaces for the reference compound.
Fig. S6 Hydrogen bonding geometry in compound 2.
S15
References
1. Enraf-Nonius 1994. CAD-4 Express Software. Enraf-Nonius, Delft, Netherlands.
2.
Harms, K. & Wocadlo, S. 1995, XCAD-4. Program for Processing CAD-4 Diffractometer Data. University of Marburg, Germany.
3. Sheldrick, G. M. 1997, SHELXS97 and SHELXL97. Program for Crystal Structure
Solution and Refinement. University of Gottingen, Germany.
4. Farrugia, L. J. WinGX. Program for Crystallography Package. J. Appl. Cryst. 32
(1999) 837.
5. Wilson, A.J.C. 1992, Ed. International Tables for Crystallography, Volume C, Kluwer Academic Publishers, Dordrecht, The Netherlands.
6. Spek, A. L., J. Appl. Cryt. 36, 7-13 (2008).
7. Mercury: visualization and analysis of crystal structures C. F. Macrae, P. R. Edgington, P. McCabe, E. Pidcock, G. P. Shields, R. Taylor, M. Towler and J. van de Streek, J. Appl. Cryst., 39, 453-457 (2006). 8. Bandichhor, R.; Thivierge, C.; Bhuvanesh, N. S. P.; Burgess, K. Acta. Cryst., Sect. E, 62, 4310 (2006).
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All bond lengths (Å) and angles (°°°°)
Compound (1)
B F 1.381(5)
N C1 1.350(5)
N C4 1.395(5)
B N 1.530(6)
C1 C2 1.394(6)
C1 C5 1.500(6)
C3 C2 1.372(6)
C3 C6 1.499(6)
C4 C7 1.389(5)
C4 C3 1.419(6)
C8 C7 1.489(8)
C9 C8 1.392(5)
C10 C9 1.388(6)
C10 C11 1.390(5)
C10 C12 1.524(6)
C12 C13 1.519(6)
C14 C12 1.531(7)
C15 C12 1.529(7)
Compound (2)
F1 B 1.384(4)
F2 B 1.380(4)
N1 C1 1.346(4)
N1 C4 1.405(3)
N1 B 1.533(4)
N2 C13 1.349(4)
N2 C10 1.398(4)
N2 B 1.538(5)
C1 C5 1.492(5)
C2 C1 1.410(4)
C2 C6 1.499(5)
C3 C2 1.385(4)
C3 C8 1.502(4)
C4 C9 1.399(4)
C4 C3 1.430(4)
C6 C7 1.522(5)
C9 C18 1.489(4)
C10 C9 1.397(4)
C10 C11 1.418(4)
C11 C12 1.385(4)
C11 C14 1.514(4)
C12 C13 1.402(4)
C12 C15 1.499(5)
C13 C17 1.505(4)
C16 C15 1.516(5)
C18 C19 1.374(4)
C19 C20 1.387(4)
C21 C22 1.384(4)
C21 C20 1.390(4)
C21 C24 1.534(4)
C23 C22 1.379(4)
C23 C18 1.383(4)
C24 C25 1.515(5)
C24 C26 1.530(5)
C27 C24 1.530(5)
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Compound (1)
F B Fi
108.9(7)
F B Ni
110.0(2)
F B N 110.11(19)
Ni
B N 107.7(6)
C1 N C4 107.9(4)
C1 N B 126.6(5)
C4 N B 125.5(5)
C9 C10 C11 116.9(5)
C9 C10 C12 122.1(4)
C11 C10 C12 121.0(4)
C7 C4 N 119.2(5)
C7 C4 C3 133.0(5)
N C4 C3 107.8(4)
C13 C12 C10 112.8(4)
C13 C12 C15 108.0(5)
C10 C12 C15 109.3(4)
C13 C12 C14 108.3(4)
C10 C12 C14 108.7(4)
C15 C12 C14 109.7(5)
C10 C11 C10i
123.7(7)
C2 C3 C4 106.5(4)
C2 C3 C6 123.8(5)
C4 C3 C6 129.7(5)
C10 C9 C8 122.0(5)
N C1 C2 109.2(4)
N C1 C5 123.7(5)
C2 C1 C5 127.1(5)
C9 C8 C9i
118.5(6)
C9 C8 C7 120.7(3)
C4 C7 C4i
122.8(6)
C4 C7 C8 118.6(3)
C4i
C7 C8 118.6(3)
C3 C2 C1 108.6(4)
Symmetry code i: 1-x, y, 1/2-z
Compound (2)
F2 B F1 108.9(3)
F2 B N1 110.3(3)
F1 B N1 110.0(3)
F1 B N2 109.8(3)
F2 B N2 110.3(3)
N1 B N2 107.6(3)
B N1 C1 126.9(3)
B N1 C4 125.4(3)
B N2 C10 125.3(3)
B N2 C13 126.6(3)
C1 N1 C4 107.7(3)
N1 C1 C2 110.4(3)
N1 C1 C5 122.4(3)
N1 C4 C9 120.0(3)
N1 C4 C3 107.6(3)
N2 C10 C9 120.3(3)
N2 C10 C11 107.2(3)
N2 C13 C12 110.1(3)
N2 C13 C17 122.3(3)
C13 N2 C10 108.1(3)
C1 C2 C6 124.8(3)
C2 C1 C5 127.3(4)
C2 C3 C4 107.1(3)
C2 C3 C8 124.5(3)
C2 C6 C7 113.0(3)
C3 C2 C1 107.2(3)
C3 C2 C6 128.0(3)
C4 C3 C8 128.4(3)
C4 C9 C18 119.3(3)
C9 C4 C3 132.4(3)
C9 C10 C11 132.5(3)
C10 C11 C14 128.2(3)
C10 C9 C4 121.3(3)
C10 C9 C18 119.3(3)
C11 C12 C13 106.8(3)
C11 C12 C15 127.0(3)
C12 C11 C10 107.8(3)
C12 C11 C14 124.0(3)
C12 C13 C17 127.7(3)
C12 C15 C16 112.3(3)
C13 C12 C15 126.1(3)
C18 C19 C20 121.2(3)
C19 C18 C23 117.8(3)
C19 C18 C9 120.3(3)
C19 C20 C21 121.9(3)
C20 C21 C24 122.5(3)
C21 C24 C27 109.1(3)
C22 C21 C20 115.6(3)
C22 C21 C24 121.9(3)
C22 C23 C18 120.4(3)
C23 C18 C9 121.9(3)
C23 C22 C21 123.0(3)
C25 C24 C26 108.4(3)
C25 C24 C21 112.3(3)
C25 C24 C27 109.3(3)
C26 C24 C21 110.7(3)
C26 C24 C27 106.9(3)
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