Highly emitting 8-propargylaminoBODIPY (8-PAB) 2 was
prepared in 94% yield. Unlike any other BODIPY structure
hitherto described in the literature, 2 displays efficient emission in
the blue region of the visible spectrum with a fluorescence
quantum yield up to 0.94 and high laser efficiency (35%) at
483 nm.Grants GTO-2007-C02-69094 (CONCyTEG) (Mexico),
MAT2007-65778-C02-01 and -02 of the Spanish MICINN
are gratefully acknowledged. V. Martin thanks CSIC for her
JAE-postdoctoral contract.Peer reviewe

Bañuelos Prieto, Jorge

Costela, A.

Garcia-Moreno, I.

Gómez-Durán, C.F.A.

López Arbeloa, Fernando

López Arbeloa, Iñigo

Martin, Virginia

Peña-Cabrera, Eduardo

Sastre, Roberto

Costela González, Ángel

Digital.CSIC

 S1Electronic Supplementary Information for 8-PropargylaminoBODIPY: Unprecedented Blue-emitting Pyrromethene Dye. Synthesis, Photophysics and Laser Properties. C. F. Azael Gómez-Durán,† Inmaculada García-Moreno,*,ǂ Angel Costela,ǂ Virginia Martin,ǂ Roberto Sastre,¥ Jorge Bañuelos,§ Fernando López Arbeloa,*,§ Iñigo López Arbeloa,§ and Eduardo Peña-Cabrera.*,† Departamento de Química, Universidad de Guanajuato. Col. Noria Alta S/N. Guanjuato, Gto. Mexico, Instituto de Química-Física “Rocasolano”, CSIC, Serrano 119, 28006 Madrid, Spain, Instituto de Ciencia y Tecnología de Polímeros, CSIC, Juan de la Cierva 3, 28006 Madrid, Spain, and Departamento de Química Física, Universidad del País Vasco-EHU Apartado 644, 48080 Bilbao, Spain.. eduardop@quijote.ugto.mx    Table of Contents S2……………………………………..General Section S3 – S5………………………………..Procedures S6   ………………………………….. Table S1 S7……………………………………...Figures S1-S1 S8………………………………………References S9 ………………………………………1H NMR spectrum of 8-PAB in CDCl3 S10………………………………………1H NMR spectrum of 8-PAB in CD3CN   Supplementary Material (ESI) for Chemical CommunicationsThis journal is (c) The Royal Society of Chemistry 2010 S2      General. 1H and 13C NMR spectra were recorded on a Varian Gemini 200 (200 MHz) spectrometer in deuteriochloroform (CDCl3)  with either tetramethylsilane (TMS) (0.00 ppm 1H, 0.00 ppm 13C) or chloroform (7.26 ppm 1H, 77.00 ppm 13C) or  as internal reference, unless otherwise stated.  Data are reported in the following order:  chemical shift in ppm, multiplicities (br (broadened), s (singlet), d (doublet), t (triplet), q (quartet), sex (sextet), hex (hextet), m (multiplet), exch (exchangeable), app (apparent)), coupling constants, J (Hz), and integration. Infrared spectra were recorded on a Perkin-Elmer FTIR 1600 series spectrophotometer.  Peaks are reported (cm-1) with the following relative intensities: s (strong, 67-100%), m (medium 40-67%), and w (weak 20-40%).  Melting points were determined on a Stanford Research Systems EZ-Melt apparatus and are not corrected. Materials. Solvents for laser and photophysical studies were of spectroscopic grade (Merck, Aldrich or Sigma) and were used without purification. Those used in synthetic work were purified by standard methods. Other reagents were from commercial sources, and used as received. The commercial laser dye Coumarin 480, also called Coumarin 102 (laser grade, Exciton) was used as received with a purity >99% (checked by spectroscopic and chromatographic methods). ThiomethylBODIPY 1 is commercially available; alternatively, it can be prepared according to the literature starting from thiophosgene.[1]  Propargylamine is commercially available and was used as received. Supplementary Material (ESI) for Chemical CommunicationsThis journal is (c) The Royal Society of Chemistry 2010 S3 Synthesis of 8-PAB. A 20 mL scintillation vial was charged with thiomethylBODIPY 1  (100 mg, 0.42 mmol, 1 equiv.), a stir-bar, and dicloromethane (2 mL), then  propargylamine (35 mg, 0.63 mmol, 1.5 equiv.) was added via syringe. The vial was capped and after 60 min, 1 was consumed. The solvent was removed under vacuum, and the product was purified by crystallization (CH2Cl2/petroleum ether) to give a yellow crystalline powder (97 mg, 94 % yield). TLC (30% EtOAc/hexanes, Rf = 0.17); mp 176-178 °C (dec); IR (KBr, cm-1): 3379 (m), 3363 (m), 3282 (m), 1592 (s), 1554 (s), 1402 (s); 1H NMR (200 MHz, CDCl3) δ: 7.67 (br s, 2H), 7.13 (br s, 2H), 6.70 (br s, 1H), 6.51 (br s, 2H), 4.52 (m, 2H), 2.56 (t, J = 2.6 Hz, 1H; 13C (50 MHz, Acetone-d6) δ: 149.5, 136.3, 133.0, 126.2, 125.7, 122.9, 117.5, 115.7, 114.4, 78.0, 75.8, 36.8. Anal. Calcd for C12H10BF2N3: C, 58.82; H, 4.11; N, 17.15. Found: C, 58.66; H, 4.05; N, 17.25.  Sample preparation. The intrinsic photophysical properties of 8-PAB in solution were registered in diluted solutions (2×10−6 M) using a 1 cm optical pathway quartz cuvettes. The samples were prepared by adding the corresponding solvent to an adequate amount of a concentrated stock solution (ca. 10−3 M) of the dye in acetone, after vacuum evaporation of the solvent.  Spectroscopic techniques. UV-Vis absorption and fluorescence spectra were recorded on a Varian model CARY 4E spectrophotometer and a SPEX Fluorolog 3-22 spectrofluorimeter, respectively. Fluorescence quantum yield (φ) was obtained using an ethanolic solution of Coumarin 1 as reference (φr =0.75).[2] Radiative decay curves were registered with the time correlated single-photon counting technique (Edinburgh Supplementary Material (ESI) for Chemical CommunicationsThis journal is (c) The Royal Society of Chemistry 2010 S4Instruments, model FL920, with picosecond time-resolution). Emission was monitored at the maximum emission wavelength after excitation at 370 nm by means of a diode laser (PicoQuant, model LDH370). The recorded fluorescence decay curves were deconvoluted from the pulse signal by means of an iterative software supplied with the instrument.  Computational details. All the quantum mechanical calculations were performed by means of the Gaussian 03 package. Ground and excited state geometries were optimised at the Density Functional Theory (DFT) method (using the B3LYP) and the Configuration Interaction Singles (CIS) ab initio method, respectively. In both cases the 6-31G* basis set was used.  Laser experiments. Liquid solutions of dyes were contained in 1 cm optical-path quartz cells that were carefully sealed to avoid solvent evaporation during experiments. The liquid cells of the blue-edge dyes were transversely pumped at 355 nm with 5.5 mJ, 12 ns FWHM pulses from the third-harmonic of Q-switched Nd:YAG laser (Spectron  SL282G) at a repetition rate of up to 10 Hz. The exciting pulses were line-focused onto the cell, providing pump fluences on the active medium of 180 mJ/cm2. The oscillation cavity (2 cm length) consisted of a 90% reflectivity aluminum mirror, with the end face of the sample as output coupler.  The photostability of the dyes was evaluated by irradiating under lasing conditions 10 µL of a solution in ethanol. The solutions were contained in a cylindrical Pyrex tube (1 cm height, 1 mm internal diameter) carefully sealed to avoid solvent evaporation during the experiments. Monitoring of sample photolysis was carried out by recording the laser-induced fluorescence emission, excited transversally to the capillary with the same pump Supplementary Material (ESI) for Chemical CommunicationsThis journal is (c) The Royal Society of Chemistry 2010 S5pulses from the Nd:YAG laser used for producing dye laser emission, as a function of the pump pulses at 1 Hz repetition rate. The fluorescence emission was monitored perpendicular to the exciting beam, collected by an optical fiber, and imaged onto the input slit of a monochromator (Acton Research corporation) and detected with a charge-coupled device (CCD) (SpectruMM:GS128B). The fluorescence emission was recorded by feeding the signal to the boxcar (Stanford Research, model 250) to be integrated before being digitized and processed by a computer. Each experience was repeated at least three times. The estimated error of the energy measurements was 10% and the experimental error in the photostabilty measurements was estimated to be on the order of 7%. Details of the experimental setup can be found elsewhere.[3,4]  Narrow-line-width laser emission and tuning ranges of dye solutions were obtained by placing the samples in a home-made Shoshan-type oscillator[5] consisting of full-reflecting aluminum back and tuning mirrors, and a 2400 lines·mm−1 holographic grating in grazing incidence, with outcoupling via the grating zero order. Wavelength tuning was accomplished by rotation of the tuning mirror. Tuning mirror and grating (both from Optometrics) were 5 cm wide and the angle of incidence on the grating was 88.5°. Laser line width was measured with a Fabry-Perot etalon (IC Optical Systems) with a free spectral range of 15.9 GHz. Supplementary Material (ESI) for Chemical CommunicationsThis journal is (c) The Royal Society of Chemistry 2010 S6Table S1. Photophysicala properties of 8-PAB in different solvents. Solvent λab εmax λfl ∆νSt φb τ kfl knr H2O 398.0 2.6 481.5 4360 0.32 2.04c - - CF3CH2OH 404.0 2.9 480.5 3940 0.88 6.33 1.4 0.2 MeOH 405.0 3.3 464.5 3160 0.52 3.22 1.6 1.5 EtOH 406.5 3.2 463.0 3010 0.66 3.81 1.7 0.9 Me2CO 406.0 3.1 466.5 3190 0.86 4.92 1.7 0.4 EtOAc 408.5 3.3 469.5 3180 0.94 5.13 1.8 0.2 c-hexane 422.5 3.5 482.0 2920 0.93 5.35 1.7 0.1 a Absorption (λab) and fluorescence (λfll) wavelengths (±0.5 nm), molar absorption coefficient  at maximal absoprtion (εmax  in 104 M-1 cm-1), fluorescence quantum yield (φ, ±0.05 ), lifetime (τ, ±0.05 ns), Stokes shift(∆νSt, in cm-1) and rate constant of radiative and non-radiative deactivation (kfl and knr, in 108 s-1) b using coumarin 1 in ethanol (φ=0.75[6]) as reference. c Decay curve analyzed as a two-exponential decay: τ2=4.96 ns with a minor contribution (A2 < 4%).   Supplementary Material (ESI) for Chemical CommunicationsThis journal is (c) The Royal Society of Chemistry 2010 S7   Concentration (mM)Laser efficiency(%)051015202530354.0 5.5 7.0 8.7  Figure S1. Lasing efficiency of 8-PAB as a function of the dye concentration in ethyl acetate registered in the non-tunable-plane cavity. As it was expected, the lasing efficiency of the dye increased rapidly with the dye concentration until a maximum value for a solution with an optical density of ca. 18. From this point on, further increases in the dye concentration result in a slight decrease of the lasing efficiency which is related to the effect of reabsorption/reemission phenomena on the emission intensity, because the possibility of exciting molecules by absorption of a photon previously emitted by another molecule in the medium depends on the overlapping between absorption and fluorescence spectra, which is affected by the dye concentration.[7]       05101520253035EtOAc Acetone EtOH F3-EtOHSolventsLaser efficiency(%)470 480 490 500 Laser emission (u.a.)Wavelength (nm)  Figure S2. Efficiency and spectra of the laser emission of the dye 8-PAB (7×10-4 M) in different solvents: EtOAc (ethyl acetate, dashed line); acetone (dark grey line); EtOH (ethanol, light grey line) and F3-EtOH (2,2,2-trifluoroethanol, black line).  Supplementary Material (ESI) for Chemical CommunicationsThis journal is (c) The Royal Society of Chemistry 2010 S8References [1]  T. V. Glould; A. Tutar; J.-F. Biellmann, Tetrahedron 2006, 62, 5084 [2] F. López Arbeloa; T. López Arbeloa; I. López Arbeloa, Materials for Solid-State Dye   Lasers, in Handbook of Advanced Electronic and Photonic Materials and Devices, Vol. 7,      2001, pp 209-245. [3] A. Costela; I. García-Moreno; D. del Agua; O. García; R. Sastre,  J. Appl. Phys. 2007,     101, 73110. [4] A. Costela; I. García-Moreno; C. Gómez; R. Sastre; F. Amat-Guerri; M. Liras;  F. López Arbeloa; J. Bañuelos Prieto; I. López Arbeloa, J. Phys. Chem. A, 2002, 106, 7736. [5] I. Soshan; N. N. Danon;  U. Oppenheim, J. Appl. Phys. 1977, 48, 2295. [6]  T. López Arbeloa, F. López Arbeloa, M.J. Tapia, I  López Arbeloa. J. Phys. Chem. 1993, 97, 4704. [7] I. López Arbeloa,  J. Photochem. 1980, 14, 97.                        Supplementary Material (ESI) for Chemical CommunicationsThis journal is (c) The Royal Society of Chemistry 2010 S9  Supplementary Material (ESI) for Chemical CommunicationsThis journal is (c) The Royal Society of Chemistry 2010 S10 Supplementary Material (ESI) for Chemical CommunicationsThis journal is (c) The Royal Society of Chemistry 2010

8-PropargylaminoBODIPY: unprecedented blue-emitting pyrromethene dye. Synthesis, photophysics and laser properties

8-PropargylaminoBODIPY: unprecedented blue-emitting pyrromethene dye. Synthesis, photophysics and laser properties

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