Transient absorption of symmetrical carbocyanines

Abstract Transient absorption in several symmetrical cyanine and carbncyanine dyes is measured by time-resolved spectroscopy with subpicosecond white-light continuum in a wide spectral range (0.35–1 μm). The results are compared with data available in the literature on ultrashort and long-lived transients. The linear shift law observed here for the S1Sn absorption bands in the wavelength scale allows one to predict the main induced absorption bands for members of several carbocyanine families (vinylogous series) which have not yet been studied. In the case of the shortest methine chains (cyanines and monocarbocyanines) a tew transient absorption bands are assigned to the formation of photoisomers. The absolute values of the excited-state or photoisomer cross sections of polymethine carbocyanines are evaluated by global spectral analysis, from the measured differential optical density spectra. Several cases of large values (higher than 10) of the absorption cross section ratio (excited/ground state) are found at new wavelengths, which allows applications of photo-induced absorption to photonics and laser technologies over a broad spectral range.

[2]  R. Negri,et al.  Temperature dependence of fluorescence and photoisomerization in symmetric carbocyanines. Influence of medium viscosity and molecular structure , 1994 .

[3]  M. Kurz,et al.  Photochemistry of carbocyanine alkyltriphenylborate salts: intra-ion-pair electron transfer and the chemistry of boranyl radicals , 1990 .

[4]  Heinz-Helmut Perkampus,et al.  UV-VIS atlas of organic compounds , 1992 .

[5]  J. Mialocq,et al.  Picosecond study of pinacyanol photophysics , 1982 .

[6]  G. Schuster,et al.  External iodine atoms influence over the intersystem crossing rate of cyanine iodide ion pair in benzene solution , 1991 .

[7]  T. Kobayashi,et al.  The rates of internal conversion and photoisomerization of some carbocyanine dyes as revealed from picosecond time-resolved spectroscopy , 1977 .

[8]  M. Dawson,et al.  Picosecond and femtosecond pulse generation near 1000 nm from a frequency-doubled Nd:YAG-pumped cw dye laser. , 1987, Optics letters.

[9]  S. Rentsch Modeling of the fast photoisomerisation process in polymethine dyes , 1982 .

[10]  Brian S. Wherrett,et al.  The saturation limit to picosecond, induced absorption in dyes , 1993 .

[11]  P. J. Mccartin Observation of Metastable Geometrical Isomers of Cyanines by Flash Photolysis , 1965 .

[12]  J. Fouassier,et al.  Etude physicochimique d’une série de cyanines. Partie IV : rigidification, photoisomerisation et effet laser , 1982 .

[13]  Jean-Pierre Fouassier,et al.  Étude photophysique d'une série de cyanines , 1977 .

[14]  Quincy L. Mattingly,et al.  Steady-state and picosecond laser fluorescence studies of nonradiative pathways in tricarbocyanine dyes Implications to the design of near-IR fluorochromes with high fluorescence efficiencies , 1994 .

[15]  S. Rentsch,et al.  On the mechanism of photoisomerization and the structure of the photoisomers of cyanine dyes , 1985 .

[16]  G. Berthier,et al.  Theoretical study of trans-cis photoisomerism in polymethine cyanines , 1988 .

[17]  Y. Meyer,et al.  Ultrafast excited singlet state absorption/gain spectroscopy of perylene in solution , 1995 .

[18]  J. Fouassier,et al.  Excited states and laser properties of tricarbocyanine dyes , 1976 .

[19]  J. Fouassier,et al.  Transient absorptions in a polymethine laser dye , 1975 .

[20]  A. Taylor,et al.  The absorption characteristics and recovery dynamics of the tricarbocyanine dye DTP , 1991 .

[21]  A. P. Darmanyan,et al.  Study of sterically hindered short-lived isomers of polymethine dyes by laser photolysis , 1978 .

[22]  M. I. Demchuk,et al.  The influence of the anion on the excited-state relaxation time of cationic polymethine dyes , 1988 .

[23]  M. Maroncelli,et al.  Subpicosecond Measurements of Polar Solvation Dynamics: Coumarin 153 Revisited , 1995 .

[24]  F. Grum,et al.  Stereoisomerism in cyanine dyes--meso-substituted thiacarbocyanines , 1967 .

[25]  R. Gadonas,et al.  Ultrafast physical effects in cyanine dyes subjected to tunable picosecond excitation , 1983 .

[26]  W. Helman,et al.  Extinction Coefficients of Triplet–Triplet Absorption Spectra of Organic Molecules in Condensed Phases: A Least‐Squares Analysis , 1987 .

[27]  J. Taylor,et al.  A femtosecond hybrid mode locked Rhodamine B dye laser , 1986 .

[28]  P. M. Henrichs,et al.  DIRECT AND SENSITIZED PHOTOOXIDATION OF CYANINE DYES , 1976, Photochemistry and photobiology.

[29]  R. H. Sprague,et al.  Color and Constitution. X.1 Absorption of the Merocyanines2 , 1951 .

[30]  R. Gadonas,et al.  Picosecond time-resolved kinetic studies on the formation of short-lived pseudoisocyanine iodide photoisomers in methanol and ethylene glycol , 1981 .

[31]  R. Redmond,et al.  PHOTOPHYSICAL PROPERTIES OF 3,3′‐DIALKYLTHIACARBOCYANINE DYES IN HOMOGENEOUS SOLUTION , 1993, Photochemistry and photobiology.

[32]  H. Tashiro,et al.  Ultrafast absorption spectroscopy of laser dyes using a streak camera , 1976 .

[33]  R. Gadonas,et al.  Picosecond kinetics and transient spectra of pseudoisocyanine monomers and J-aggregates in aqueous solution , 1981 .

[34]  Hans Kuhn,et al.  A Quantum‐Mechanical Theory of Light Absorption of Organic Dyes and Similar Compounds , 1949 .

[35]  V. Sundström,et al.  A discussion of the problem of determining multiple lifetimes from picosecond absorption recovery data as encountered in two carbocyanine dyes , 1983 .

[36]  K. Eisenthal,et al.  Ultrafast Phenomena IV , 1984 .

[37]  F. Grieser,et al.  Excited-state torsional relaxation in 1,1'-dihexyl-3,3,3',3'-tetramethylindocarbocyanine iodide: application to the probing of micelle structure , 1985 .

[38]  M. Martin,et al.  Generation of tunable subpicosecond pulses using low-Q dye cavities. , 1992, Applied optics.

[39]  G. Hartland,et al.  ULTRAFAST INVESTIGATION OF VIBRATIONAL RELAXATION IN THE S1 ELECTRONIC STATE OF HITC , 1996 .

[40]  T. Yajima,et al.  Picosecond absorption spectroscopy of excited states of dye molecules , 1974 .

[41]  E. Vauthey Isomerisation dynamics of a thiacarbocyanine dye in different electronic states and in different classes of solvents , 1995 .

[42]  R. Gadonas,et al.  Ultrafast Photophysical processes in pinacyanol after selective excitation , 1981 .

[43]  V. Sundström,et al.  Transient absorption spectra of pinacyanol and cyanine photoisomers obtained with a sync-pumped picosecond dye laser and independently tunable probe light , 1983 .

[44]  T. Elsaesser,et al.  Vibronic excitations of large molecules in solution studied by two-color pump-probe experiments on the 20 fs time scale , 1996 .

[45]  M. Dawson,et al.  Synchronous and hybrid mode-locking of a Styryl 13 dye laser , 1988 .

[46]  H. Tashiro,et al.  Ultrafast Absorption Spectroseopy of Polymethine Laser Dyes Using a Streak Camera , 1976 .

[47]  W. Sibbett,et al.  Substituent and environmental effects on the picosecond lifetimes of the polymethine cyanine dyes , 1981 .

[48]  G. V. Zakharova,et al.  Photorelaxation Processes in Covalently Linked Indocarbocyanine and Thiacarbocyanine Dyes , 1995 .

[49]  A. Weissberger,et al.  Special topics in heterocyclic chemistry , 1977 .

[50]  G. Schuster,et al.  ELECTRONIC RELAXATION IN A SERIES OF CYANINE DYES : EVIDENCE FOR ELECTRONIC AND STERIC CONTROL OF THE ROTATIONAL RATE , 1995 .

[51]  A. Penzkofer,et al.  Fluorescence spectroscopic analysis of N and P isomers of DODCI , 1990 .

[52]  C. H. Wang,et al.  Dicarbocyanine dyes in methanol solution probed by depolarized Rayleigh and hyper‐Rayleigh light scattering , 1996 .

[53]  G. Ponterini,et al.  Electronic spectra and trans—cis photoisomerism of carbocyanines. A theoretical (CS INDO CI) and experimental study , 1993 .

[54]  T. Farrar,et al.  Transverse nuclear spin relaxation of fluorine-19 and phosphorus-31 in phosphofluoridate(2-) in high magnetic fields , 1987 .

[55]  J. Taylor,et al.  Passive mode locking in the near infrared , 1984 .

[56]  D. Doizi,et al.  Photosensitized electron-transfer reaction in the first excited singlet state of a polymethine-cyanine dye , 1987 .

[57]  J. Jasny,et al.  Nanosecond transient absorption spectrophotometer with dye laser probe , 1981 .

[58]  Shammai Speiser,et al.  Photoquenching parameters for commonly used laser dyes , 1985 .

[59]  C. J. Tredwell,et al.  Picosecond time resolved fluorescence lifetimes of the polymethine and related dyes , 1979 .

[60]  Hideo Tashiro,et al.  Excited state absorption of 1,3,3,1′,3′,3′-hexamethylindotricarbocyanine Iodide: A quantitative study by ultrafast absorption spectroscopy , 1977 .

[61]  A. Ischchenko,et al.  Effect of the polymethine chain length on the fluorescence spectrum of symmetric cyanine dyes , 1992 .

[62]  G. Ponterini,et al.  Trans-cis photoisomerization mechanism of carbocyanines : experimental check of theoretical models , 1991 .

[63]  V. Sundström,et al.  Solvent-dependent barrier heights of excited-state photoisomerization reactions , 1985 .

[64]  T. Morrow,et al.  Photochemical characteristics of cyanine dyes. Part 1.—3,3′-diethyloxadicarbocyanine iodide and 3,3′-diethylthiadicarbocyanine iodide , 1972 .

[65]  S. Braslavsky,et al.  Combination of laser-induced optoacoustic spectroscopy (LIOAS) and semiempirical calculations for the determination of molecular volume changes : the photoisomerization of carbocyanines , 1994 .

[66]  V. Sundström,et al.  Femtosecond spectral evolution monitoring the bond-twisting event in barrierless isomerization in solution , 1994 .

[67]  J. Fabian,et al.  Light absorption of organic colorants , 1980 .

[68]  C. Rullière Laser action and photoisomerisation of 3,3′-diethyl oxadicarbocyanine iodide (DODCI): Influence of temperature and concentration , 1976 .

[69]  D. Waldeck,et al.  Breakdown of Kramers theory description of photochemical isomerization and the possible involvement of frequency dependent friction , 1983 .

[70]  C. Weisbuch,et al.  CW dye laser emission beyond 1000 nm , 1978 .