Abstract

A detailed study of the visible spectra in solution and the infrared spectra of the dyes in the solid state have been made for the following vinylogous series of cyanine dyes: [2-bis (3-ethylthiazolinyl)] cyanine iodides, I; [2-bis (3-ethyl-4-methylthiazolyl)] cyanine iodides, II; and [2-bis (3-ethyl-4,5-diphenylthiozolyl] cyanine iodides, III. Each dye, to be acceptable for study, had to be chromatographically pure, give a correct microchemical elemental analysis, and be free of electron-spin resonance (free radical) signals. These vinylogous series of dyes from a systematic group. That is, in series I there is only a resonant conjugated chain of alternate single and double bonds present between the two nitrogen atoms; in series II there are additional olefinic unsaturated bonds which are in conjugation with the resonant conjugated chain; and in series III there are additional phenyl rings in conjugation with the entire pi bond system present in II. The characteristic red shift of the principal absorption maxima was observed for these dyes in the visible as the number of methine linkages increased. Furthermore, a small relative red shift of the absorption maxima has been observed for this group of dyes and has been interpreted on the basis of the type of unsaturation present in conjugation with the resonant conjugated chain. Assignments of vibrational modes to separate absorption regions have been made for these vinylogous series of dyes. A correlation of the dye structure with the absorption bands has been made. Each vinylog gave rise to a characteristic pattern of resonant conjugated stretching modes in the region 1600 to 1400 cm⁻¹. These modes exhibited a low frequency shift as the resonant conjugated chain-length increased. For a constant number of polymethine linkages these modes are a function of the type of unsaturation present which is in conjugation with the resonant conjugated chain.

Alternation and saturation effects in the chain-length dependences of the third-order hyperpolarizabilities of cyanines

W. Werncke, M. Pfeiffer, A. Lau, W. Grahn, H.-H. Johannes, and L. Dähne
J. Opt. Soc. Am. B 15(2) 863-870 (1998)

Optical nonlinearities in symmetric cyanine dyes and related systems

I. D. L. Albert, P. K. Das, and S. Ramasesha
J. Opt. Soc. Am. B 10(8) 1365-1371 (1993)

Photoconductivity of Some Cyanine Dyes*

R. C. Nelson
J. Opt. Soc. Am. 46(1) 10-13 (1956)

Infrared Measurements with a Cesium Iodide Prism

Nicolo Acquista and Earle K. Plyler
J. Opt. Soc. Am. 43(11) 977-979 (1953)

Near-infrared photoluminescence spectra in Bi-doped CsI crystal: evidence for Bi-valence conversions and Bi ion aggregation

Liangbi Su, Hengyu Zhao, Hongjun Li, Lihe Zheng, Xiao Fan, Xiantao Jiang, Huili Tang, Guohao Ren, Jun Xu, Witold Ryba-Romanowski, Radosław Lisiecki, and Piotr Solarz
Opt. Mater. Express 2(6) 757-764 (2012)