Merocyanines

If an ideal solution is formed, then the actual molecular A is just Aav (and Aex = 0). The same result obtains if the components are completely immiscible as illustrated in Fig. IV-21 for a mixture of arachidic acid and a merocyanine dye [116]. These systems are usually distinguished through the mosaic structure seen in microscopic evaluation. 

Fig. IV-21. Surface pressure versus area for monolayers of immiscible components a monolayer of pure cadmium arachidate (curve 1) and monolayers of mixed merocyanine dye, MC2, and cadmium arachidate of molar ratio r = 1 10 (curve 2) 1 5 (curve 3), 1 2 (curve 4), and pure MC2 (curve 5). The subphase is 2.5 x 0 M CdC, pH = 5.5 at 20°C. Curve 3a (O) was calculated from curves 1 and 5 using Eq. IV-44. (From Ref. [116].)...

Merocyanines belong to the class of nonionic methine dyes combining two nuclei, one of which is a ketomethylene of acidic nature such as pyrazolone, rhodanine, oxazolone, thiohydantoin,. 

Merocyanines with selenazolidine nuclei are obtained in 70 to 80°/o yield from the appropriate derivatives of lepidine or quinaldine (Scheme 79) (84). 

Carbocyanine or merocyanine dyes prepared from selenazole or selenazoline rings have a particular interest in photography. 

The simplest PMDs include the polymethines (2), streptocyanines (3), oxonols (4), and merocyanines (5). 

Solvent Influence. Solvent nature has been found to influence absorption spectra, but fluorescence is substantiaHy less sensitive (9,58). Sensitivity to solvent media is one of the main characteristics of unsymmetrical dyes, especiaHy the merocyanines (59). Some dyes manifest positive solvatochromic effects (60) the band maximum is bathochromicaHy shifted as solvent polarity increases. Other dyes, eg, highly unsymmetrical ones, exhibit negative solvatochromicity, and the absorption band is blue-shifted on passing from nonpolar to highly polar solvent (59). In addition, solvents can lead to changes in intensity and shape of spectral bands (58). 

Other Electrophilic Reactants. ReversibHity of the electrophilic reactions enables substituted dye derivatives to be obtained. Thus, the halogenation of cyanines, oxonoles, and merocyanines has been studied (3,65,66). Halogen atoms are mobHe in the polymethine chain, and the derivatives themselves can function as halogenation reagents. 

If the dye contains no mobile substituents ia the chain, nucleophiles attack primarily the end carbon atoms (changing of terminal residues). Streptocyanines can be hydroly2ed ia aqueous alkaline solution to form the corresponding merocyanines and then the oxonoles (71,72). These processes are reversible. Nucleophilic reactions with the methylene bases of the corresponding heterocycles result ia polymethines containing new end groups (Fig. 

The reverse reaction, the photochemical ring opening of sphopyranes (22b), takes place by absorption ia the short-wave uv region of the spectmm and the merocyanine isomer (22a) is obtained. The electron transition of (22a) is ia the visible spectral region, whereas (22b) is colorless. As a result, the dye solution can change from colorless to a colored solution (87,88). These photochromic reactions can be used for technical appHcations (89). 

A monolayer of the pyridine-substituted alkyl merocyanine (12) was prepared in the 1970s (67), and a noncentro symmetric multilayer stmcture of merocyanine amphiphiles was later prepared (68) using derivatives, but introducing long-chain amines as the counter layer in an ABABAB system (69,70). 

Nitro-substituted indolino spiroben2opyrans or indolino spironaphthopyrans are photochromic when dissolved in organic solvents or polymer matrices (27). Absorption of uv radiation results in the colorless spiro compound [1498-88-0], C22H2gN202, being transformed into the colored, ring-opened species. This colored species is often called a photomerocyanine because of its stmctural similarity to the merocyanine dyes (see Cyanine dyes). Removal of the ultraviolet light source results in thermal reversion to the spiro compound. 

The cyanine class of dyes is also useful in biological, medical, laser, and electro-optic appHcations. Dyes marketed as Povan [3546-41-6] (5) and Dithiazanine [7187-55-5] (6) are useful anthelmintics, and Indocyanine Green [3599-32-4] (7) is an infrared-absorbing tracer for blood-dilution medical diagnoses. "Stains-AU." is a weU-studied biological stain (8) and Merocyanine 540 s photochemotherapeutic activity is known in some detail (9). Many commercially available red and infrared laser dyes are cyanines (10). 

Fig. 3. Examples of nuclei occurring in important cyanine dyes, (a) = basic terminal groups for cyanines and merocyanines (b) = acidic terminal groups...

Acidic Heterocycles. A similar classification is made for the acidic electron-accepting terminal groups used in dipolar (merocyanine) chromophores. The unsymmetrical dyes again incorporate the -dimethylarninophenyl group, coimected to the acidic group (Fig. 3) by one or three methine carbon atoms as in the merocyanine(9), n = 0 [23517-90-0]-, n = 1 [42906-02-5]-, n = 2 [66037-49-8]-, n = 3 [66037-48-7]. 

Fig. 4. Usehil cyanine dyes. (10) Green spectral sensiti2er (11) Merocyanine 540 (12) IR-140 laser dye (13) Stains-All.

Reaction with vatious nucleophilic reagents provides several types of dyes. Those with simple chromophores include the hernicyanine iodide [16384-23-9] (20) in which one of the terminal nitrogens is nonheterocyclic enamine triearbocyanine iodide [16384-24-0] (21) useful as a laser dye and the merocyanine [32634-47-2] (22). More complex polynuclear dyes from reagents with more than one reactive site include the trinuclear BAB (Basic-Acidic-Basic) dye [66037-42-1] (23) containing basic-acidic-basic heterocycles. Indolizinium quaternary salts (24), derived from reaction of diphenylcyclopropenone [886-38-4] and 4-picoline [108-89-4] provide trimethine dyes such as (25), which absorb near 950 nm in the infrared (23). 

Several types of nitrogen substituents occur in known dye stmetures. The most useful are the acid-substituted alkyl N-substituents such as sulfopropyl, which provide desirable solubiUty and adsorption characteristics for practical cyanine and merocyanine sensitizers. Patents in this area are numerous. Other types of substituents include N-aryl groups, heterocycHc substituents, and complexes of dye bases with metal ions (iridium, platinum, zinc, copper, nickel). Heteroatom substituents directly bonded to nitrogen (N—O, N—NR2, N—OR) provide photochemically reactive dyes. 

A wide variety of stmetures exist in the cyanine, merocyanine, and oxonol classes of dyes. Properties that may affect toxicity vary widely also. These include solubihty, propensity to be oxidized or reduced, aggregation tendency, and diffusion through membranes. Specific acute toxicity data are Hsted in Table 2, and the LD q data vary widely with the test used. 

A useful classification of sensitizing dyes is the one adopted to describe patents in image technology. In Table 1, the Image Technology Patent Information System (ITPAIS), dye classes and representative patent citations from the ITPAIS file are Hsted as a function of significant dye class. From these citations it is clear that preferred sensitizers for silver haUdes are polymethine dyes (cyanine, merocyanine, etc), whereas other semiconductors have more evenly distributed citations. Zinc oxide, for example, is frequendy sensitized by xanthene dyes (qv) or triarylmethane dyes (see Triphenylmethane and related dyes) as well as cyanines and merocyanines (see Cyanine dyes). 

Dyes, polymethine used for dyes having at least one electron donor and one electron acceptor group linked by methine groups or aza analogues aUopolar cyanine, dye bases, complex cyanine, hemicyanine, merocyanine, oxonol, streptocyanine, and styryl. Supersensitization has been reported for these types—18 cites for cyanines, 3 for merocyanine, and 6 for all other polymethine types. 

Fig. 3. Spectral sensitizing dyes for silver haUdes. (a) Blue sensitizers (400—500 nm) are designated BN (b) green sensitizers (500—600 nm) are designated GN (the ring oxygen may be replaced by N(R)) (c) red sensitizers (600—700 nm) are designated RN (d) MN designates a merocyanine dye and (e),...

Photopolymerization reactions are widely used for printing and photoresist appHcations (55). Spectral sensitization of cationic polymerization has utilized electron transfer from heteroaromatics, ketones, or dyes to initiators like iodonium or sulfonium salts (60). However, sensitized free-radical polymerization has been the main technology of choice (55). Spectral sensitizers over the wavelength region 300—700 nm are effective. AcryUc monomer polymerization, for example, is sensitized by xanthene, thiazine, acridine, cyanine, and merocyanine dyes. The required free-radical formation via these dyes may be achieved by hydrogen atom-transfer, electron-transfer, or exciplex formation with other initiator components of the photopolymer system. 

Other solvatochromic probes have been proposed. Mukerjee et al. used nitrox-ides for this purpose, finding that their transition energies correlate linearly with Z and t (30). Brooker et al. prepared a polar merocyanine that shows a blue shift... 

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