Merocyanine chromophores

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]. 

The large molecular hyperpolarizability of the merocyanine chromophore (4,5) and the highly polar environment of the quasicrystals has prompted studies of the second order nonlinear optical properties of these materials (6). 

Meridional tridendate ligand, 7 578 Merino wool, 26 370-371, 373, 374, 380 amino acid composition of, 26 377t Merocyanine 540 (MC540), 9 517 Merocyanine chromophores, 20 506 Merocyanine dyes, 9 503, 504, 511—512 ... 

Demonstration of the photorelease has been done in particular with Sr + [46]. This process was monitored on several time scales providing evidence for (1) the delayed formation in 9 ps of the charge transfer state of the merocyanine chromophore following ultrafast photodisruption of the nitrogen - cation interaction, (2) the cation movement away from the excited chromophore into the bulk in 400 ps, (3) recombination of the complex in the ground in about 120 ns. These three steps are respectively illustrated in Fig. 7.17a, b, c (see caption for details). Similar transient absorption studies have been carried out on a PDS-crown-Ca + complex, where PDS is an aza-crown derivative of a substituted stilbene [47]. The spectrodynamics observed on the short time scale are very similar to those found in step (1) of the above description, with in particular a delayed rise of a stimulated emission band attributed to a solvent-separated cation-probe pair. Although the full scenario of the cation photoejection from the DCM-crown-Sr, is complex [46], the spectra shown in Fig. 7.17 demonstrate that at least part of the photoexcited complexes does eject the ion into the bulk. 

At pH 4—7 (63H) is extremely sensitive to oxygen. By reaction with one mole of oxygen a red crystalline product with a merocyanine chromophore is formed, for which constitution (67) has been proposed. 

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). 

Fohlisch99 reported a remarkable dependence of the electron spectra of quino-cyclopropenes on their structure. As shown in Table 9, the merocyanine-like quino-cyclopropenes show positive solvatochromy when they contain an anthraquinonoid chromophore (198), but negative solvatochromy when they contain a benzoquino-noid system (199). This can be interpreted in terms of a markedly increased participation of dipolar resonance forms in the ground state of the benzoquinonoid 199 compared to the anthraquinonoid 198. From the dipole moment of 198 (9.4 D99 ) the dipolar contribution was estimated to be in the range of 23%. 

Chromophores with a rather high optical anisotropy are the merocyanines (77), especially in the cyanine limit with equal contributions of the apolar and zwitterionic resonance structures [319]. Thus, they also have been proposed as promising candidates for photorefractive systems based on molecular glasses. For 77, doped with a photosensitizer, a refractive index modulation of 0.01 at an electrical field of 22 V/pm was reported. 

Another water-soluble (3-CD (105) bearing seven naphthoyl chromophores forms very stable 1 1 complexes with a merocyanine laser dye DCM-OH [90], The energy transfer from the naphthoyl antenna chromophores to the included dye is shown to occur with 100% efficiency (antenna effect) (Scheme 3). 

Supramolecular chiral induction into dye chromophores can also be achieved in totally synthetic systems. Interpenetrated ion pairs of cyanine dyes and chiral borate anions show that the twisting of the dye is important for the observation of the induced optical activity by CD spectroscopy [225]. The incorporation of merocyanine dyes into synthetic self-assembled systems provides important information about their stability and chirality [226]. 

Figure 6 illustrates clearly the significance of Tg concerning the free volume available for molecular motions and ring-dosure of the merocyanine side groups. Similar diagrams are obtained for azo chromophores present in several copolymers . 

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