Conjugated chains

Knott s rule concerns the importance of the place of the nitrogen atom replacing a methine carbon in the conjugated chain when the atom is separated from the active auxochromic atoms by an odd number of conjugated atoms, the shift is bathochromic. It is hypsochromic when there is an even number, Tne importance of the shift could establish a measure of M effect of various heterocyclic nuclei (79. 124). Many papers have been published, and examples have been given to verify these rules (79-84). 

The length of the conjugated chain in the chiomophoie and the nature of the terminal nuclei are important factors in estabhshing the wavelengths at... 

Bleaching and decolorization can occur by destroying one or more of the double bonds in the conjugated chain, by cleaving the conjugated chain, or by oxidation of one of the other moieties in the conjugated chain. The result of any one of the three reactions is an increase in the energy gap between the... 

Color in Organic Compounds. In organic molecules, particularly those containing conjugated chains of alternating single and double... 

Hemicya.nines, These half-cyanine dyes may be represented by stmcture (48). They may be considered as cyanines in which a benzene ring has been inserted into the conjugated chain. Hemicyanines provide some bright fluorescent red dyes for polyacrylonitrile. 

Figure 8.12. A conjugated chain in poly(acetylene). (a) changes to (b) when a charge passes along the backbone of the molecule, (c) and (d) show chains of poly(acetylene) and poly(para phenylene) respectively, each containing solitons (after Windle 1996).

Gas Phase to Solid State Evolution of the Electronic and Optical Properties of Conjugated Chains A Theoretical Investigation... 

According to a large number of experimental studies, the most stable phologen-erated species in the lowest excited stales of conjugated chains are electron-hole pairs bound by Coulomb attraction and associated to a local deformation of the backbone, i.e., polaron-excilons [18]. A good insight into the properties of these species can be provided by quantum-chemical calculations our recent theoretical... 

In the following section, step by step a qualitative picture is formed describing the impact of intcrmolecular interactions oil the absorption and luminescence of organic conjugated chains. The present calculations do not distinguish between dimers and aggregates (for which the wavefunctions of adjacent chains interact in the ground state, due to, for instance, solid-state effects) and excimers (where overlap occurs only upon photoexcitation) [29]. 

Analogy between the Delocalized Orbitals of a Hydrocarbon Skeleton (Ethylene, Ethane, Allene, Propane, etc.) and the T Delocalized Orbitals of Conjugated Chains... 

Conjugated chains, 14, 46 Correlation diagrams, 44, 50 Cyclobutadiene, 171 Cyclobutane, 47, 222 orbital ordering, 26 through-space interactions, 26 Walsh orbitals, 27 Cyclobutene, 200 Cyclohexane, 278 Cyclohexene (half-boat), 274 Cyclopen tadiene, 225 Cvclopen tadienone, 269 Cyclopentadienyl anion, 237 Cyclopentane, 254 Cyclopen ten e, 241 Cyclopropane, 41, 47, 153 construction of orbitals, 19, 22 Walsh orbitals, 22, 36, 37 Cyclopropanone, 48, 197 bond lengths, 38 Cyclopropen e, 49, 132 reactivity, 40... 

An increase in polarizability of the w-electron system in a PCS is expected to be followed by an easy transfer of the chemical behavior along the conjugation chain and by a decrease in the internal energy of the PCS, thus enhancing the thermal stability of the polymers and the rigidity of the main chain. 

In the process of radical polymerization a monomolecular short stop of the kinetic chain arises from the delocalization of the unpaired electron along the conjugated chain and from the competition of the developing polyconjugated system with the monomer for the delivery of rr-electrons to the nf-orbitals of a transition metal catalyst in the ionic coordination process. Such a deactivation of the active center may also be due to an interaction with the conjugated bonds of systems which have already been formed. 

We have already pointed out that the reduction in conjugation efficiency in PCSs is followed by a short-wave shift of the CTC transfer band. This accounts for the fact that poly(schiff base)s and polyazines having conjugated sections separated by oxygen and sulfur atoms are characterized by a short-wave shift of the transfer band of CTC with all acceptors compared to the respective polymers having no interruption of the conjugated chain. This shift may reach 20-50 nm. 

In Table III are given calculated values of the resonance energy for straight conjugated chains containing two, three, and four double bonds and a branched chain with three double bonds (the list could be easily extended). In each case the secular equation was solved as a quadratic, all first-excited structures being given the same... 

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