Conjugation phenomena

Conjugation phenomena, which can modify the reactivity of the second vinyl group, will not be considered here. 

In the extreme carbocation limit of (3.163) and (3.164), the stereoelectronic secondary-hyperconjugation effects therefore blend seamlessly into ordinary pi-type conjugation phenomena (Section 3.3), the two extremes always being linked by electronic continuity. 

Although the diagram does not give a quantitative interpretation of the heat-bodying phenomena of linseed oil it allows an easy comparison of the conjugation and polymerization reactions under different conditions. Chemical and physical analytical methods for the determination of conjugated double bonds (diene value, ultraviolet absorption spectra) confirmed the conclusions about the conjugation phenomena. 

Regarding hydrochloric acid, in a concentration range of 30.10 4 to 300.10 4 mol/L, equivalent conductance assumes an extremely low and constant value of 0.03 S cm2/mol, as seen in Figure 3. This behavior certainly cannot be explained on the basis of simple dissociation phenomena. Thus we have interpreted these results on the basis of theoretical work by Caruso and co-workers (31) who consider the conductometric, potentiometric, and spectrophotometric behavior of weak acids and bases in nonaqueous solvents. In these solvents a weak acid, HA, besides undergoing simple ionic dissociation, also may undergo conjugation phenomena by the H+ and A" ions which lead to the formation of ionic complex species A(HA)/ or H(HA)/. Caruso shows that the... 

A diagnostic criterion for the efficiency of delocalization is the bond length alternation [123]. Furthermore, physical properties directly correlated to conjugation phenomena are optical transitions, redox potentials and nonlinear optical effects. 

INFLUENCE OF THE CONJUGATION PHENOMENON ON THE INFRARED ABSORPTION BANDS /1600-1250 /CM-1/ OF THE BENZENE CYCLE. 

The molecule of 1,3-butadiene is also often used as an example to explain the conjugation phenomenon. This molecule can be described by three limit forms, two of which make the charges appear. These limit forms are presented in Figure 9.7. 

We have found for polypropynoic acid that this series of polymers reveals selective fluorescence spectra together with nonselective absorption. To account for this phenomenon, a scheme was proposed according to which PCSs are characterized by energy transfer from excited levels of some conjugation sections to the lower levels of other sections, followed by luminescence from the latter40 41,246,248,249,253. ... 

First, these copolymers undergo decarboxylation more readily than any of the homopolymers. Second, decarboxylation involves the units of acrylic add at temperatures which do not affect homopolymers of acrylic acid. In our view, the first phenomenon is accounted for by the effect of separation of conjugation blocks exemplified by this particular chemical reaction. As to the second observation, we believe that decarboxylation under relatively mild conditions (160—170 °C) affects, apparently, the fragments of acrylic acid located at the junctions of the blocks. 

The elimination of all investigated cannabinoids has been observed to be very poor finding occasionally higher concentrations of these compounds in effluent than in influent waters, which may be related to deconjugation of excreted conjugated forms not yet investigated. The same phenomenon may be attributed to the persistence of LSD in some of the investigated effluent samples. 

The results of our calculations based on both the static and dynamic theories show that most of the nonbenzenoid cyclic conjugated systems examined exhibit in a greater or lesser degree a marked double-bond fixation. The static theory indicates that even in benzene there exists a hidden tendency to distort into a skewed structure and that such a tendency is actually realized in [4n-f-2] annulenes larger than a certain critical size. In nonalternant hydrocarbons bond distortion is a rather common phenomenon. Fulvenes, fulvalenes and certain peri-condensed nonalternant hydrocarbons undergo a first-order bond distortion, and... 

Porphyrin is a multi-detectable molecule, that is, a number of its properties are detectable by many physical methods. Not only the most popular nuclear magnetic resonance and light absorption and emission spectroscopic methods, but also the electron spin resonance method for paramagnetic metallopor-phyrins and Mossbauer spectroscopy for iron and tin porphyrins are frequently used to estimate the electronic structure of porphyrins. By using these multi-detectable properties of the porphyrins of CPOs, a novel physical phenomenon is expected to be found. In particular, the topology of the cyclic shape is an ideal one-dimensional state of the materials used in quantum physics [ 16]. The concept of aromaticity found in fuUerenes, spherical aromaticity, will be revised using TT-conjugated CPOs [17]. 

In addition to the aforementioned types of intermolecular homoconjugates, there are also intramolecular homoconjugates, examples of which we have already mentioned with regard to the titrations of (a) ethylenediamine with acid (p. 248) and (b) of salicylic acid with base (p. 245). This phenomenon of intramolecular hydrogen bonding is usually called chelation, and so the conjugates concerned are preferably designated chelates. 

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