N-Conjugation

By the criterion of Exercise 2-9, is an eigenvalue of the matrix in a and p. There are two secular equations in two unknowns for ethylene. For a system with n conjugated sp carbon atoms, there will be n secular equations leading to n eigenvalues . The family of , values is sometimes called the spectrum of energies. Each secular equation yields a new eigenvalue and a new eigenvector (see Chapter 7). 

The dimension of the matrix is the number of atoms in the n conjugated system. Let us take the three-carbon system allyl as our next step. Concentrate on the end... 

It should be noted that not all electron-attracting groups enhance reactivity. The sulfonyl and trifluoro groups, which cannot participate in diis type of n conjugation, retard the rate of substitution at an adjacent caibon. ... 

A lrLL[uently encountered problem requires estimating a failure probability based on the number of failures, M, in N tests. These updates are assumed to be binomially distributed (equation 2.4-10) as p r N). Conjugate to the binomial distribution is the beta prior (equation 2.6-20), where / IS the probability of failure. 

Paarling, n. conjugated substance (jOld Chem.) copula (Biol.) allelomorph. Paarung, /. pairing, coupling, conjugation, paarweise, adv. in pairs, in couples. 

Acetylenes XCCY with n conjugated substituents, X and Y, on both carbon atoms have planar or perpendicular conformations. The substituents can be electron-donating or -accepting. The planar conformers are linear conjugate D-TI-D, D-IT-A, or A-IT-A systems whereas the perpendicular conformers are composed of ri-D and IT-A not in conjugation with each other. The orbital phase is continuous only in the planar conformations of D-TI-A (Scheme 23, cf. Scheme 4). The acetylenes with X=D (OR, NR ) and Y=A (RCO, ROCO) prefer planar conformations. When both substituents are electron-donating or accepting, the phase is discontinuous. The acetylenes then prefer perpendicular conformations. The predicted conformational preference was confirmed by ab initio molecular orbital calculations [32]. Diacetylenic molecules show similar conformational preference, which is, however, reduced as expected [32]. 

C-C a bond is replaced by a C=C n bond. The relative stability can also be nnder-stood by the analogy of the cross and linear n conjugation in the TMM and BD dianions (Schemes 6 and 7). Lone pair orbitals for the anion centers correspond to the bonds. The branched butene is more stable than the hnear isomer. 

Polymers with n-conjugated backbones are an important class of materials that have captured the imagination of the scientific community due to their remarkable properties and exciting applications [91-95]. While most of the work on n-conjugated polymers has focused on all-carbon systems, there has been considerable interest in incorporating heteroatoms into the n-conjugated backbone (i.e.,polythiophene, polypyrrole, polyaniline) to tune their properties. 

This review has shown that the analogy between P=C and C=C bonds can indeed be extended to polymer chemistry. Two of the most common uses for C=C bonds in polymer science have successfully been applied to P=C bonds. In particular, the addition polymerization of phosphaalkenes affords functional poly(methylenephosphine)s the first examples of macromolecules with alternating phosphorus and carbon atoms. The chemical functionality of the phosphine center may lead to applications in areas such as polymer-supported catalysis. In addition, the first n-conjugated phosphorus analogs of poly(p-phenylenevinylene) have been prepared. Comparison of the electronic properties of the polymers with molecular model compounds is consistent with some degree of n-conjugation in the polymer backbone. 

The Rise of Organophosphorus Derivatives in n-Conjugated Materials Chemistry... 

The second strategy is to replace the vinylene bridges of PPV (B) by a heteroatom possessing a lone pair that can participate in the n-conjugation [4]. Representative examples of this class of derivative (D) (Fig. 1) are the polyanilines and poly(p-phenylenesulfide) [la,b]. 

This account will summarise results in the development of n-conjugated materials incorporating phosphorus moieties with emphasis on the conceptual design and specific properties that result directly from the presence of the P-atom. Polyphosphazenes, which are the most familiar synthetic polymers incorporating phosphorus [8], will not be included in this review since they do not display the type of n-conjugation as sought in systems (A)-(D). 

Two types of symmetric fused dithienophospholes exist, which differ according to the position of the S atoms as illustrated by compounds (53) [54] and (54) [50] (Scheme 15). The a A -dithieno[3,2-fo 2, 3 -d]phosphole (55) has recently been considered as a potential subunit for the construction of n-conjugated materials [55] (Scheme 15). Exploitation of the reactivity of the nucleophilic P-atom of (55) allows access to derivatives (56) and complexes (57) (Scheme 15). The absorption and emission behaviour of these species varies with the nature of the P-moieties. Upon oxidation of the P-centre of (55),bathochromic shifts of Ajnax Aejn were observed Aj ax 344 nm for (55) and ca. 373 nm for (56), and Agjn 422 nm for (55) and ca. 460 nm for (56) [55]. These results nicely illustrate... 

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