acetylene chermistry by F. Diederich, P. J. Stang, R. R. Tykwinski

By F. Diederich, P. J. Stang, R. R. Tykwinski

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Insertion of a second triple bond or/and a phenylene unit results in a reduced coupling relative to a linkage made of a single triple bond, although replacement of the phenylene with an anthracenylene enhances the coupling markedly. 5 Hybrid sp-sp3 Oligoacetylenic Molecules Several b-diynes (or “skipped” diynes [99]) X(CaCH)2 (X = CRl2, SiRl2, PRl, S,…) are known, but the elusiveness of the unsubstituted diethynyl ether (X = O) [100] motivated comparative ab initio theoretical comparisons with the analogues X = S [101] or X = Se [102].

3) expands the conjugation in two dimensions, and was expected to enhance the second hyperpolarizability [75]. 3). The calculated variation of the second hyperpolarizabilities with the nature of the spacer is in good agreement with experimentally obtained results. 3 Oligo(triacetylene) chromophores with a central heterospacer between two diethynylene units [74]. 2 Linear Acetylenic Scaffolds Let us finally mention that the poly(triacetylene) hexamer served as an illustrative example of the applicability of the new program SIXW.

The detailed mechanism of this phenomenon, and especially the role of the triplet excitations, is not yet established. 4 R = NO2, R' =NH2 V Vc R =H, R' =Et Schematic representation of the MRTD and NDR properties of OEPs. order to describe the singlet and triplet excited states of OEPs [82]. Intersystem crossing from the singlet to the triplet manifold by spin-orbit coupling is possible, and results in a mixing of the singlet and triplet wavefunctions. The role of chain length and of ring twisting on the intersystem crossing process has been studied.

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