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Notes: ESR. and ENDOR. studies are reported for the radical anions of 1,2-diphenylcyclopentene (3) and its di(pe+deuteriophenyl)-derivative (3-D10). Comparison of the coupling constants of the phenyl protons in 3\documentclass{article}\pagestyle{empty}\begin{document}$ ^{\ominus \atop \dot{}} $\end{document}. with the analogous values for the radical anions of 1,2-diphenyl substituted cyclopropene (1) and cyclobutene (2) reveals regular changes in the sequence 1\documentclass{article}\pagestyle{empty}\begin{document}$ ^{\ominus \atop \dot{}} $\end{document}, 2\documentclass{article}\pagestyle{empty}\begin{document}$ ^{\ominus \atop \dot{}} $\end{document}, 3\documentclass{article}\pagestyle{empty}\begin{document}$ ^{\ominus \atop \dot{}} $\end{document}, which are caused by an increasing twist of the phenyl groups about the C(1), C(1′)- and C(2), C(1″)-bonds linking them to the ethylene fragment. Such a twist is shown to be also responsible for the large difference in the coupling constants of the methylene β-protons in 3\documentclass{article}\pagestyle{empty}\begin{document}$ ^{\ominus \atop \dot{}} $\end{document}. (0.659 and 0.293 mT). It is suggested that - in order to minimize the losses caused by this twist in the π-delocalization energy - the 2 pz-axes at the centres 1 and 2 deviate from a perpendicular orientation to the mean plane of the cyclopentene ring. A deviation by 19° from such an orientation is required to account for the observed β-proton coupling constants in terms of their conventional cos2-dependence on the dihedral angles θ.

Notes: The radical anions of the following substituted [2.2]paracyclophanes have been characterized by ESR. and ENDOR. spectroscopy: 4, 16-dicyano- (o-2), 4, 12-dicyano- (p-2), 4,5,12,13-tetracyano- (3) and 4,5,12,13-tetrakis (alkoxycarbonyl)- [2.2]paracyclophanes (4-R, where R = Me, Et, iPr or tBu is the ester alkyl group); 4,5-bis(methoxycarbonyl)[2.2]paracyclophane-12, 13-dicarboxylic anhydride (5); [2.2]paracyclophane-4,5:12, 13-tetracarboxylic bisanhydride (6) and bisimides (7-R, where R = H, D, Me or Ph is the substituent at the imide N-atom). Comparison of the hyperfine data for these radical anions with those for analogously substituted derivatives of benzene indicates that the most prominent coupling constants are approximately halved on passing from the latter to the former. Lowering of the symmetry, as a consequence of ion pairing, has been observed for the radical anions 4-iPr\documentclass{article}\pagestyle{empty}\begin{document}$^{\ominus \atop \dot{}}$\end{document} and 4-tBu\documentclass{article}\pagestyle{empty}\begin{document}$^{\ominus \atop \dot{}}$\end{document} associated with the counterion K⊕ in 1,2-dimethoxyethane at 183 K, but not for 4-Me\documentclass{article}\pagestyle{empty}\begin{document}$^{\ominus \atop \dot{}}$\end{document} and 4-Et\documentclass{article}\pagestyle{empty}\begin{document}$^{\ominus \atop \dot{}}$\end{document} under the same conditions. This result suggests that the migration of K⊕ between the preferred sited in two equivalent ion pairs is slowed down by the steric hindrance arising from the bulky iPr and tBu ester groups.

Notes: The radical anions of 6a-thiathiophthenes ([1,2]dithiolo[1,5-b] [1,2]dithioles), I(R), convert into those of 4H-thiapyran-4-thiones, III(R), via cis-trans isomerization. The reaction is slowed down when the size of the substituent R in the 2,5-positions of 6a-thiathiophthene increases, and it is prevented by the introduction of a 3,4-polymethylene bridge. The primary and the secondary radical anions, I(R)\documentclass{article}\pagestyle{empty}\begin{document}$ ^{\ominus \atop \dot{}} $\end{document} and III(R)\documentclass{article}\pagestyle{empty}\begin{document}$ ^{\ominus \atop \dot{}} $\end{document}, respectively, exhibit very similar hyperfine splitting patterns. E.g., in the case of the unsubstituted 6a-thiathiophthene, I(H), and 4H-thiapyran-4-thione, III(H), the proton coupling constants are aH2,5=6.72 and aH3,4=1.73 Gauss for I(H)\documentclass{article}\pagestyle{empty}\begin{document}$ ^{\ominus \atop \dot{}} $\end{document}, and aH2,6=6.35 and aH3,5=2.07 Gauss for III(H)\documentclass{article}\pagestyle{empty}\begin{document}$ ^{\ominus \atop \dot{}} $\end{document}. In contrast to I(H)\documentclass{article}\pagestyle{empty}\begin{document}$ ^{\ominus \atop \dot{}} $\end{document}, cis-trans isomerization could not thus far be proved to occur with its 1,6-dioxa-analogue, IV(H)\documentclass{article}\pagestyle{empty}\begin{document}$ ^{\ominus \atop \dot{}} $\end{document}, since no ESR. spectrum of the radical anion of 4H-pyran-4-thione, V(H), was detected upon reduction of IV(H).

Notes: The ESR. spectrum of the relatively unstable radical anion of diphenylcyclo-propenone (II) has been observed upon electrolytic reduction of II in N,N-di-methylformamide and 1,2-dimethoxyethane. Simple MO models account well for the π-spin distribution and for the restricted rotation of the phenyl substituents in II\documentclass{article}\pagestyle{empty}\begin{document}$ ^{\ominus \atop \dot{}} $\end{document}. A rather facile loss of a CO molecule by II\documentclass{article}\pagestyle{empty}\begin{document}$ ^{\ominus \atop \dot{}} $\end{document} results in formation of the radical anion of tolane (diphenylacetylene; III). No ESR. spectra could be obtained for the radical anions of dialkylcyclopropenones which are even shorter-lived than II\documentclass{article}\pagestyle{empty}\begin{document}$ ^{\ominus \atop \dot{}} $\end{document}, although decay by decarbonylation seems to be less favoured with them than with II\documentclass{article}\pagestyle{empty}\begin{document}$ ^{\ominus \atop \dot{}} $\end{document}. In presence of air, electrolytic reduction of either II or its dimethyl and di-t-butyl analogues yields the correspondingly disubstituted semidione anions.

Notes: Proton hyperfine data have been determined for the radical anions and cations of dibenzo [b,f]pentalene (III) and its 5, 10-dimethyl derivative (IV). The assignment of the coupling constants to pairs of equivalent protons follows from a simple MO model, the use of which enables one to reproduce satisfactorily the experimental values. The proton hyperfine data, aHμThe meaning of aHμis aH—C(x),H—C(y),whereas only x and y are given in the particular cases., for the radical anion III⊖. correlate fairly well with the π-charge populations ∊μ derived from 1H-NMR. spectra for the carbon centres μ in the dianion III2⊖. The analogous correlation is less good in the case of the radical cation III⊕. and the dication III2⊕., presumably due to the rough approximations involved in the evaluation of the numbers ∊μ for the latter species. The coupling constants aH5,10 for III⊖. and III⊕. are very close to the corresponding values aH4,6 for the radical ions of 1,3,5-tri-t-butylpentalene (II), in accord with the prediction of the MO model. A similarity is also found between the proton hyperfine data for III⊖. and those for the radical anions of structurally related 1,4-diphenyl-1,3-butadiene (V). On the other hand, there are striking changes in the coupling constants of the analogous protons on passing from III⊖. to the radical anions of dibenzo [a,e] cyclooctene (VI) and [16] annulene (VII), as a consequence of raising the symmetry from C2h to D2h and D4h, respectively.

Notes: The rearrangement products obtained upon reduction of 1,6-methano[10]-annulene (1) and its 11-halogen derivatives have been studied by ESR. and, in part, by ENDOR. spectroscopy. These derivatives comprise 11,11-difluoro- (2), 11-fluoro- (3), 11,11-dichloro- (4) and 11-bromo-1,6-methano[10]annulene (5), as well as the 2,5,7,10-tetradeuteriated compounds 2-D4 and 3-D4. The studies of the secondary products in question have been initiated by the finding that the radical anion of 11,11-dimethyltricyclo[4.4.1.01,6]undeca-2,4,7,9-tetraene (12), i.e., the prevailing valence isomer of 11,11-dimethyl-1,6-methano[10]annulene, undergoes above 163 K a rearrangement to the radical anion of 5,5-dimethylbenzocycloheptene (14). A rearrangement of this kind also occurs for the radical anion of the parent compound 1, albeit only above 323 K. The lower reactivity of 1\documentclass{article}\pagestyle{empty}\begin{document}$ 1^{\ominus \atop \dot{}} $\end{document} relative to 12\documentclass{article}\pagestyle{empty}\begin{document}$ 1^{\ominus \atop \dot{}} $\end{document} is rationalized by the assumption that the first and rate determining step in the case of 1\documentclass{article}\pagestyle{empty}\begin{document}$ 1^{\ominus \atop \dot{}} $\end{document} is the valence isomerization to the radical anion of tricyclo[4.4.1.01,6]undeca-2,4,7,9-tetraene (1a). In the reducing medium used in such reactions (potassium in 1,2-dimethoxyethane), the final paramagnetic product of 1\documentclass{article}\pagestyle{empty}\begin{document}$ 1^{\ominus \atop \dot{}} $\end{document} is not 5H-benzocycloheptene (15), but the benzotropylium radical dianion (). This product () is also obtained from the radical anions of the halogen-substituted 1,6-methano[10]annulenes, 2 to 5, in the same medium. The temperatures required for the conversion of 2\documentclass{article}\pagestyle{empty}\begin{document}$ 1^{\ominus \atop \dot{}} $\end{document} and 3\documentclass{article}\pagestyle{empty}\begin{document}$ 1^{\ominus \atop \dot{}} $\end{document} into lie above 293 and 243 K, respectively, whereas the short-lived species 4\documentclass{article}\pagestyle{empty}\begin{document}$ 1^{\ominus \atop \dot{}} $\end{document} and 5\documentclass{article}\pagestyle{empty}\begin{document}$ 1^{\ominus \atop \dot{}} $\end{document} undergo such a rearrangement already at 163 K. The stability of the four halogen-substituted radical anions thus decreases in the sequence 2\documentclass{article}\pagestyle{empty}\begin{document}$ 1^{\ominus \atop \dot{}} $\end{document} 〉 3\documentclass{article}\pagestyle{empty}\begin{document}$ 1^{\ominus \atop \dot{}} $\end{document} 〉 4\documentclass{article}\pagestyle{empty}\begin{document}$ 1^{\ominus \atop \dot{}} $\end{document} ≈ 5\documentclass{article}\pagestyle{empty}\begin{document}$ 1^{\ominus \atop \dot{}} $\end{document}. Replacement of 2\documentclass{article}\pagestyle{empty}\begin{document}$ 1^{\ominus \atop \dot{}} $\end{document} and 3\documentclass{article}\pagestyle{empty}\begin{document}$ 1^{\ominus \atop \dot{}} $\end{document} by 2-D4\documentclass{article}\pagestyle{empty}\begin{document}$ 1^{\ominus \atop \dot{}} $\end{document} and 3-D4\documentclass{article}\pagestyle{empty}\begin{document}$ 1^{\ominus \atop \dot{}} $\end{document}, respectively, leads to 1,4,5,8-tetradeuteriobenzotropylium radical dianion (). Experimental evidence and theoretical arguments indicate that the rearrangements in question are initiated by a loss of one (3\documentclass{article}\pagestyle{empty}\begin{document}$ 1^{\ominus \atop \dot{}} $\end{document} and 5\documentclass{article}\pagestyle{empty}\begin{document}$ 1^{\ominus \atop \dot{}} $\end{document}) or two (2\documentclass{article}\pagestyle{empty}\begin{document}$ 1^{\ominus \atop \dot{}} $\end{document} and 4\documentclass{article}\pagestyle{empty}\begin{document}$ 1^{\ominus \atop \dot{}} $\end{document}) halogen atoms. Such a reaction step must involve the intermediacy of the radical 19 · (see below) which rapidly isomerizes to the benzotropylium radical 16:. Support for the transient existence of 19. is provided by the thermolysis of 1,6-methano [10]annulene-11-t-butylperoxyester (6) which yields 16. in a temperature dependent equilibrium with a mixture of its dimers (162).In the hitherto unreported ESR. spectra of 2\documentclass{article}\pagestyle{empty}\begin{document}$ 1^{\ominus \atop \dot{}} $\end{document}. and 3\documentclass{article}\pagestyle{empty}\begin{document}$ 1^{\ominus \atop \dot{}} $\end{document}, the coupling constants of the ring protons differ considerably from the analogous values for the radical anions of other 1,6-bridged [10]annulenes. These differences strongly suggest that the fluoro-substitution substantially affects the character of the singly occupied orbital.

Notes: MO-LCAO Calculations on Polymethines. IX. On the Chromaticity of Coupled Oxonol and Cyanine DyesStreptopolymethines display low-energy electronic transitions with a high transition probability and possess, moreover, a high capability to accept or to release electrons. These properties account for the absorption colour of polymethine dyes consisting of two molecular fragments. Scope and limitations of a composite-molecule approach can be recognized by subjecting the electronic wavefunctions to the so-called configuration analysis. Colour-structure relationships are derived from inspection of key orbital interactions between the molecular fragments.

Notes: Ausgehend von einer quantenchemischen Charakterisierung des Polymethinzustandes, die in den vorangegangenen Arbeiten behandelt wurde, wird die Bedeutung der Streptopolymethin-Teilsysteme für komplizierte molekulare Strukturen untersucht. Um die Elektronenstruktur des zusammengesetzten Systems mit denen der partizipierenden Teilsysteme zu vergleichen, werden die elektronischen Wellenfunktionen der Konfigurationsanalyse unterworfen. Die Lokalisierbarkeit in atomare und molekulare Subsysteme wird durch Indizes bewertet. Danach können zahlreiche Strukturen aus polymethinischen, polyenischen und aromatischen Fragmenten zusammengesetzt gedacht werden. Bei einigen carbo- und heterocyclischen π-Systemen ist das Baukastensystem nur begrenzt anwendbar. Die Anwendungsbreite des Modells kann aber durch Anwendung der einfachen Störungstheorie 2. Ordnung leicht erkannt werden.