Electronic spectra and electronic structures of [2.2]paracyclophane and related compounds

Iwata, Suehiro; Fuke, Kiyokazu; Sasaki, Michiko; Nagakura, Saburo; Otsubo, Tetsuo; Misumi, Soichi

doi:10.1016/0022-2852(73)90022-2

Cited by 59 publications

(28 citation statements)

References 24 publications

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“…Another class of compounds where interaction of 'IT-electron clouds through space can easily be studied are the paracyclophanes [13] and other phanes [14][15][16] in which two aromatic units are kept in a face-to-face arrangement by methylene bridges. Luminescence and absorption was studied by EI-Sayed [17], Rice and co-workers [18][19][20] and more recently Nagakura and co-workers [21,22] for the JlIacyclophanes and by Froines et a\. [23] for the [2.21 (l,4)-naphthalenophanes.…”

Section: Introductionmentioning

confidence: 99%

Transannular interactions in [2,2] phanes as studied by magnetic resonance and optical spectra

Schweitzer¹,

Colpa²,

Behnke³

et al. 1975

Chemical Physics

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The interaction of IT-eleetrons in [2.2] phanes was studied both experimcntally and theoretically. The fluorescence and phosphorescence spectra were measured at liquid helium temperature; in addition, the zero field splitting parameters D and E were detcrmined by ODMR in zero field and by ordinary ESR at X·band. The results for the phanes with two identical aromatic units can be summarized as follows: The rather small reduction of the D and E values of the order of 10% with respect to the monomrrs indicates, in agreement with the theoretical treatment given in part II, that the two unpaired electrons of the excited triplet state have a high probability to be at a given time in the same half of the molecule. While the fluorescence spectra show the typical behaViour of emission spectra of dimers or excimers, the phosphorescence spectra CKhibit some remaining structure. This behaviour which indicates a somewhat weaker coupling among the triplet orbitals as compared to the singlet orbitals can also be understood on the basis of theoretical considerations. for a phane with two different aromatic units thl! behaviour is found t~ be more Similar to the corresponding aromatic monomer with the lower ex" cited states with some pcrtu~bation by the other part of the phane also.in agreement with theoretical expectation.

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Section: Introductionmentioning

confidence: 99%

Transannular interactions in [2,2] phanes as studied by magnetic resonance and optical spectra

Schweitzer¹,

Colpa²,

Behnke³

et al. 1975

Chemical Physics

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“…In the absorption spectrum shown in Figure 3, five absorption bands are observed for 1; a detailed assignment of the absorption spectrum for this molecule has been discussed in our previous work. 37 Iwata et al 38 observed an additional band at 188.7 nm. We have calculated the six lowest excited states, of which one with an excitation wavelength shorter than 200 nm.…”

Section: The Journal Of Physical Chemistry Amentioning

confidence: 95%

“…Absorption and emission spectroscopic studies of 1 and 4 have been reported. − Among these reports, Shen et al published the absorption spectrum for the transition to the first excited state of 1 in the region between 307 and 326 nm. Melzer et al .…”

Section: Introductionmentioning

confidence: 99%

Structure, NMR and Electronic Spectra of [m.n]Paracyclophanes with Varying Bridges Lengths (m, n = 2–4)

et al. 2016

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Extending our earlier studies on cyclophanes, we here report the structure, chemical shifts, spin-spin coupling constants, absorption and emission properties of [m.n]paracyclophanes, m, n = 2-4, obtained using a combination of experimental and computational techniques. Accurate values of proton chemical shifts as well as of JHH for the bridges are determined. The experimental chemical shifts, coupling constants, absorption and emission wavelengths are satisfactorily reproduced using density functional theory calculations, using both the B3LYP and ωB97X-D functionals. The geometries predicted using a functional that includes dispersion corrections (ωB97X-D) are in a better agreement with available experimental values than those obtained using the B3LYP method. Up to 8 UV-vis absorption/emission bands have been observed (or anticipated in the region below 200 nm) and assigned on the basis of quantum-chemical calculations. Optimized excited-state geometries showed that the distances between the aromatic bridgehead carbon atoms of all the [m.n]paracyclophanes in the excited state decrease compared to the ground-state geometries by ca. 0.2-0.9 Å, the largest being for [4.4]paracyclophane, though the rather large differences in the calculated emission wavelength compared to experiment cast some doubts on the accuracy of the excited-state geometries.

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“…Iwata et al [82] have investigated the electronic spectra and the electronic structures of [2.2]paracyclophane (14), tetramethyl [2,2]paracyclophane (97), and the re- Otsubo et al [83] have synthesized triple-layered [2.2][2.2]naphthalenophane (100) and investigated its structure and properties. In this compound, the outer naphthalene rings are bent into a boat form and the inner naphthalene ring is bent into a twist form.…”

Section: Multi-layered Cyclophanesmentioning

confidence: 99%

UV/Vis Spectra of Cyclophanes

Rademacher

2004

Modern Cyclophane Chemistry

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Electronic spectra and electronic structures of [2.2]paracyclophane and related compounds

Cited by 59 publications

References 24 publications

Transannular interactions in [2,2] phanes as studied by magnetic resonance and optical spectra

Transannular interactions in [2,2] phanes as studied by magnetic resonance and optical spectra

Structure, NMR and Electronic Spectra of [m.n]Paracyclophanes with Varying Bridges Lengths (m, n = 2–4)

UV/Vis Spectra of Cyclophanes

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