Charge-transfer complexes in the excited state. Laser photolysis studies

Electrostatic attraction by oppositely charged ions leads to ion pairing. The influence of solvent polarity, the size and the charge of the ions as well as the electron-pair donor and acceptor strength on the equilibrium constant of ion-pair formation is discussed.

Photoinduced electron transfer in ion pairs

The formation of complexes between electron donors and acceptors has long been recognized a s an important phenomenon. Many of themolecular complexes are colored and give rise to new absorption bands in the electronic spectra. These molecular complexes have been investigated by employing a variety of physical methods such as optical spectroscopy, magnetic resonance spectroscopy, calorimetry, dielectric measurements, and X-ray diffraction. Studies of donor-acceptor complexes are of value in understanding various types of reaction mechanisms, including molecular phenomena in biological systems. Some of the relatively recent developments in the study of molecular complexes are: the classification of donors and acceptors by Mulliken [l], vibrational spectroscopy, particularly in the very-low-frequency region [2,3], estimation of the per cent charge transfer by dipole moment measurements [4–6], studies of weak interactions (contact pairs) [7], spectra and thermodynamics of complexes in vapor phase [8,...

Spectroscopy of electron donor-acceptor systems

Charge-transfer-absorption, CT-emission- and ESR-spectroscopy with zone-refined crystals of anthracene-pyromellitic dianhydride

Triplet excimers favoured by charge transfer in electron-donor-acceptor-complexes: (Excimer-phosphorescence and triplet-triplet-absorption of triplet-excimers)

zenz beobachtet werden. Die Lage der CT-Bande ist abhängig vom Anion und vom Lösungsmittel. Bei Beobachtung mit dem Phosphoroskop wird zusätzlich die Phosphoreszenz des Kations beobachtet. Die mittlere Lebensdauer des Kation-Triplettanregungszustandes der Ionenpaare ist in einigen Fällen relativ zu den freien Kationen verkürzt. Es wird der Mechanismus des Energieüberganges vom CT-Anregungszustand zum Triplettzustand des Kations, sowie die Verkürzung der Abklingzeit in Abhängigkeit vom Anion diskutiert.

Fluoreszenz und Phosphoreszenz in Ionenpaaren durch interionaren Elektronenaustausch1

The influence of the charge transfer complexing on the phosphorescenceand the triplet-(T)-absorption spectra and on the kinetics of the decay of the concentration of the locally triplet excited donors phenanthrene (P), naphthalene (N) and naphthalene-de in the complexes with the acceptors tetrachlorophthalic-anhydride (TCPA) and pyromellitic-dianhydride (PMDA) has been investigated in glassy solutions of ra-propyl-ether (n PÄ) in dépendance of the temperature (96°—118°K) and of the concentration of D and A1. On considering all the experimental results it has to be distinguished between the species of complexes (3D A) and of the excimers (D 3D A) according to the temperature and the concentration quotient q = cd/caFurthermore we observed the charge transfer-(CT*)-absorption bands corresponding to a transfer of an electron from the locally triplet excited donor to an unoccupied energy level of the acceptor. The plot of the extinction of T-absorption vs. the time after irradiation is not exponential in the range of short times but becomes quite well exponential when the time of measurement increases. The kinetics were quantitatively analyzed and the lifetime of the locally triplet excited D in (3D A) and in (D 3D A) was calculated. For analyzing the T-extinction decay curves it was necessary to distinguish between different spectral ranges of the absorption. Furthermore the influence of concentration and of temperature has to be taken into account.

Emissions- und Absorptions-Spektren von Naphthalin und Phenanthren im Triplett-Anregungszustand in Donator-Akzeptor-Komplexen mit Tetrachlorphthalsäureanhydrid und Pyromellitsäuredianhydrid

Electron Transfer from Solvent to a Triplet Excited Acceptor Molecule

Elektronenüberführung vom Lösungsmittel auf ein im Triplett‐Zustand angeregtes Acceptor‐Molekül

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