Quinones as electron acceptors. X-ray structures, spectral (EPR, UV-vis) characteristics and electron-transfer reactivities of their reduced anion radicals as separated vs contact ion pairs.

Successful isolation of a series of pure (crystalline) salts of labile quinone anion radicals suitable for X-ray crystallographic analysis allows for the first time their rigorous structural distinction as "separated" ion pairs (SIPs) vs "contact" ion pairs (CIPs). The quantitative evaluation of the precise changes in the geometries of these quinones (Q) upon one-electron reduction to afford the anion radical (Q-*) is viewed relative to the corresponding (two-electron) reduction to the hydroquinone (H2Q) via the Pauling bond-length/bond-order paradigm. Structural consequences between such separated and contact ion pairs as defined in the solid state with those extant in solution are explored in the context of their spectral (EPR, UV-vis) properties and isomerization of tightly bound CIPs. Moreover, the SIP/CIP dichotomy is also examined in intermolecular interactions for rapid (self-exchange) electron transfer between Q-* and Q with second-order rate constants of kET approximately equal to 10(8) M-1 s-1, together with the spectral observation of the paramagnetic intermediates [Q,Q-*]leading to 1:1 adducts, as established by X-ray crystallography.

Very fast electron migrations within p-doped aromatic cofacial arrays leading to three-dimensional (toroidal) pi-delocalization.

The charge-resonance phenomenon originally identified by Badger and Brocklehurst lies at the core of the basic understanding of electron movement and delocalization that is possible within p-doped aromatic (face-to-face) arrays. To this end, we now utilize a series of different aryl-donor groups (Ar) around a central platform to precisely evaluate the intramolecular electron movement among these tethered redox centers. As such, the unique charge-resonance (intervalence) absorption bands observed upon the one-electron oxidation or p-doping of various hexaarylbenzenoid arrays (Ar6C6) provide quantitative measures of the reorganization energy (lambda) and the electronic coupling element (H(ab)) that are required for the evaluation of the activation barrier (deltaG(ET)) for electron-transfer self-exchange according to Marcus-Hush theory. The extensive search for viable redox centers is considerably aided by the application of a voltammetric criterion that has led in this study to Ar = N,N-dialkyl-p-anilinyl, in which exceptionally low barriers are shown to lie in the range deltaG(ET) = 0.3-0.7 kcal mol(-1) for very fast electron hopping or peregrination around the hexagonal circuit among six equivalent Ar sites. Therefore, at transition temperatures T(t) > 0.5/R or roughly -20 degrees C, the electron-transfer dynamics become essentially barrierless since the whizzing occurs beyond the continuum of states and effectively achieves complete pi-delocalization.

"Separated" versus "contact" ion-pair structures in solution from their crystalline states: dynamic effects on dinitrobenzenide as a mixed-valence anion.

Qualitative structural concepts about dynamic ion pairs, historically deduced in solution as labile solvent-separated and contact species, are now quantified by the low-temperature isolation of crystalline (reactive) salts suitable for direct X-ray analysis. Thus, dinitrobenzenide anion (DNB(-)) can be prepared in the two basic ion-paired forms by potassium-mirror reduction of p-dinitrobenzene in the presence of macrocyclic polyether ligands: L(C) (cryptand) and L(E) (crown-ethers). The crystalline "separated" ion-pair salt isolated as K(L(C))(+)//DNB(-) is crystallographically differentiated from the "contact" ion-pair salt isolated as K(L(E))(+)DNB(-) by their distinctive interionic separations. Spectral analysis reveals pronounced near-IR absorptions arising from intervalence transitions that characterize dinitrobenzenide to be a prototypical mixed-valence anion. Most importantly, the unique patterns of vibronic (fine-structure) progressions that also distinguish the "separated" from the "contact" ion pair in the crystalline solid state are the same as those dissolved into THF solvent and ensure that the same X-ray structures persist in solution. Moreover, these distinctive NIR patterns are assigned with the aid of Marcus-Hush (two-state) theory to the "separated"ion pair in which the unpaired electron is equally delocalized between both NO(2)-centers in the symmetric ground state of dinitrobenzenide, and by contrast, the asymmetric electron distribution inherent to "contact"ion pairs favors only that single NO(2)-center intimately paired to the counterion. The labilities of these dynamic ion pairs in solution are thoroughly elucidated by temperature-dependent ESR spectral changes that provide intimate details of facile isomerizations, ionic separations, and counterion-mediated exchanges.

Synthesis and structure of multicomponent crystals of fullerenes and metal tetraarylporphyrins.

The preparation of fullerene complexes with metal tetraarylporphyrins in the presence of excess ferrocene (Cp(2)Fe) results in the formation of new solvent-free and multicomponent molecular crystals. New isomorphous complexes of C(60) with PyZnTPP (ZnTPP identical with zinc 5,10,15,20-tetraphenyl-21H,23H-porphyrinate) and PyCoTPP (CoTPP identical with cobalt(II) 5,10,15,20-tetraphenyl-21H,23H-porphyrinate) containing Cp(2)Fe and the isostructural C(70) complex with PyZnTPP have been prepared. The crystal structures of the new layered C(60) complexes CoTMPP x C(60) (obtained in the presence of Cp(2)Fe) and CoTMPP x 2C(60) x 3C(7)H(8) (obtained in the absence of Cp(2)Fe) have been described (CoTMPP identical with cobalt(II) 5,10,15,20-tetrakis(p-methoxyphenyl)-21H,23H-porphyrinate). Cobalt atoms of the PyCoTPP and CoTMPP molecules are weakly coordinated to C(60) with Co...C(C(60)) distances in the 2.64-2.82 A range, whereas zinc atoms of PyZnTPP, as well as cobalt atoms of the CoTMPP molecules in the solvent-free phase, form only van der Waals contacts with fullerenes. Different packing arrangements in the crystals of fullerene-porphyrin complexes have been discussed.