A wide variety of monomeric and oligomeric, donor-substituted 1,1,4,4-tetracyanobutadienes (TCBDs) have been synthesized by [2+2] cycloaddition between tetracyanoethylene (TNCE) and donor-substituted alkynes, followed by electrocyclic ring opening of the initially formed cyclobutenes. Reaction yields are often nearly quantitative but can be affected by the electron-donating power and steric demands of the alkyne substituents. The intramolecular charge-transfer (CT) interactions between the donor and TCBD acceptor moieties were comprehensively investigated by X-ray crystallography, electrochemistry, UV-visible spectroscopy, and theoretical calculations. Despite the nonplanarity of the new chromophores, which have a substantial twist between the two dicyanovinyl planes, efficient intramolecular CT interactions are observed, and the crystal structures demonstrate a high quinoid character in strong donor substituents, such as N,N-dimethylanilino (DMA) rings. The maxima of the CT bands shift bathochromically upon reduction of the amount of conjugative coupling between strong donor and acceptor moieties. Each TCBD moiety undergoes two reversible, one-electron reduction steps. Thus, a tri-TCBD derivative with a 1,3,5-trisubstituted benzene core shows six reversible reduction steps within an exceptionally narrow potential range of 1.0 V. The first reduction potential E(red,1) is strongly influenced by the donor substitution: introduction of more donor moieties causes an increasingly twisted TCBD structure, a fact that results in the elevation of the LUMO level and, consequently, a more difficult first reduction. The potentials are also strongly influenced by the nature of the donor residues and the extent of donor-acceptor coupling. A careful comparison of electrochemical data and the correlation with UV-visible spectra made it possible to estimate unknown physical parameters such as the E(red,1) of unsubstituted TCBD (-0.31 V vs Fc+/Fc) as well as the maxima of highly broadened CT bands. Donor-substituted TCBDs are stable molecules and can be sublimed without decomposition. With their high third-order optical nonlinearities, as revealed in preliminary measurements, they should become interesting chromophores for ultra-thin film formation by vapor deposition techniques and have applications in opto-electronic devices.

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Donor-acceptor molecules with 4-(dimethylamino)phenyl donor and 1,1,4,4-tetracyanobuta-1,3-diene acceptor moieties are readily prepared by short, high-yielding routes. The quite small chromophores are characterised by X-ray crystallography and feature intense intramolecular charge-transfer bands, substantial quinoid character in the donor rings, reversible electrochemical reductions and oxidations and powerful third-order optical nonlinearities.

The macrocyclization between buckminsterfullerene, C,,, and bis-malonate derivatives in a double Singe1 reaction provides a versatile and simple method for the preparation ofcovalent bis-adducts of C,, with high regioand diastereoselectivity. A combination of spectral analysis, stereochemical considerations, and X-ray crystallography ( Fig. 2 ) revealed that out of the possible in-in, in-out, and out-out stereoisomers, the reaction of bis-malonates linked by 0-, ni-, or p-xylylene tethers afforded only the out-out ones (Scheme I). In contrast, the use of larger tethers derived from 1,lO-phenanthroline also provided a first example, (*)-19 (Scltemr 2), of an in-out product. Starting from optically pure bis-malonate derivatives, the new bis-functionalization method permitted the diastereoselective preparation of optically active fullerene derivatives (Schemes 4 and 5 ) and, ultimately, the enantioselective preparation (enantiomeric excess ee > 97 YO) of optically active cis-3 bis-adducts whose chirality results exclusively from the addition pattern (Fig. 6). The macrocyclic fixation of a bis-malonate with an optically active, 9,9-spirobi[9H-fluorene]-derived tether to C,, under generation of 24 and ent-24 with an achiral addition pattern (Scheme 4 ) was found to induce dramatic changes in the chiroptical properties of the tether chromophore such as strong enhancement and reversal of sign of the Cotton effects in the circular dichroism (CD) spectra (Figs. 4 and 5). By the same method, the functionalized bis-adducts 50 and 51 (Schemes 10 and If) were prepared as initiator cores for the synthesis of the fullerene dendrimers 62, 63, and 66 (Schemes 12 and 13) by convergent growth. Finally, the new methodology was extended to the regio-and diastereoselective construction of higher cycbpropanated adducts. Starting from mono-adduct 71, a clipping reaction provided exclusively the all-cis-2 tris-adduct (&)-72 (Scheme 14), whereas the similar reaction of bis-adduct 76 afforded the all-cis-2 tetrakis-adduct 77 (Scheme 15). Electrochemical investigations by steady-state voltammetry (Table 2) in CH,CI, ( + 0 . 1~ Bu,NPF,) showed that all macrocyclic bis(niethan0)fullerenes underwent multiple reduction steps, and that regioisomerism was not much influencing the redox potentials. All cis-2 bis-adducts gave an instable dianion which decomposed during the electrochemical reduction. In CH,CI,, the redox potential of the fullerene core in dendrimers 62, 63, and 66 is not affected by differences in size and density of the surrounding poly(ether-amide) dendrons. The all-cis-2 tris-and tetrakis(methano)fullerenes (5)-72 and 77, respectively, are reduced at more negative potential than previously reported all-e tris-and tetrakis-adducts with methano bridges that are also located along an equatorial belt. This indicates a larger perturbation of the original fullerene rr-chromophore and a larger raise in LUMO energy in the former derivatives.') Present address: Groupe des Matkriaux Organiques,

Until very recently the Ni and Cu corroles, already described in the sixties, were regarded as the MII complexes 1 (M = Ni, Cu). Some doubt arose about this interpretation after the existence of FeIV corroles demonstrated that corroles can stabilize metals in unusual oxidation states. Thorough physical studies have now shown that the metal atoms in the Ni and Cu corroles do in fact have the formal oxidation state +III (2).