Mixed-Isocyanide Complexes of Technetium under Steric and Electronic Control.

Reactions of the alkyl isocyanide fac-[Tc(CO)3(CNR)2Cl] complexes (2) (CNR = CNnBu or CNtBu) with the sterically encumbered isocyanide CNp-FArDarF2 [DArF = 3,5-(CF3)2C6H3] allow a selective exchange of the carbonyl ligands of 2 and the isolation of the mixed-isocyanide complexes mer,trans-[Tc(CNp-FArDarF2)3(CNR)2Cl] (3). Depending on the steric requirements of the residues R, the remaining chlorido ligand can be replaced by another isocyanide ligand. Cationic complexes such as mer-[Tc(CNp-FArDarF2)3(CNnBu)3]+ (4a) or mer,trans-[Tc(CNp-FArDarF2)3(CNnBu)2(CNtBu)]+ (6) have been prepared in this way and isolated as their PF6- salts. mer,trans-[Tc(CNp-FArDarF2)3(CNnBu)2(CNtBu)](PF6) represents to the best of our knowledge the first transition-metal complex with three different isocyanides in its coordination sphere. Since the degree of the ligand exchange seems to be controlled both by the electronic and steric measures of the incoming isocyanides, we undertook similar reactions with the sterically less demanding p-fluorophenyl isocyanide, CNPhpF, which indeed readily led to the hexakis(isocyanide)technetium(I) cation through an exchange of all ligands in the staring materials [Tc2(CO)6(µ-Cl)3]- or fac-[Tc(CO)3(CNR)2Cl]. The influence of the substituents at the isocyanide ligands in such reactions has been reasoned with the density functional theory-derived electrostatic potential at the accessible surface of the corresponding isocyanide carbon atoms.

Metal Phthalocyanine-Fullerene Dyads: Promising Lamellar Columnar Donor-Acceptor Liquid Crystal Phases.

Liquid crystal (LC) shape-amphiphiles with a disc tethered to a fullerene have been intensely studied for the application in photovoltaics, and helical nanosegregation of C60 has been claimed around the π-stacking disks based on X-ray results. The most promising materials reported to date have been resynthesized and studied comprehensively by XRS, density measurements, modelling, and electron density reconstruction. In contrast to previous reports, the results indicate that metal phthalocyanine-fullerene mesogens pack in lamellar columnar phases with p2gm symmetry. Fullerenes assemble in layers and are flanked by phthalocyanine columns, thus explaining the balanced charge carrier mobility of electrons and holes. Such variable donor-acceptor structures are promising for organic electronic applications.