Cationic and mixed-valent forms of Fe3O(CO2)6 trigonal prismatic clusters have been linked by ditopic links, namely, 1,4-benzenedicarboxylate (1,4-BDC) and 1,3-benzenedicarboxylate (1,3-BDC), to produce two 3-periodic metal-organic frameworks (MOFs), [Fe3O(1,4-BDC)3 (DMF)3][FeCl4] x (DMF)3 (MOF-235) and Fe3O(1,3-BDC)3 (py)3 x (py)0.5(H2O)1.5 (MOF-236) (DMF = N,N-dimethylformamide, py = pyridine), respectively. These MOFs exemplify a new, high-symmetry topology termed acs which we identify here as the default arrangement for linking trigonal prisms together.

To combine the stability of alpha-oligothiophenes with the planarity of acenes, fully fused oligothienoacenes were synthesized and their properties compared to the nonfused alpha-oligothiophenes. By employing removable solubilizing groups, our synthetic methodology made it possible to efficiently prepare and purify oligothienoacenes with up to seven fused rings. The key steps involved the halogen dance reaction and Pd-catalyzed coupling of Bu3SnSSnBu3 to introduce sulfur linkages. This approach eliminates alpha-beta anion equilibration, a significant improvement over the traditional method of introducing sulfur linkages via Li-Br exchange. X-ray diffraction data indicate that pentathienoacene and heptathienoacene adopt pi-stacked packing motifs in contrast to the herringbone packing of nonfused oligothiophenes. On the basis of the linear dependence of the longest lambdamax on the reciprocal number of double bonds of thienoacenes with three to seven rings, the band gap of polythienoacene is extrapolated to be 2.21 eV.

By employing a rigid adamantane-based unit as a spacer, a coordination solid with an open channel layered structure results showing the first observation of metal sulfonate clusters. The design approach employed enforces a structural mismatch of metal and ligand coordinative preferences.