A triangular macrocyclic molecule has been synthesized which consists of substituted phenanthrene vertices interconnected by 1,3-diethynylbicyclo[1.1.1]pentane sides. The molecule is the very first example of exploiting the bicyclopentane motif in the construction of a shape persistent macrocycle's backbone. It carries new features such as bulkiness, nonconjugated σ-bonding, and a certain conformational flexibility due to its easy longitudinal rotation. We have used some of the features in order to rationalize the observed tendency of the compound to form films on various surfaces.

Symmetrical bridgehead-to-bridgehead coupling of bicyclo[1.1.1]pentane cages has been effected in 48−70% yields by the cuprate oxidation method.

1,3‐Diethynylbicyclo[1.1.1]pentane (DEBCP) has been found to be a valuable molecular building block mostly for the synthesis of extended, rigid, rod‐like molecules. With its straightforward linear geometry, DEBCP can be used as a nonconjugated alternative to more frequently used π‐conjugated, rod‐like building blocks. Examples of reactions that introduce DEBCP into larger structures are (1) the reaction of DEBCP lithium acetylides with electrophiles such as TMSCl, CO2, and Ph2PCl, (2) Sonogashira–Hagihara cross‐coupling reactions with aryl or heteroaryl iodides or bromides, and (3) umpolung reactions that afford the corresponding dibromo and diiodo derivatives of DEBCP, which then successfully react with tert‐C‐cuprates derived from p‐ and m‐dicarbadodecaboranes or bicyclopentanes. These umpolung reactions afforded a new class of molecular rods that combine carborane or bicyclo[1.1.1]pentane cages with ethynylene linkers. Many of the DEBCP derivatives were studied by single‐crystal X‐ray diffraction. They form well‐organized arrays of molecular rotors, the DEBCP units, and so can be considered as examples of artificial molecular‐size machines.

Derivatives of bicyclo[1.1.1]pentane differentially substituted in bridgehead (1,3) and bridge (2,4) positions have been synthesized. They represent a new T-shaped structural module consisting of a rigid rod with a nearly freely rotating side arm, possibly useful as a molecular building block in syntheses of more complex covalent or supramolecular scaffolds useful in bottom-up construction of molecular level devices or materials. For good chemical connectivity in the axial direction, carboxylates, ethynyls, and acetylsulfanyl groups were installed at the bridgeheads. Quinoxalines were attached in the transverse direction through a highly reactive alpha-diketone system located at the bridges.