The combination of two heteroaromatic boronic acids with pentaerythritol gave self-complementary tectons which were suitable for the generation of 2D and 3D molecular networks.

Homo- and hetero-leptic Zn and Cu complexes of dipyrrin type ligands bearing mono- and di-cyanophenyl groups when combined with silver cations lead to the formation of Ag(I)-C=C double bond interactions unprecedented in the crystalline phase.

An unprecedented mode of assembly of helical motives and Ag(I)  ions in the crystalline state is described. The combination of a Zn(II) helicate based on a 2,2'-bisdpm bearing peripheral benzonitrile moieties with AgX salts, leads to the formation of a tetranuclear core containing Ag-π interactions. Depending on the coordinating ability of the X(-) anion and the solvents used, the tetranuclear complex self-assembles into coordination polymers of varying dimensionality. From the sequence of coordination events (Ag-π or Ag-peripheral site), one may envisage two possible construction scenarios. However, the Ag-π as primary event seems reasonable owing to the rather weak binding propensity of the nitrile group and the chelating nature of the π-clefts.

A series of N-containing boronic esters have been prepared by combination of 3-pyridineboronic acid (3-pyba), 4-pyridineboronic acid (4-pyba), and 5-isoquinolineboronic acid (5-iqba) with ethanol, 1,2-ethanediol, and 1,3-propanediol. The resulting self-complementary tectons (SCTs) assembled further through N → B bond formation to give one tetranuclear macrocyclic and four one-dimensional polymeric boron complexes: [(3-py)B(OEt) 2 ] 4 (2), [(3-py)B(OCH 2 CH 2 O)] n (3), [(4-py)B(OEt) 2 ] n (4), [(5-iq)B(OCH 2 CH 2 O)] n (6), and [(5-iq)B(OCH 2 CH 2 CH 2 O)] n (7). In conjunction with the previously reported pentadecanuclear boroxine cage (1) and high-dimensional assemblies derived from pentaerythritol, [(4-py), it was shown that a single class of self-complementary boron-based tectons can give a varied series of finite and infinite supramolecular aggregates. A comparative structural characterization of boron complexes 2−4 and 6−7 by single-crystal X-ray diffraction analysis and quantum-chemical calculations revealed that the corresponding SCTs could have been organized in all cases in the form of tetrameric macrocycles, as it occurred for 2, indicating that intermolecular noncovalent interactions during crystallization probably play a significant role in the output of the assembly process and influence the formation of supramolecular isomers. This observation was supported by a comparison of the molecular geometries of a series of tetranuclear macrocyclic and related linear oligomeric boronic esters derived from 3-pyba, 4-pyba, and 5-iqba, whose structures have been optimized by quantum-chemical calculations at the (B3LYP/cc-pVDZ) level of theory. The calculated structure of [(3-py)B(OEt) 2 ] 4 was in good agreement with the structure obtained experimentally by single-crystal X-ray diffraction analysis. For the cyclo-tetramers derived from 3-pyba and 5-iqba, all common conformers known from calixarene chemistry have been analyzed (cone, 1,3-alternate, 1,2-alternate, and partial cone), showing that the boronic ester group has a significant influence on their relative stability.