This thesis details one supramolecular assembly approach to solid state construction whereby rigid, trigonal phenylacetylene nitrile ligands crystallized with trigonally coordinating silver trifluoromethanesulfonate predictably yields a porous, crystalline channels structure. Materials based on this combination of symmetries are shown to have the following properties: (1) The channel dimension can be controlled by ligand size variation. Hexagonal void spaces up to 27.3 A x 29.8 A (for 1,3,5-tris(4-(4-ethynylbenzonitrile)benzoethynyl)benzene $\cdot$AgOTf) are constructed by insertion of spacer groups in the ligand backbone. (2) The pore shape can be controlled by ligand modification. Substitution of pendant groups on the trigonally shaped backbone allows control of the cavity environment by introduction of such moieties as alcohols, alkenes, ethers, and chiral substituents without destruction of the hexagonal structure. (3) The cavities will function as a host to a variety of guest molecules. One examined channel dimension (for 1,3,5-tris(4-ethynylbenzonitrile)benzene$\cdot$AgOTf) allows for the after crystallization enclathration of various aliphatic and aromatic molecules (up to 1:3.5 host:guest). (4) The channels can be completely voided of guests without destruction of the host network. Rapid thermal evacuation produces an 'apohost' material retaining the original hexagonal channel motif. The apohost material selectively enclathrates only aromatic (1:3.5 host:guest) and no aliphatic molecules. (5) Solid state reaction between the host network with pendant alcohol and guest silyl triflates occur. A cross-linked host can be formed by the reaction with di-t-butylsilyl bis(trifluoromethanesulfonate) which does not destroy the channels.