Molecular vessels having defined dimensions and stability, resorcin[4]arenes or calix[4]arenes, have been used for the construction of various supramolecular systems such as container molecules and self-assembling molecular capsules, which are prototypes having a defined inner cavity with substantial activation energy barriers for complexationdecomplexation process of their complementary guests. When complexed, these prototypes showed many unprecedented isomers called carceroisomers, twistomers, social isomers, constellation isomers, and orientational isomers. These isomers could work as molecular switches when they could be aligned on a matrix and their equilibrium could be controlled by an energy efficient method. Aligning container molecules on gold surface was successful by self-assembling of a carceplex having thia groups on feet of a hemispheric part. Especially the net-work of container molecules would also be an efficient method for these purposes. Self-assembled net works of container molecules will become unique materials due to uniform dimensions, high stablilities, and dense properties. For the purpose of 2D square grid network of container molecules as illustrated in Figure 1, 4-directionally functionalized hemicarcerands 4 and 5 were designed and synthesized by the shell closing reactions between tetrol 1 and bridging reagents 2 or 3 as shown in Scheme 1. The bridging reagent 3,5-bis(bromomethyl)benzonitrile 2 was prepared from 5-iodo-m-xylene through two step reactions, cyanation and then NBS bromination. The bridging reagent 3,5-bis(bromomethyl)-1-bromobenzene 3 was prepared from 5-bromo-m-xylene by NBS bromination. The shell closing reactions, 8-bonds formation in one step, in a mixture of tetrol 1, bridging reagents 2 or 3, and Cs2CO3 in NMP at 25-60 C gave hemicarcerands 4 and 5 in moderate yields, 11 and 7%, respectively. The network of container molecules will be useful only if the orientation of complexed guest can be confirmed and manipulable. For hemicarceplexes to be isolable enough at ambient temperature, the sizes and shapes of potential guests must be complementary enough to the host's portals and inner cavities so that the constrictive and intrinsic binding interactions work together properly. Hemicarceplexes, guest@4, were synthesized by heating a mixture of free host 4 and an excess amount of guest (> 1000 fold), cooling reaction mixture, and then flooding with MeOH. The precipitated hemicarceplex was filtered and dried in vacuo. The H NMR spectral changes of guest