Crystal Engineering of Coordination Networks Using Multi-interactive Ligands

Multi-interactive Coordination Network Featuring a Ligand with Topologically Isolated p Orbitals

“…3−5 Network ligands that are capable of participating in a greater variety of secondary interactions are of particular interest because they could stabilize metastable structures and provide synthetic access to a larger number of kinetic intermediates. 6 Therefore, considering the steric and electronic factors together, we previously reported a 2,5,8-tris(4′-pyridyl)-1,3,4,6,7,9-hexaazaphenalene (4-TPHAP) ligand (Figure 1a), which has topologically isolated p orbitals on an interactive HAP skeleton. Because of its multi-interactive nature, 4-TPHAP readily formed a variety of coordination networks, either by rapid crystallization of metastable kinetic structures 6,7 or through the use of different additives during the synthesis.…”

“…The shape and size of the pore surroundings as well as the overall flexibility of the network structure dictate the steric effects . On the contrary, the electronic effects are derived primarily from frontier orbitals of the network components and directly influence the redox and electrostatic potentials of the pore surface. − Network ligands that are capable of participating in a greater variety of secondary interactions are of particular interest because they could stabilize metastable structures and provide synthetic access to a larger number of kinetic intermediates . Therefore, considering the steric and electronic factors together, we previously reported a 2,5,8-tris­(4′-pyridyl)-1,3,4,6,7,9-hexaazaphenalene (4-TPHAP) ligand (Figure a), which has topologically isolated p orbitals on an interactive HAP skeleton.…”

“…Therefore, considering the steric and electronic factors together, we previously reported a 2,5,8-tris­(4′-pyridyl)-1,3,4,6,7,9-hexaazaphenalene (4-TPHAP) ligand (Figure a), which has topologically isolated p orbitals on an interactive HAP skeleton. Because of its multi-interactive nature, 4-TPHAP readily formed a variety of coordination networks, either by rapid crystallization of metastable kinetic structures , or through the use of different additives during the synthesis . In this study, a lower-symmetry derivative of the HAP ligand containing three 3-pyridyl groups (3-TPHAP) was developed (Figure ).…”

Selective Formation of Conductive Network by Radical-Induced Oxidation

“…A few redox-active ligands have been synthesized, using mostly TCNQ, TTF, pyrene, or naphthalene diimide skeletons . We prepared various coordination networks based on tripyridyl hexaazaphenalene (TPHAP), which was designed to show the importance of multi-interactivity of the ligand for kinetic network formation . Because TPHAP is not redox-active, we designed another tripyridyl ligand, 2,5,8-tri­(4-pyridyl)­1,3-diazaphenalene (TPDAP or H + 1 – ) to introduce redox activity while keeping the same molecular shape as TPHAP.…”