By substituting the bidentate linker with the tridentate tppa, we initiated the formation of a three-dimensional (3D) structural framework, which had not been achievable with the previously used bidentate linkers. The reaction proceeded in a similar manner to our previous syntheses, yielding a Cu6 cluster node analogous to the previously characterized Cu6-bpd CAM. The core architecture of the Cu6 cluster node remained consistent with our earlier findings (Fig. ); however, the attachment of six tppa linker molecules significantly altered its connectivity to the auxiliary ligands (Fig. ). Instead of being attached to the cluster node, the CF3COO⁻ units were present as counter anions. Due to the tridentate nature of the linker molecule, each Cu6 cluster node is now connected to twelve neighboring cluster nodes from different planes, forming a robust 3D network (Fig. ). The distance between adjacent cluster nodes was measured to be 17.402 Å, both along and across the axes.