Tuning the Structure–PropertyRelationshipsof Metallophthalocyanine-Based Two-Dimensional Conductive Metal–OrganicFrameworks with Different Metal Linkages

Metallophthalocyanine (MPc)-linked conductive two-dimensional (2D) metal–organic frameworks (MOFs) hold tremendous promise as modular 2D materials in sensing, catalysis, and energy-related applications due to their combinatory bimetallic system from the MPc core and bridging metal nodes, endowing them with high electrical conductivity and multifunctionality. Despite significant advances, there is a gap in fundamental understanding regarding the periodic effects of metal nodes on the structural properties of MPc-linked 2D MOFs. Herein, we report a series of highly crystalline MOFs wherein copper phthalocyanine (CuPc) is linked with Ni, Cu, and Zn nodes (CuPc-O-M, M: Ni, Cu, Zn). The prepared CuPc-O-M MOFs exhibit <i>p</i>-type semiconducting properties with an exceptionally high range of electrical conductivity. Notably, the differences in the 3<i>d</i> orbital configurations of the Ni, Cu, and Zn nodes in CuPc-O-M MOFs lead to perturbations of the interlayer stacking patterns of the 2D framework materials, which ultimately affect material properties, such as semiconducting band gaps and charge transport within the framework. The Cu²⁺ (3<i>d</i>⁹) metal node within the eclipsed interlayer stacking of CuPc-O-Cu MOF demonstrates excellent charge transport, which results in the smallest band gap of 1.14 eV and the highest electrical conductivity of 9.3 S m^–1, while the Zn²⁺ (3<i>d</i>¹⁰) metal node within CuPc-O-Zn results in a slightly inclined interlayer stacking, leading to the largest band gap of 1.27 eV and the lowest electrical conductivity of 2.9 S m^–1. These findings form an important foundation in the strategic molecular design of this class of materials for multifaceted functionality that builds upon the electronic properties of these materials.