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 MP-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 p-type semiconducting properties with an exceptionally high range of electrical conductivity. Notably, the differences in the 3d 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+ (3d9) 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+ (3d10) 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. 
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                            Bimetallic Two‐Dimensional Metal‐Organic Frameworks for Chemiresistive Detection of Carbon Monoxide
                        
                    
    
            This paper describes the demonstration of a series of heterobimetallic, isoreticular 2D conductive metal–organic frameworks (MOFs) with metallophthalocyanine (MPc, M=Co and Ni) units interconnected by Cu nodes towards low-power chemiresistive sensing of ppm-levels of carbon monoxide (CO). Devices achieve sub-part-per-million (ppm) limits of detection (LOD) of 0.53 ppm toward CO at low driving voltages of 0.1 V. MPc-based Cu-linked MOFs can continuously detect CO at 50 ppm, the permissible exposure limit required by Occupational Health and Safety Assessment Series, for multiple exposures and realize CO detection in air and humid environment. Diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS), density functional theory (DFT) calculations, and comparison experiments suggest the contribution of Cu nodes for CO binding and the essential role of MPc units in tuning and amplifying the sensing response. 
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                            - PAR ID:
- 10304091
- Date Published:
- Journal Name:
- Angewandte Chemie International Edition
- ISSN:
- 1433-7851
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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