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Abstract: : Metalloporphyrins have been shown to bind axial ligands in a variety of environments including the vacuum/solid and solution/solid interfaces. Understanding the dynamics of such interactions is a desideratum for the design and implementation of next generation molecular devices which draw inspiration from biological systems to accomplish diverse tasks such as molecular sensing, electron transport, and catalysis to name a few. In this article, we review the current literature of axial ligand coordination to surface-supported porphyrin receptors. We will focus on the coordination process as monitored by scanning tunneling microscopy (STM) that can yield qualitative and quantitative information on the dynamics and binding affinity at the single molecule level. In particular, we will address the role of the substrate and intermolecular interactions in influencing cooperative effects (positive or negative) in the binding affinity of adjacent molecules based on experimental evidence and theoretical calculations.
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This content will become publicly available on May 22, 2026
Exploring the Influence of Chalcogens on Metalloporphyrins: A DFT Study
Metalloporphyrins and porphyrins (MPs) have garnered increasing attention as potential candidates for molecular-based electronic devices and single-atom catalysis. Recent studies have found that electronic structure calculations are important factors in controlling the performance of MPs as building blocks for single-molecule devices. Our study investigates metalloporphyrins with central 3d-metals from Sc to Cu and chalcogen containing anchoring groups such as -SH, -SeH, and -TeH substituted at the meso-position of the porphyrin rings. We carried out Density Function Theory (DFT)-based calculations to determine the ground state geometry, spin multiplicity, spatial distribution of the molecular orbitals, and electronic structure descriptors to gain insights into the reactivity trends and possible impact on factors influencing electron transport properties. The results suggest that the central metal shapes the spin multiplicity, while variations between sulfur, selenium, and tellurium play a role in charge distribution. This study provides insights into how the selection of the central metal and control of spin channels influence the electronic structure and reactivity of metalloporphyrin molecules. The knowledge provided here can play a role in the design of porphyrin-based molecular materials for diverse applications in molecular junctions, catalysis, photovoltaics, and sensing.
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- Award ID(s):
- 2055668
- PAR ID:
- 10599303
- Publisher / Repository:
- MDPI
- Date Published:
- Journal Name:
- Molecules
- Volume:
- 30
- Issue:
- 11
- ISSN:
- 1420-3049
- Page Range / eLocation ID:
- 2254
- Subject(s) / Keyword(s):
- Porphyrins density functional theory quantum spin
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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