期刊
JOURNAL OF PHYSICAL CHEMISTRY B
卷 123, 期 41, 页码 8814-8822出版社
AMER CHEMICAL SOC
DOI: 10.1021/acs.jpcb.9b07506
关键词
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资金
- SIUC
- Advanced Coal & Energy Research Center through an Energy Boost Seed Grant
- Department of Chemistry and Biochemistry, SIUC
- NSF [CHE0959568]
Metal-organic frameworks (MOFs) are an emerging class of compositions for electro- and photoelectrocatalytic energy conversion processes. Understanding and improving the charge-transport processes within these high surface area molecular redox catalyst assemblies are critical since the charge carrier conductivity is inherently limited in MOFs. Here, we examine a series of four chemically identical but structurally different hydrolytically robust Zr-IV-MOFs constructed from tetrakis(4-carboxyphenyl)porphyrinato iron(III), TCPP(Fe-III )to understand how their topological construction affects redox hopping conductivity. While a structural variation fixes center-to-center distances to define the hopping rate, we probe that altering the central metal spin-state can further tune the TCPP(FeIII/II) reorganization energy of the self-exchange process. Significant increase in the hopping rate was observed upon axial coordination of 1-methyl imidazole (MIM), which converts a weakly halide bound high-spin (HS) TCPP(FeIII/II) to the six-coordinated low-spin (LS) complex. Our electrochemical and resonance Raman data reveal that pore geometry that defines the Fe-Fe distance in these frameworks dictate the steric demand to accommodate two MIM-molecules, and thus, the population of LS vs HS species is a function of topology in the presence of an excess ligand.
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