1 – Optical Spectra and Electronic Structure of Porphyrins and Related Rings

Several small molecule species formally known primarily as toxic gases have, over the past 20 years, been shown to be endogenously generated signaling molecules. The biological signaling associated with the small molecules NO, CO, H₂S (and the nonendogenously generated O₂), and their derived species have become a topic of extreme interest. It has become increasingly clear that these small molecule signaling agents form an integrated signaling web that affects/regulates numerous physiological processes. The chemical interactions between these species and each other or biological targets is an important factor in their roles as signaling agents. Thus, a fundamental understanding of the chemistry of these molecules is essential to understanding their biological/physiological utility. This review focuses on this chemistry and attempts to establish the chemical basis for their signaling functions.

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Small Molecule Signaling Agents: The Integrated Chemistry and Biochemistry of Nitrogen Oxides, Oxides of Carbon, Dioxygen, Hydrogen Sulfide, and Their Derived Species

Solid-State Structures of Metalloporphyrin NOx Compounds

The development of chemical systems with switchable molecular spins could lead to the architecture of materials with controllable magnetic or spintronic properties. Here, we present conclusive evidence that the spin of an organometallic molecule coupled to a ferromagnetic substrate can be switched between magnetic off and on states by a chemical stimulus. This is achieved by nitric oxide (NO) functioning as an axial ligand of cobalt(II)tetraphenylporphyrin (CoTPP) ferromagnetically coupled to nickel thin-film (Ni(001)). On NO addition, the coordination sphere of Co(2+) is modified and a NO-CoTPP nitrosyl complex is formed, which corresponds to an off state of the Co spin. Thermal dissociation of NO from the nitrosyl complex restores the on state of the Co spin. The NO-induced reversible off-on switching of surface-adsorbed molecular spins observed here is attributed to a spin trans effect.

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Controlling spins in adsorbed molecules by a chemical switch

Nitric oxide complexes of metalloporphyrins : an overview of some mechanistic studies

Spectroscopic studies for tetraphenylporphyrincobalt(II) complexes of carbon monoxide, nitrogen oxide, molecular oxygen, methylisonitrile, and trimethyl phosphite, and a bonding model for complexes of carbon monoxide, nitrogen oxide, and molecular oxygen with cobalt(II) and iron(II) porphrins

Spectroscopic studies for tetraphenylporphyrincobalt(ii) complexes of co, no, o2, ch3nc, and (ch3o)3p, and a bonding model for complexes of co, no, and o2 with cobalt(ii) and iron(ii) porphyrins

J. V. Minkiewicz

Papers

Spectroscopic studies for tetraphenylporphyrincobalt(II) complexes of carbon monoxide, nitrogen oxide, molecular oxygen, methylisonitrile, and trimethyl phosphite, and a bonding model for complexes of carbon monoxide, nitrogen oxide, and molecular oxygen with cobalt(II) and iron(II) porphrins

Spectroscopic studies for tetraphenylporphyrincobalt(ii) complexes of co, no, o2, ch3nc, and (ch3o)3p, and a bonding model for complexes of co, no, and o2 with cobalt(ii) and iron(ii) porphyrins