Light induced structural changes are the cornerstone of energy conversion reactions in photochemical energy storage. To date, our group has utilized x-ray photocrystallography to interrogate systems of importance with regards to energy storage, namely photohalogen elimination. Using this technique, we have turned our attention to a privileged compound in photolysis studies, potassium ferrioxalate, K3[Fe(C2O4)3]. Potassium ferrioxalate is a compound commonly used in laser actinometry with a quantum yield of 1 between 254 – 578 nm. In the solid state, this compound forms a coordination polymer of Fe(III) oxalate octahedra bridged by potassium counterions. To be discussed is the light-induced structural changes determined by x-ray crystallography of K3[Fe(C2O4)3] upon photolysis in the solid state at ~ 15 K. In addition to x-ray photocrystallography, potassium ferrioxalate is probed using a host of additional techniques, including Mössabuer, time-resolved EPR, transient-absorption methods and vibrational studies to establish relevance between the structure observed via x-ray photocrystallography and the suite of aforementioned spectroscopic techniques. These results are compared with prior solution studies to shed light on the light-induced decomposition of this iconic compound and provide clues as to what may be expected from photolysis of coordination polymers.

New look at an old compound: X-ray photocrystallography studies of potassium ferrioxalate upon photolysis in the solid state

2019 Fall National Meeting

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