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The 21st IUPAC International Conference on Physical Organic Chemistry (ICPOC 21) was organised by the RSC Physical Organic Chemistry Group. ICPOC is the leading international conference on Physical Organic Chemistry and Chemical Reactivity. The conference consisted of plenary, invited and contributed lectures, as well as poster sessions. ICPOC-21 brought together the organic chemistry, catalysis and physical chemistry communities from academia and industry to discuss the current state of the art, the development and future of physical organic chemistry. Although traditionally considered as the study of mechanism, reactivity, structure and binding in organic systems, especially leading to the quantitative, molecular level understanding of their properties, physical organic chemistry nowadays also encompasses a wider range of contexts (such as biology and materials) than ever before.