Synchronic Transformations of Molecular States and Macroscopic Phases in Valence‐Tautomeric Complexes. Issue 5 (27th November 2012)

• Record Type: Journal Article
• Authors: Chang, Ho‐Chol; Kiriya, Daisuke
• Other Names: Murray Keith S. sponsoringEditor.; Oshio Hiroki sponsoringEditor.; Real Jose Antonio sponsoringEditor.
• Is Part Of: European journal of inorganic chemistry. Issue 5/6(2013)
• Page Start: 642
• Page End: 652
• Publication Date: 2012-11-27
• Subjects: Phase transitions -- Valence isomerization -- Tautomerism -- Quinones -- Synchronization -- Electron transfer -- Melting; Chemistry, Inorganic -- Periodicals; Organometallic chemistry -- Periodicals; Bioinorganic chemistry -- Periodicals; Solid state chemistry -- Periodicals; 546
• DOI: 10.1002/ejic.201201087
• Languages: English
• ISSNs: 1434-1948

Abstract

Abstract: Valence tautomerism (VT) refers to equilibria between two or more different tautomers differing in their charge distributions. This contribution shows how molecular VT occurring in metal–dioxolene complexes (metal = cobalt, manganese) functionalized with long alkyl chains can be coupled with several types of macroscopic phase transformations, such as solid‐to‐solid and solid‐to‐liquid transitions and the double‐melting phenomenon. Observations of simultaneous transformation of molecular and macroscopic states have led to the concept of synchronic bistability. The central focus in this microreview is on molecular design, thermodynamic basis, and kinetic control of the synchronic bistability. It is demonstrated that a key factor in designing a synchronic transformation is to build up strong interdependent correlations between molecules and their assembled states. Abstract : This microreview summarizes molecular strategy directed towards synchronous transformations of molecular states and macroscopic phases. The coexistence of valence‐tautomeric Co– or Mn–dioxolene cores with structurally flexible long alkyl tails leads to rich molecular bistability that synchronously occurs with a macroscopic phase transformation, such as the solid‐to‐liquid phase transition.