Redox Chemistry Mediated Control of Morphology and Properties in Electrically Conductive Coordination Polymers: Opportunities and Challenges

Abstract

Coordination polymers (CPs) and metal–organic frameworks (MOFs) have attracted significant research interest in the past several decades due to their reticular structures and modularity. However, realizing electrically conductive CPs or MOFs with comparable properties to classic conducting organic polymers has only been a recent development. This emerging class of materials has found wide application in many fields due to the combined features of structural rigidity, chemical tunability, porosity, and charge transport. Alongside many studies revealing myriad design approaches to access these materials, the role that redox chemistry plays in both material synthesis and modulation of electronic properties has been an emerging theme. This Perspective provides a brief overview of select examples where redox chemistry mediates the control of morphology and properties in electrically conductive CPs/MOFs. The challenges and limitations in this area are also discussed. Particular challenges include the characterization of redox states in these materials and measuring and understanding highly correlated electronic properties and other unusual physical phenomena that may be important for potential applications.

Rational Construction of Two-Dimensional Conjugated Metal–Organic Frameworks (2D c-MOFs) for Electronics and Beyond

“…Upon reevaluation, the fundamental uniqueness of 2D c-MOFs lies in their planar MX 4 d-π conjugated Secondary Building Units (SBUs). The synthesis of 2D c-MOFs involves employing redox-driven coordination polymerization reactions to link organic conjugated ligands containing adjacent dihydroxy, diamino, or dithiol functionalities with metal ions, forming 2D d-π conjugated planes. , These planes are subsequently assembled into three-dimensional bulk materials through interlayer π–π interactions. As a result, 2D c-MOFs possess intrinsic unpaired electrons located on the organic conjugated parts, realized by the redox coordination chemistry without additional doping.…”