Spectroelectrochemical studies of the redox active tris[4-(triazol-1-yl)phenyl]amine linker and redox state manipulation of Mn()/Cu() coordination frameworks

• Published in: Dalton transactions : an international journal of inorganic chemistry Vol. 48; no. 27; pp. 1122 - 1128
• Main Authors: Ngue, Chin-May, Liu, Yen-Hsiang, Wen, Yuh-Sheng, Leung, Man-Kit, Chiu, Ching-Wen, Lu, Kuang-Lieh
• Format: Journal Article
• Language: English
• Published: England Royal Society of Chemistry 21.07.2019
• Subjects: Absorption spectra; Coordination; Copper; Crystallography; Electrochromism; Manganese; Optical properties
• ISSN: 1477-9226; 1477-9234
• DOI: 10.1039/c9dt01729a

This work describes the successful incorporation of a redox active linker, tris(4-(1 H -1,2,4-triazol-1-yl)phenyl)amine (TTPA) into Mn( ii )/Cu( ii ) based coordination frameworks. Solution state in situ spectroelectrochemistry of EPR and UV/Vis/NIR of the TTPA ligand were measured to gain a deeper understanding of the charge delocalization of the triphenylamine backbone. The assignments of the absorption bands for the radical cations in UV/Vis/NIR spectroelectrochemistry were supported by DFT calculations. For Mn( ii )/Cu( ii ) based coordination frameworks, solid state electrochemical and in situ spectroelectrochemical methods were applied to elucidate the accessible redox states and the optical properties of the frameworks. The findings provide a basic comprehension of the interconversion of different redox states and how an electroactive framework can be potentially used in applications of electrochromic and optical devices. In situ spectroelectrochemical methods were conducted to investigate the redox active tris(4-(1 H -1,2,4-triazol-1-yl)phenyl)amine (TTPA) ligand and its incorporation into the solid state of Mn( ii ) and Cu( ii ) frameworks.