In Situ Spectroelectrochemical Investigations of the Redox-Active Tris[4-(pyridin-4-yl)phenyl]amine Ligand and a Zn(2+) Coordination Framework

Carol Hua; Amgalanbaatar Baldansuren; Floriana Tuna; David Collison; Deanna M D'Alessandro

doi:10.1021/acs.inorgchem.6b00981

In Situ Spectroelectrochemical Investigations of the Redox-Active Tris[4-(pyridin-4-yl)phenyl]amine Ligand and a Zn(2+) Coordination Framework

Inorg Chem. 2016 Aug 1;55(15):7270-80. doi: 10.1021/acs.inorgchem.6b00981. Epub 2016 Jul 15.

Authors

Carol Hua¹, Amgalanbaatar Baldansuren², Floriana Tuna², David Collison², Deanna M D'Alessandro¹

Affiliations

¹ School of Chemistry, The University of Sydney , Sydney, New South Wales 2006, Australia.
² School of Chemistry and Photon Science Institute, The University of Manchester , Manchester M13 9PL, United Kingdom.

PMID: 27419690
DOI: 10.1021/acs.inorgchem.6b00981

Abstract

An investigation of the redox-active tris[4-(pyridin-4-yl)phenyl]amine (NPy3) ligand in the solution state and upon its incorporation into the solid-state metal-organic framework (MOF) [Zn(NPy3)(NO2)2·xMeOH·xDMF]n (MeOH = methanol and DMF = N,N-dimethylformamide) was conducted using in situ UV/vis/near-IR, electron paramagentic resonance (EPR), and fluorescence spectroelectrochemical experiments. Through this multifaceted approach, the properties of the ligand and framework were elucidated and quantified as a function of the redox state of the triarylamine core, which can undergo a one-electron oxidation to its radical cation. The use of pulsed EPR experiments revealed that the radical generated was highly delocalized throughout the entire ligand backbone. This combination of techniques provides comprehensive insight into electronic delocalization in a framework system and demonstrates the utility of in situ spectroelectrochemical methods in assessing electroactive MOFs.