title: In Situ Spectroelectrochemical Investigations of the Redox-Active Tris[4-(pyridin-4-yl)phenyl]amine Ligand and a Zn(2+) Coordination Framework.
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.
authors.affiliation: School of Chemistry, The University of Sydney , Sydney, New South Wales 2006, Australia.
authors.forename: Carol
authors.initials: C
authors.lastname: Hua
authors.affiliation: School of Chemistry and Photon Science Institute, The University of Manchester , Manchester M13 9PL, United Kingdom.
authors.forename: Amgalanbaatar
authors.initials: A
authors.lastname: Baldansuren
authors.affiliation: School of Chemistry and Photon Science Institute, The University of Manchester , Manchester M13 9PL, United Kingdom.
authors.forename: Floriana
authors.initials: F
authors.lastname: Tuna
authors.affiliation: School of Chemistry and Photon Science Institute, The University of Manchester , Manchester M13 9PL, United Kingdom.
authors.forename: David
authors.initials: D
authors.lastname: Collison
authors.affiliation: School of Chemistry, The University of Sydney , Sydney, New South Wales 2006, Australia.
authors.forename: Deanna M
authors.initials: DM
authors.lastname: D'Alessandro