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.
Original language | English |
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Pages (from-to) | 7270-7280 |
Number of pages | 11 |
Journal | Inorganic Chemistry |
Volume | 55 |
Issue number | 15 |
DOIs | |
Publication status | Published - 15 Jul 2016 |
Keywords
- Journal Article
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CCDC 1473613: Experimental Crystal Structure Determination
Hua, C. (Contributor), Baldansuren, A. (Contributor), Tuna, F. (Contributor), Collison, D. (Contributor) & D'Alessandro, D. M. (Contributor), Cambridge Crystallographic Data Centre, 1 Jan 2016
DOI: 10.5517/ccdc.csd.cc1lgdxc, http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.5517/ccdc.csd.cc1lgdxc&sid=DataCite
Dataset
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CCDC 1473614: Experimental Crystal Structure Determination
Hua, C. (Contributor), Baldansuren, A. (Contributor), Tuna, F. (Contributor), Collison, D. (Contributor) & D'Alessandro, D. M. (Contributor), Cambridge Crystallographic Data Centre, 1 Jan 2016
DOI: 10.5517/ccdc.csd.cc1lgdyd, http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.5517/ccdc.csd.cc1lgdyd&sid=DataCite
Dataset
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CCDC 1473615: Experimental Crystal Structure Determination
Hua, C. (Contributor), Baldansuren, A. (Contributor), Tuna, F. (Contributor), Collison, D. (Contributor) & D'Alessandro, D. M. (Contributor), Cambridge Crystallographic Data Centre, 1 Jan 2016
DOI: 10.5517/ccdc.csd.cc1lgdzf, http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.5517/ccdc.csd.cc1lgdzf&sid=DataCite
Dataset