The physical and electronic properties of Metal–Organic Frameworks containing dipyridylthiazolo[5,4-d]thiazole

Felix J. Rizzuto; Shyam C. Pal; Eleanor R. Kearns; Carol Hua; Marcello B. Solomon; Patrick W. Doheny; Thomas B. Faust; Cameron J. Kepert; Madhab C. Das; Deanna M. D'Alessandro

doi:10.1039/D3CE00541K

The physical and electronic properties of Metal–Organic Frameworks containing dipyridylthiazolo[5,4-d]thiazole†

Felix J. Rizzuto,

^bc Shyam C. Pal,

^d Eleanor R. Kearns,^ab Carol Hua,

^e Marcello B. Solomon,

^ab Patrick W. Doheny,

^b Thomas B. Faust,

^b Cameron J. Kepert,

*^b Madhab C. Das

*^d and Deanna M. D'Alessandro

*^ab

Author affiliations

* Corresponding authors

^a School of Chemical and Biomolecular Engineering, Faculty of Engineering, The University of Sydney, New South Wales 2006, Australia
E-mail: deanna.dalessandro@sydney.edu.au

^b School of Chemistry, The University of Sydney, New South Wales 2006, Australia
E-mail: cameron.kepert@sydney.edu.au

^c School of Chemistry, The University of New South Wales, Australia

^d Department of Chemistry, Indian Institute of Technology Kharagpur, Kharagpur 721302, WB, India
E-mail: mcdas@chem.iitkgp.ac.in

^e School of Chemistry, The University of Melbourne, Parkville, Victoria 3010, Australia

Abstract

Five Metal–Organic Frameworks ({[M₂(tdc)₂(L)₂]·2DMF}, tdc = 2,5-thiophenedicarboxylate, M = Zn^II (1–Zn), Cu^II (1–Cu), Mn^II (1–Mn), {[Zn(oba)(L)]·DMF·H₂O} (2–Zn), oba = 4,4′-oxybisbenzoate, and {[Zn₂(bpdc)₂(L)₂]·L}, (3–Zn) bpdc = 4,4′-biphenyldicarboxylate) that incorporate the redox-active 2,5-dipyridylthiazolo[5,4-d]thiazole (DPTzTz) ligand (L) have been synthesised and their electronic properties elucidated. The ligand-based organic radicals were generated using in situ techniques and monitored using a suite of solid-state spectroelectrochemistry techniques. The absence of a near infra-red band (NIR), indicating through-space intervalence charge transfer (IVCT), in all analysed materials suggests that both the inter-ligand distance between cofacial TzTz moieties and the flexibility of the TzTz moiety affect the through-space IVCT.

CrystEngComm

The physical and electronic properties of Metal–Organic Frameworks containing dipyridylthiazolo[5,4-d]thiazole†

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The physical and electronic properties of Metal–Organic Frameworks containing dipyridylthiazolo[5,4-d]thiazole

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