Details

Autor(en) / Beteiligte

• Fürpaß, Katharina M.
• Peschel, Lydia M.
• Schachner, Jörg A.
• Borisov, Sergey M.
• Krenn, Heinz
• Belaj, Ferdinand
• Mösch‐Zanetti, Nadia C.

Titel

Vapochromism and Magnetochemical Switching of a Nickel(II) Paddlewheel Complex by Reversible NH3 Uptake and Release

Ist Teil von

• Angewandte Chemie (International ed.), 2021-06, Vol.60 (24), p.13401-13404

Auflage

International ed. in English

Ort / Verlag

Weinheim: Wiley Subscription Services, Inc

Erscheinungsjahr

2021

Link zum Volltext

Quelle

Alma/SFX Local Collection

Beschreibungen/Notizen

• Reaction of [NiCl2(PnH)4] (1) (PnH=6‐tert‐butyl‐pyridazine‐3‐thione) with NiCl2 affords the binuclear paddlewheel (PW) complex [Ni2(Pn)4] (2). Diamagnetic complex 2 is the first example of a PW complex capable of reversibly binding and releasing NH3. The NH3 ligand in [Ni2(Pn)4(NH3)] (2⋅NH3) enforces major spectroscopic and magnetic susceptibility changes, thus displaying vapochromic properties (λmax(2)=532 nm, λmax(2⋅NH3)=518 nm) and magnetochemical switching (2: S=0; 2⋅NH3: S=1). Upon repeated adsorption/desorption cycles of NH3 the PW core remains intact. Compound 2 can be embedded into thin polyurethane films (2P) under retention of its sensing abilities. Therefore, 2 qualifies as reversible optical probe for ammonia. The magnetochemical switching of 2 and 2⋅NH3 was studied in detail by SQUID measurements showing that in 2⋅NH3, solely the Ni atom coordinated the NH3 molecule is responsible for the paramagnetic behavior. The Ni2 paddlewheel complex can reversibly bind ammonia. This triggers spin‐state switching from dia‐ to paramagnetic and a change of color. Coordination of NH3 is fully reversible in solution, in solid state as well as encapsulated in a polyurethane foil.