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

Katharina M. Fürpaß; Lydia M. Peschel; Jörg A. Schachner; Sergey M. Borisov; Heinz Krenn; Ferdinand Belaj; Nadia C. Mösch-Zanetti

doi:10.1002/anie.202102149

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

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

^*Korrespondierende/r Autor/-in für diese Arbeit

Institut für Analytische Chemie und Lebensmittelchemie (6450)

Publikation: Beitrag in einer Fachzeitschrift › Artikel › Begutachtung

Abstract

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 (λ_max(2)=532 nm, λ_max(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 (2^P) 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.

Originalsprache	englisch
Seiten (von - bis)	13401-13404
Seitenumfang	4
Fachzeitschrift	Angewandte Chemie - International Edition
Jahrgang	60
Ausgabenummer	24
DOIs	https://doi.org/10.1002/anie.202102149
Publikationsstatus	Veröffentlicht - 7 Juni 2021

ASJC Scopus subject areas

Katalyse
Allgemeine Chemie

Zugriff auf Dokument

10.1002/anie.202102149

Andere Dateien und Links

Verknüpfung zur Publikation in Scopus

Dieses zitieren

@article{82ba44642d6e4b23b3ce02b613f030bb,

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

abstract = "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.",

keywords = "ammonia, nickel complexes, paddlewheel complexes, spin-state switching, vapochromism",

author = "F{\"u}rpa{\ss}, {Katharina M.} and Peschel, {Lydia M.} and Schachner, {J{\"o}rg A.} and Borisov, {Sergey M.} and Heinz Krenn and Ferdinand Belaj and M{\"o}sch-Zanetti, {Nadia C.}",

note = "Funding Information: The authors gratefully acknowledge Prof. C. Slugovc from the Graz University of Technology for providing a TGA measurement of complex ⋅NH and support from NAWI Graz. 2 3 Publisher Copyright: {\textcopyright} 2021 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH",

year = "2021",

month = jun,

day = "7",

doi = "10.1002/anie.202102149",

language = "English",

volume = "60",

pages = "13401--13404",

journal = "Angewandte Chemie - International Edition",

issn = "1433-7851",

publisher = "Wiley-VCH ",

number = "24",

}

TY - JOUR

T1 - Vapochromism and Magnetochemical Switching of a Nickel(II) Paddlewheel Complex by Reversible NH3 Uptake and Release

AU - Fürpaß, Katharina M.

AU - Peschel, Lydia M.

AU - Schachner, Jörg A.

AU - Borisov, Sergey M.

AU - Krenn, Heinz

AU - Belaj, Ferdinand

AU - Mösch-Zanetti, Nadia C.

N1 - Funding Information: The authors gratefully acknowledge Prof. C. Slugovc from the Graz University of Technology for providing a TGA measurement of complex ⋅NH and support from NAWI Graz. 2 3 Publisher Copyright: © 2021 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH

PY - 2021/6/7

Y1 - 2021/6/7

N2 - 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.

AB - 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.

KW - ammonia

KW - nickel complexes

KW - paddlewheel complexes

KW - spin-state switching

KW - vapochromism

UR - http://www.scopus.com/inward/record.url?scp=85105072203&partnerID=8YFLogxK

U2 - 10.1002/anie.202102149

DO - 10.1002/anie.202102149

M3 - Article

C2 - 33773004

AN - SCOPUS:85105072203

SN - 1433-7851

VL - 60

SP - 13401

EP - 13404

JO - Angewandte Chemie - International Edition

JF - Angewandte Chemie - International Edition

IS - 24

ER -