Coordination-induced spin crossover (CISCO) through axial bonding of substituted pyridines to nickel-porphyrins: sigma-donor versus pi-acceptor effects

Chemistry : a European Journal
Steffen ThiesRainer Herges

Abstract

Nickel-porphyrins, with their rigid quadratic planar coordination framework, provide an excellent model to study the coordination-induced spin crossover (CISCO) effect because bonding of one or two axial ligands to the metal center leads to a spin transition from S=0 to S=1. Herein, both equilibrium constants K(1S) and K(2), and for the first time also the corresponding thermodynamic parameters DeltaH(1S), DeltaH(2), DeltaS(1S), and DeltaS(2), are determined for the reaction of a nickel-porphyrin (Ni-tetrakis(pentafluorophenyl)porphyrin) with different 4-substituted pyridines by temperature-dependent NMR spectroscopy. The association constants K(1S) and K(2) are correlated with the basicity of the 4-substituted pyridines (R: OMe>H>CO(2)Et>NO(2)) whereas the DeltaH(1S) values exhibit a completely different order (OMe<H>CO(2)Et>NO(2)). 4-Nitropyridine exhibits the largest binding enthalpy, which, however, is overcompensated by a large negative binding entropy. We attribute the large association enthalpy of nitropyridine with porphyrin to the back donation of electrons from the Ni d(xz) and d(yz) orbitals into the pi orbitals of pyridine, and the negative association entropy to a decrease in vibrational and internal rotation entro...Continue Reading

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Citations

Dec 27, 2011·Acta Crystallographica. Section E, Structure Reports Online·Steffen ThiesRainer Herges
Sep 25, 2015·Inorganic Chemistry·Marcel DommaschkRainer Herges
Aug 25, 2015·The Journal of Organic Chemistry·M DommaschkR Herges
Nov 22, 2016·Scientific Reports·Mohammed NooriColin J Lambert
Apr 13, 2017·Chemistry : a European Journal·Cosima StählerAtsuhiro Osuka
May 24, 2017·Dalton Transactions : an International Journal of Inorganic Chemistry·Yoshifumi SasanoHiromitsu Maeda
Oct 23, 2014·Dalton Transactions : an International Journal of Inorganic Chemistry·M DommaschkR Herges
Sep 5, 2014·Chemical Communications : Chem Comm·Marcel DommaschkRainer Herges
Jun 24, 2016·Dalton Transactions : an International Journal of Inorganic Chemistry·Gernot HeitmannRainer Herges
Oct 24, 2012·Chemistry : a European Journal·Steffen ThiesRainer Herges
Sep 25, 2019·Chemistry : a European Journal·Atsumi YagiHiroshi Shinokubo
Mar 19, 2013·Beilstein Journal of Organic Chemistry·Philipp GütlichYann Garcia
May 17, 2012·Acta Crystallographica. Section E, Structure Reports Online·Steffen ThiesRainer Herges
Jan 5, 2018·Dalton Transactions : an International Journal of Inorganic Chemistry·Michaela KlaßFelix Tuczek
Jan 1, 2016·Chemical Science·Richard WichtMartin Bröring
Jul 14, 2018·Acta Crystallographica. Section E, Crystallographic Communications·Morten K PetersRainer Herges
Nov 27, 2019·Molecules : a Journal of Synthetic Chemistry and Natural Product Chemistry·Alex-Adrian Farcaș, Attila Bende
Jun 22, 2013·Chemistry : a European Journal·Azin HassanpourFélix Zamora
Mar 21, 2013·Angewandte Chemie·Christian WäckerlinNirmalya Ballav
Nov 28, 2013·Angewandte Chemie·Jens HasserodtFaycal Touti
Sep 22, 2020·Beilstein Journal of Organic Chemistry·Jannis LudwigRainer Herges
Aug 17, 2016·Chemistry : a European Journal·Marat M Khusniyarov
Dec 16, 2017·Dalton Transactions : an International Journal of Inorganic Chemistry·Mahbod MorshediNicholas G White
Jun 9, 2018·Sensors·Huynh Thien NgoGenki Yoshikawa
Nov 3, 2020·Beilstein Journal of Organic Chemistry·Jannis LudwigRainer Herges
Nov 19, 2020·Dalton Transactions : an International Journal of Inorganic Chemistry·Obaid Ali QamarHuaibo Ma
Feb 27, 2021·Journal of the American Chemical Society·Hannah KurzBirgit Weber
Jul 25, 2021·Molecules : a Journal of Synthetic Chemistry and Natural Product Chemistry·Alexander V ShokurovYulia G Gorbunova
Mar 10, 2012·The Journal of Organic Chemistry·Thore WendlerRainer Herges
Apr 29, 2015·Journal of the American Chemical Society·Marcel DommaschkRainer Herges
Feb 14, 2020·Journal of the American Chemical Society·Thuy-Ai D NguyenEric J Schelter
Oct 21, 2014·Chemical Research in Toxicology·Nina E WezynfeldTomasz Frączyk

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