Synthesis and Magnetism of Neutral, Linear Metallocene Complexes of Terbium(II) and Dysprosium(II)

Journal of the American Chemical Society
Colin A GouldJeffrey R Long

Abstract

The divalent metallocene complexes Ln(CpiPr5)2 (Ln = Tb, Dy) were synthesized through the KC8 reduction of Ln(CpiPr5)2I intermediates and represent the first examples of neutral, linear metallocenes for these elements. X-ray diffraction analysis, density functional theory calculations, and magnetic susceptibility measurements indicate a 4f n 5d1 electron configuration with strong s/d mixing that supports the linear coordination geometry. A comparison of the magnetic relaxation behavior of the two divalent metallocenes relative to salts of their trivalent counterparts, [Ln(CpiPr5)2][B(C6F5)4], reveals that lanthanide reduction has opposing effects for dysprosium and terbium, with magnetic relaxation times increasing from TbIII to TbII and decreasing from DyIII to DyII. The impact of this effect is most notably evident for Tb(CpiPr5)2, which displays an effective thermal barrier to magnetic relaxation of 1205 cm-1 and a 100-s blocking temperature of 52 K, the highest values yet observed for any nondysprosium single-molecule magnet.

References

Apr 24, 2003·Journal of the American Chemical Society·William J EvansJoseph W Ziller
Jul 17, 2003·Journal of the American Chemical Society·Naoto IshikawaYoukoh Kaizu
Feb 24, 2006·Chemical Communications : Chem Comm·Florian JaroschikLouis Ricard
May 15, 2010·Journal of the American Chemical Society·Jeffrey D RinehartJeffrey R Long
Oct 27, 2011·Physical Chemistry Chemical Physics : PCCP·Liviu Ungur, Liviu F Chibotaru
Oct 29, 2011·Journal of the American Chemical Society·Matthew JeleticMuralee Murugesu
May 16, 2012·Journal of the American Chemical Society·Matthew R MacDonaldWilliam J Evans
Apr 5, 2013·Chemical Reviews·Daniel N WoodruffRichard A Layfield
May 24, 2013·Journal of the American Chemical Society·Matthew R MacDonaldWilliam J Evans
Jul 25, 2013·Nature Chemistry·Robin J BlaggRichard E P Winpenny
Aug 24, 2013·Journal of the American Chemical Society·Fatemah HabibMuralee Murugesu
Oct 8, 2013·Nature Communications·Nicholas F ChiltonAlessandro Soncini
Nov 6, 2013·Journal of the American Chemical Society·Katie R Meihaus, Jeffrey R Long
Nov 16, 2013·Dalton Transactions : an International Journal of Inorganic Chemistry·Grégory Nocton, Louis Ricard
Nov 11, 2014·Chemical Communications : Chem Comm·Nicholas F ChiltonRichard E P Winpenny
Jul 15, 2015·Chemical Society Reviews·Stephen T Liddle, Joris van Slageren
Feb 18, 2016·Journal of the American Chemical Society·Yan-Cong ChenMing-Liang Tong
Apr 8, 2016·Journal of the American Chemical Society·Jiang LiuMing-Liang Tong
Jan 6, 2017·Dalton Transactions : an International Journal of Inorganic Chemistry·Alexander F R Kilpatrick, F Geoffrey N Cloke
Jun 7, 2017·Angewandte Chemie·Fu-Sheng GuoRichard A Layfield
Aug 25, 2017·Nature·Conrad A P GoodwinDavid P Mills
Mar 2, 2018·Chemical Society Reviews·Jun-Liang LiuMing-Liang Tong
Mar 31, 2018·Nature Communications·Mikkel A SørensenJesper Bendix
Aug 1, 2018·Chemical Communications : Chem Comm·Conrad A P GoodwinDavid P Mills
Aug 10, 2018·Accounts of Chemical Research·Benjamin M DayRichard A Layfield
Aug 1, 2016·Chemical Science·Sandeep K GuptaRamaswamy Murugavel

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Citations

Nov 12, 2019·Dalton Transactions : an International Journal of Inorganic Chemistry·Thaige P GompaHenry S La Pierre
Nov 9, 2019·Dalton Transactions : an International Journal of Inorganic Chemistry·Moritz Malischewski, Konrad Seppelt
Feb 19, 2020·Dalton Transactions : an International Journal of Inorganic Chemistry·Xingrui GaoPeng Chen
Mar 12, 2020·Dalton Transactions : an International Journal of Inorganic Chemistry·Si-Guo WuMing-Liang Tong
Feb 25, 2020·Angewandte Chemie·Peng-Bo JinYan-Zhen Zheng
Apr 23, 2020·Chemical Communications : Chem Comm·Peter EvansDavid P Mills
Jun 11, 2020·Dalton Transactions : an International Journal of Inorganic Chemistry·Thaige P GompaHenry S La Pierre
Aug 5, 2020·Dalton Transactions : an International Journal of Inorganic Chemistry·Raphael C A VazCynthia L M Pereira
Aug 20, 2020·Dalton Transactions : an International Journal of Inorganic Chemistry·Michael A BoreenJohn Arnold
Sep 10, 2020·Chemical Communications : Chem Comm·Angelos B CanajMark Murrie
Sep 24, 2020·Physical Chemistry Chemical Physics : PCCP·Robert L SmithKyungwha Park
Jul 16, 2020·Molecules : a Journal of Synthetic Chemistry and Natural Product Chemistry·Diamantoula ManiakiSpyros P Perlepes
Nov 7, 2019·Chemical Communications : Chem Comm·Vasilii DubrovinStanislav Avdoshenko
May 18, 2020·The Journal of Chemical Physics·Sree Ganesh BalasubramaniJason M Yu
Feb 29, 2020·Chemical Science·Hannah M NicholasDavid P Mills
Oct 7, 2020·Dalton Transactions : an International Journal of Inorganic Chemistry·Si-Guo WuMing-Liang Tong
Oct 7, 2020·Chemical Communications : Chem Comm·Aditya BorahRamaswamy Murugavel
Oct 9, 2020·Dalton Transactions : an International Journal of Inorganic Chemistry·Conrad A P Goodwin
Oct 22, 2020·Chemical Communications : Chem Comm·Min FengMing-Liang Tong
Nov 21, 2020·Dalton Transactions : an International Journal of Inorganic Chemistry·Juan SunLicun Li
Sep 24, 2020·Chemistry : a European Journal·Moya A Hay, Colette Boskovic
Oct 15, 2020·Angewandte Chemie·Luana C de CamargoRoberta Sessoli
May 12, 2021·Dalton Transactions : an International Journal of Inorganic Chemistry·Yang LiuMing-Liang Tong
Jun 5, 2021·Chemical Communications : Chem Comm·Mian HeRichard A Layfield
May 13, 2021·Chemistry : a European Journal·Jochen JungDietmar Stalke
Jul 16, 2021·The Journal of Physical Chemistry. a·Caleb HuizengaCaroline Chick Jarrold
Aug 17, 2021·Dalton Transactions : an International Journal of Inorganic Chemistry·Xiang LiFeng Gao
Nov 19, 2019·Inorganic Chemistry·Jason M Yu, Filipp Furche
Nov 22, 2019·Journal of the American Chemical Society·Peter EvansDavid P Mills
Jul 2, 2021·Chemistry : a European Journal·Maxime TricoireGrégory Nocton
Jan 20, 2021·The Journal of Physical Chemistry. a·Jarrett L MasonCaroline Chick Jarrold

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