Towards the Molecular Design of Spin-Crossover Complexes of 2,6-Bis(pyrazol-3-yl)pyridines

被引：32

作者：

Nikovskiy, Igor ^{[1
]}

Polezhaev, Alexander ^{[1
,2
]}

Novikov, Valentin ^{[1
,3
]}

Aleshin, Dmitry ^{[1
,4
]}

Pavlov, Alexander ^{[1
,3
]}

Saffiulina, Elnara ^{[1
,4
]}

Aysin, Rinat ^{[1
,3
]}

Dorovatovskii, Pavel ^{[5
]}

Nodaraki, Lydia ^{[6
]}

Tuna, Floriana ^{[6
]}

Nelyubina, Yulia ^{[1
,2
]}

机构：

[1] Russian Acad Sci, AN Nesmeyanov Inst Organoelement Cpds, Vavilova Str 28, Moscow 119991, Russia

[2] Bauman Moscow State Tech Univ, 2nd Baumanskaya Str 5, Moscow 105005, Russia

[3] Moscow Inst Phys & Technol, Inst Skiy Per 9, Dolgoprudnyi 141700, Moscow Region, Russia

[4] Mendeleev Univ Chem Technol Russia, Miusskaya Pl 9, Moscow 125047, Russia

[5] Natl Res Ctr Kurchatov Inst, Akad Kurchatova Pl 1, Moscow 123182, Russia

[6] Univ Manchester, Oxford Rd, Manchester M13 9PL, Lancs, England

来源：

CHEMISTRY-A EUROPEAN JOURNAL | 2020年 / 26卷 / 25期

基金：

俄罗斯科学基金会;

关键词：

2; 6-bis(pyrazol-3-yl)pyridine; iron(II) complexes; molecular design; NMR spectroscopy; spin-crossover; IRON(II) COMPLEXES; PARAMAGNETIC-SUSCEPTIBILITY; STATE; LIGANDS; 2,6-DI(PYRAZOL-1-YL)PYRIDINE; NMR; TRANSITION; DISTORTION; SERIES;

D O I：

10.1002/chem.202000047

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

The molecular design of spin-crossover complexes relies on controlling the spin state of a transition metal ion by proper chemical modifications of the ligands. Herein, the first N,N'-disubstituted 2,6-bis(pyrazol-3-yl)pyridines (3-bpp) are reported that, against the common wisdom, induce a spin-crossover in otherwise high-spin iron(II) complexes by increasing the steric demand of a bulky substituent, an ortho-functionalized phenyl group. As N,N'-disubstituted 3-bpp complexes have no pendant NH groups that make their spin state extremely sensitive to the environment, the proposed ligand design, which may be applicable to isomeric 1-bpp or other families of popular bi-, tri- and higher denticity ligands, opens the way for their molecular design as spin-crossover compounds for future breakthrough applications.

引用

页码：5629 / 5638

页数：10

共 77 条

[11] Surface-induced spin state locking of the [Fe(H2B(pz)2)2(bipy)] spin crossover complex [J].

Beniwal, S. ;

Zhang, X. ;

Mu, S. ;

Naim, A. ;

Rosa, P. ;

Chastanet, G. ;

Letard, J-F ;

Liu, J. ;

Sterbinsky, G. E. ;

Arena, D. A. ;

Dowben, P. A. ;

Enders, A. .

JOURNAL OF PHYSICS-CONDENSED MATTER, 2016, 28 (20)

[12] Towards catenanes using π-stacking interactions and their influence on the spin-state of a bis(2,2′:6′,2"-terpyridine)iron(II) domain [J].

Brauchli, Sven Y. ;

Constable, Edwin C. ;

Harris, Kate ;

Haeussinger, Daniel ;

Housecroft, Catherine E. ;

Roesel, Pirmin J. ;

Zampese, Jennifer A. .

DALTON TRANSACTIONS, 2010, 39 (44) :10739-10748

[13] PHI: A powerful new program for the analysis of anisotropic monomeric and exchange-coupled polynuclear d- and f-block complexes [J].

Chilton, Nicholas F. ;

Anderson, Russell P. ;

Turner, Lincoln D. ;

Soncini, Alessandro ;

Murray, Keith S. .

JOURNAL OF COMPUTATIONAL CHEMISTRY, 2013, 34 (13) :1164-1175

[14] Structural, thermal, and magnetic study of solvation processes in spin-crossover [Fe(bpp)2][Cr(L)(ox)2]2•H2O complexes [J].

Clemente-Leon, Miguel ;

Coronado, Eugenio ;

Gimenez-Lopez, M. Carmen ;

Romero, Francisco M. .

INORGANIC CHEMISTRY, 2007, 46 (26) :11266-11276

[15]

Constable EC, 1999, CHEM-EUR J, V5, P498, DOI 10.1002/(SICI)1521-3765(19990201)5:2<498::AID-CHEM498>3.3.CO

[16]

2-M

[17] Spin state behavior of iron(II)/dipyrazolylpyridine complexes. New insights from crystallographic and solution measurements [J].

Cook, Laurence J. Kershaw ;

Mohammed, Rufeida ;

Sherborne, Grant ;

Roberts, Thomas D. ;

Alvarez, Santiago ;

Halcrow, Malcolm A. .

COORDINATION CHEMISTRY REVIEWS, 2015, 289 :2-12

[18] A Unified Treatment of the Relationship Between Ligand Substituents and Spin State in a Family of Iron(II) Complexes [J].

Cook, Laurence J. Kershaw ;

Kulmaczewski, Rafal ;

Mohammed, Rufeida ;

Dudley, Stephen ;

Barrett, Simon A. ;

Little, Marc A. ;

Deeth, Robert J. ;

Halcrow, Malcolm A. .

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2016, 55 (13) :4327-4331

[19] Spin crossover complexes as building units of hydrogen-bonded nanoporous structures [J].

Coronado, Eugenio ;

Carmen Gimenez-Lopez, M. ;

Gimenez-Saiz, Carlos ;

Romero, Francisco M. .

CRYSTENGCOMM, 2009, 11 (10) :2198-2203

[20] Spin state switching in 2,6-bis(pyrazol-3-yl)pyridine (3-bpp) based Fe(II) complexes [J].

Craig, Gavin A. ;

Roubeau, Olivier ;

Aromi, Guillem .

COORDINATION CHEMISTRY REVIEWS, 2014, 269 :13-31

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