Diamagnetic Carrier-Doping-Induced Continuous Electronic and Magnetic Crossover in One-Dimensional Coordination Polymers

Yongbing Shen; Mengxing Cui; Guanping Li; Olaf Stefanczyk; Nobuto Funakoshi; Tomu Otake; Shinya Takaishi; Masahiro Yamashita; Shin-Ichi Ohkoshi

doi:10.1021/jacs.4c14013

Diamagnetic Carrier-Doping-Induced Continuous Electronic and Magnetic Crossover in One-Dimensional Coordination Polymers

J Am Chem Soc. 2024 Dec 12. doi: 10.1021/jacs.4c14013. Online ahead of print.

Authors

Yongbing Shen^{1

2}, Mengxing Cui³, Guanping Li^{1

4}, Olaf Stefanczyk¹, Nobuto Funakoshi², Tomu Otake¹, Shinya Takaishi², Masahiro Yamashita^{3

2}, Shin-Ichi Ohkoshi^{1

5}

Affiliations

¹ Department of Chemistry, School of Science, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-0033, Japan.
² Department of Chemistry, Graduate School of Science, Tohoku University, 6-3 Aramaki-Aza-Aoba, Aoba-Ku, Sendai 980-8578, Japan.
³ School of Chemical Science and Engineering, Tongji University, Siping Road 1239, Shanghai 200092, P. R. China.
⁴ Department of Chemistry, The University of Manchester, Manchester M13 9PL, U.K.
⁵ DYNACOM (Dynamical Control of Materials)-IRL2015, CNRS, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-0033, Japan.

PMID: 39668390
DOI: 10.1021/jacs.4c14013

Abstract

The potential to introduce tunable electrical conductivity and molecular magnetism through carrier doping in metal-organic coordination polymers is particularly promising for nanoelectronics applications. Precise control of the doping level is essential for determining the electronic and magnetic properties. In this study, we present a series of one-dimensional coordination polymers, {(HNEt₃)_0.5[Cu_xCo_(1-x)(L)]}_n (HNEt₃ = triethylammonium, L = 1,2,4,5-tetrakis(methanesulfonamido)benzene), doped with diamagnetic Cu¹⁺ carriers. Through comprehensive characterization of the structural, optical, and magnetic properties, we observed continuous electronic and magnetic crossover as the doping level was gradually increased. When x < 0.5, the doped compounds exhibit ferromagnetic insulating behavior with very high energy barriers (U_eff up to 560 K) and excellent slow relaxation of magnetization. At x = 0.5, {(HNEt₃)_0.5[Cu_0.5Co_0.5(L)]}_n functions as a paramagnetic semiconductor at high temperatures and a single-molecule magnet at low temperatures. When x > 0.5, the doped compounds act as diluted antiferromagnetic semiconductors with narrow band gaps (E_a = 0.2 eV). The emergence of such rich electronic and magnetic crossovers is ascribed to the cooperation of the strong electron-donating ability of the ligand and the pronounced crystal-field effects. Our findings indicate that one-dimensional (1D) coordination polymers are promising for the design of novel low-dimensional magnetic semiconductors.