Tuning single-molecule magnetism in Dy3+ complexes via a tris(aryl)alkoxide ligand

Gautier Felix; Alexander N. Selikhov; Max Kallio; Veacheslav Vieru; Anna V. Vologzhanina; Elena V. Balagurova; Yannick Guari; Joulia Larionova; Alexander A. Trifonov

doi:10.1039/d5dt02861b

Tuning single-molecule magnetism in Dy3+ complexes via a tris(aryl)alkoxide ligand

Gautier Felix
, Alexander N. Selikhov
, Max Kallio
, Veacheslav Vieru
, Anna V. Vologzhanina
, Elena V. Balagurova
, Yannick Guari
, Joulia Larionova^*
, Alexander A. Trifonov^*

^*Corresponding author for this work

Research output: Contribution to journal › Article › Academic › peer-review

Abstract

We report the synthesis, structures, and magnetic properties of two Dy ³⁺ complexes supported by a tripodal tris(aryl)alkoxide ligand (Me ₂NCH ₂-o-C ₆H ₄) ₃CO ⁻. The mononuclear complex [κ ³-O,N,N-(Me ₂NCH ₂-o-C ₆H ₄) ₃CO]DyCl ₂(THF) (1) adopts a distorted octahedral geometry, while its reaction with a dipotassium dicarbollide K ₂[7,8-Me ₂C ₂B ₉H ₉] affords a heterobimetallic coordination polymer {[K(μ-Cl)Dy(κ ³-O,N,N-(Me ₂NCH ₂-o-C ₆H ₄) ₃CO)(μ-2,3-Me ₂C ₂B ₉H ₉)]·0.5THF} _n (2·0.5THF) featuring a layered structure. Both compounds exhibit single-molecule magnet (SMM) behavior, with effective barriers of 344 K (240 cm ⁻¹) for 1 and 133 K (92.5 cm ⁻¹) for 2. Ab initio calculations indicate that 1 relaxes via the third excited Kramers doublet (KD), while 2 likely relaxes through the second KD. The relaxation pathways observed experimentally for 2 do not correspond to the computed KDs, possibly due to experimental limitations at high temperatures or fast relaxation rates undetectable by alternating current susceptibility.

Original language	English
Pages (from-to)	8901-8912
Number of pages	12
Journal	Dalton Transactions
Volume	55
Issue number	23
DOIs	https://doi.org/10.1039/d5dt02861b
Publication status	Published - 16 Jun 2026

Keywords

HIRSHFELD SURFACE-ANALYSIS
STRUCTURAL-CHARACTERIZATION
DICARBOLLIDE COMPLEXES
SLOW RELAXATION
ION MAGNET
BLOCKING
APPROXIMATION
MAGNETIZATION
ANISOTROPY
ENERGY

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@article{9dda17f39ce84b3daaaab6b75cd2a639,

title = "Tuning single-molecule magnetism in Dy3+ complexes via a tris(aryl)alkoxide ligand",

abstract = "We report the synthesis, structures, and magnetic properties of two Dy 3+ complexes supported by a tripodal tris(aryl)alkoxide ligand (Me 2NCH 2-o-C 6H 4) 3CO −. The mononuclear complex [κ 3-O,N,N-(Me 2NCH 2-o-C 6H 4) 3CO]DyCl 2(THF) (1) adopts a distorted octahedral geometry, while its reaction with a dipotassium dicarbollide K 2[7,8-Me 2C 2B 9H 9] affords a heterobimetallic coordination polymer \{[K(μ-Cl)Dy(κ 3-O,N,N-(Me 2NCH 2-o-C 6H 4) 3CO)(μ-2,3-Me 2C 2B 9H 9)]·0.5THF\} n (2·0.5THF) featuring a layered structure. Both compounds exhibit single-molecule magnet (SMM) behavior, with effective barriers of 344 K (240 cm −1) for 1 and 133 K (92.5 cm −1) for 2. Ab initio calculations indicate that 1 relaxes via the third excited Kramers doublet (KD), while 2 likely relaxes through the second KD. The relaxation pathways observed experimentally for 2 do not correspond to the computed KDs, possibly due to experimental limitations at high temperatures or fast relaxation rates undetectable by alternating current susceptibility.",

keywords = "HIRSHFELD SURFACE-ANALYSIS, STRUCTURAL-CHARACTERIZATION, DICARBOLLIDE COMPLEXES, SLOW RELAXATION, ION MAGNET, BLOCKING, APPROXIMATION, MAGNETIZATION, ANISOTROPY, ENERGY",

author = "Gautier Felix and Selikhov, \{Alexander N.\} and Max Kallio and Veacheslav Vieru and Vologzhanina, \{Anna V.\} and Balagurova, \{Elena V.\} and Yannick Guari and Joulia Larionova and Trifonov, \{Alexander A.\}",

year = "2026",

month = jun,

day = "16",

doi = "10.1039/d5dt02861b",

language = "English",

volume = "55",

pages = "8901--8912",

journal = "Dalton Transactions",

issn = "1477-9226",

publisher = "Royal Society of Chemistry",

number = "23",

}

TY - JOUR

T1 - Tuning single-molecule magnetism in Dy3+ complexes via a tris(aryl)alkoxide ligand

AU - Felix, Gautier

AU - Selikhov, Alexander N.

AU - Kallio, Max

AU - Vieru, Veacheslav

AU - Vologzhanina, Anna V.

AU - Balagurova, Elena V.

AU - Guari, Yannick

AU - Larionova, Joulia

AU - Trifonov, Alexander A.

PY - 2026/6/16

Y1 - 2026/6/16

N2 - We report the synthesis, structures, and magnetic properties of two Dy 3+ complexes supported by a tripodal tris(aryl)alkoxide ligand (Me 2NCH 2-o-C 6H 4) 3CO −. The mononuclear complex [κ 3-O,N,N-(Me 2NCH 2-o-C 6H 4) 3CO]DyCl 2(THF) (1) adopts a distorted octahedral geometry, while its reaction with a dipotassium dicarbollide K 2[7,8-Me 2C 2B 9H 9] affords a heterobimetallic coordination polymer {[K(μ-Cl)Dy(κ 3-O,N,N-(Me 2NCH 2-o-C 6H 4) 3CO)(μ-2,3-Me 2C 2B 9H 9)]·0.5THF} n (2·0.5THF) featuring a layered structure. Both compounds exhibit single-molecule magnet (SMM) behavior, with effective barriers of 344 K (240 cm −1) for 1 and 133 K (92.5 cm −1) for 2. Ab initio calculations indicate that 1 relaxes via the third excited Kramers doublet (KD), while 2 likely relaxes through the second KD. The relaxation pathways observed experimentally for 2 do not correspond to the computed KDs, possibly due to experimental limitations at high temperatures or fast relaxation rates undetectable by alternating current susceptibility.

AB - We report the synthesis, structures, and magnetic properties of two Dy 3+ complexes supported by a tripodal tris(aryl)alkoxide ligand (Me 2NCH 2-o-C 6H 4) 3CO −. The mononuclear complex [κ 3-O,N,N-(Me 2NCH 2-o-C 6H 4) 3CO]DyCl 2(THF) (1) adopts a distorted octahedral geometry, while its reaction with a dipotassium dicarbollide K 2[7,8-Me 2C 2B 9H 9] affords a heterobimetallic coordination polymer {[K(μ-Cl)Dy(κ 3-O,N,N-(Me 2NCH 2-o-C 6H 4) 3CO)(μ-2,3-Me 2C 2B 9H 9)]·0.5THF} n (2·0.5THF) featuring a layered structure. Both compounds exhibit single-molecule magnet (SMM) behavior, with effective barriers of 344 K (240 cm −1) for 1 and 133 K (92.5 cm −1) for 2. Ab initio calculations indicate that 1 relaxes via the third excited Kramers doublet (KD), while 2 likely relaxes through the second KD. The relaxation pathways observed experimentally for 2 do not correspond to the computed KDs, possibly due to experimental limitations at high temperatures or fast relaxation rates undetectable by alternating current susceptibility.

KW - HIRSHFELD SURFACE-ANALYSIS

KW - STRUCTURAL-CHARACTERIZATION

KW - DICARBOLLIDE COMPLEXES

KW - SLOW RELAXATION

KW - ION MAGNET

KW - BLOCKING

KW - APPROXIMATION

KW - MAGNETIZATION

KW - ANISOTROPY

KW - ENERGY

U2 - 10.1039/d5dt02861b

DO - 10.1039/d5dt02861b

M3 - Article

SN - 1477-9226

VL - 55

SP - 8901

EP - 8912

JO - Dalton Transactions

JF - Dalton Transactions

IS - 23

ER -

Tuning single-molecule magnetism in Dy<SUP>3+</SUP> complexes <i>via</i> a tris(aryl)alkoxide ligand

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