View Article Online

INORGANIC
View Journal

CHEMISTRY
FRONTIERS
Accepted Manuscript

This article can be cited before page numbers have been issued, to do this please use: M. A. Lemes, N.
Mavragani, P. Richardson, Y. Zhang, B. Gabidullin, J. L. Brusso, J. Moilanen and M. Murugesu, Inorg.
Chem. Front., 2020, DOI: 10.1039/D0QI00365D.

This is an Accepted Manuscript, which has been through the

Royal Society of Chemistry peer review process and has been accepted
Volume 6 | Number 1 | January 2019

for publication.

Accepted Manuscripts are published online shortly after acceptance,

before technical editing, formatting and proof reading. Using this free
service, authors can make their results available to the community, in
citable form, before we publish the edited article. We will replace this
Accepted Manuscript with the edited and formatted Advance Article as
soon as it is available.

You can find more information about Accepted Manuscripts in the

INORGANIC Information for Authors.
CHEMISTRY Please note that technical editing may introduce minor changes to the
FRONTIERS text and/or graphics, which may alter content. The journal’s standard
Terms & Conditions and the Ethical guidelines still apply. In no event
shall the Royal Society of Chemistry be held responsible for any errors
rsc.li/frontiers-inorganic
or omissions in this Accepted Manuscript or any consequences arising
from the use of any information it contains.

rsc.li/frontiers-inorganic
 Page 1 of 9 Inorganic
Please Chemistry
do not adjustFrontiers
margins

View Article Online

Journal Name
DOI: 10.1039/D0QI00365D

COMMUNICATION

Inorganic Chemistry Frontiers Accepted Manuscript

Unprecedented intramolecular pancake bonding in a {Dy2}
single-molecule magnet
Received 00th January 20xx,
Maykon A. Lemes,a Niki Mavragani,a Paul Richardson,a Yixin Zhang,a Bulat Gabidullin,a Jaclyn L.
Brusso,a* Jani O. Moilanen,b*and Muralee Murugesua*
Published on 16 April 2020. Downloaded by Université de Paris on 4/16/2020 4:57:04 AM.

Accepted 00th January 20xx

DOI: 10.1039/x0xx00000x

www.rsc.org/

The first example of unique coordination induced radical with the unpaired electrons of a metal ion effectively
intramolecular pancake bonding was achieved through the suppresses the quantum tunneling of the magnetization and fast
reduction of two bis(pyrazolyl)-tetrazine ligands, affording spin relaxation pathways involving spin excited states, thus
[MIII2(μ-(bpytz)2)(THMD)4](M = Dy, Y; bpytz = 3,6-bis(3,5- promoting a thermal relaxation pathway for magnetization
dimethyl-pyrazolyl)-1,2,4,5-tetrazine; TMHD = 2,2,6,6- reversal.3b If radicals are used as bridging units between two or
tetramethyl-3,5-heptanedionate). To provide a cohesive more metal centres, then magnetic communication between the
magneto-structural correlation, the mono bis(pyrazolyl)- metal ions can be enhanced.2c,3b-c As such, lanthanide based
tetrazine bridged congener [DyIII2(μ- SMMs containing bridging, spin-bearing ligands have attracted
bpytz)(THMD)6]·4(C6H6) was also isolated. Both metal considerable attention. Currently, the best performing
complexes exhibit single-molecule magnet behaviour under polynuclear SMM is a dinuclear metal complex containing a
an applied dc field. dinitrogen radical bridge with a blocking temperature of 20 K
and giant coercive field of Hc = 7.9 T at 10 K.3c While this
Radicals have long been considered transient, highly reactive validates the design strategy, the presence of the dinitrogen
species; however, in recent years a number of stable radical radical bridge imparts air sensitivity to the molecule.
based systems have been reported.1 Although many have been Nonetheless, this represents an excellent example in which metal
shown to be stable in the solid state, a number are still susceptible coordination stabilizes an otherwise unisolable radical.
to self-association (i.e., dimerization).While dimerization can be Although self-association of radicals can be inhibited thanks
suppressed through sterics, the increased bulkiness around the to the coordination environment dictated by the geometry of the
radical centre unfortunately inhibits close proximity of the metal ion, employing bridging radical ligands remains an
unpaired spins, thereby inhibiting potential conductive and/or ongoing challenge. This is due in large part to the access of stable
magnetic properties of the resulting materials. Alternatively, delocalized radicals that can impart efficient magnetic exchange
coordination chemistry can be employed as a useful route to between two or more metal ions.2c To that end, tetrazine based
prevent dimerization, and has been widely exploited in recent ligands offer multiple coordination pockets, while the nitrogen
years due to the potential of such systems in applications ranging content and delocalized nature of the π-system enhance the
from catalysis to molecular magnetism.2 In the case of the latter, stability towards oxygen.5 Thanks to the relatively small energy
research on single-molecule magnets (SMMs) has recently difference between the π and π* molecular orbitals, tetrazine
focused on the use of radicals as ligands to enhance the magnetic moieties can be easily reduced at low reduction potential.5i These
properties of SMMs through the exchange coupling of the features have been demonstrated using transition metals5a,b,h,2d as
radical- and metal-based spins.3 SMMs are defined as molecules well as a few examples employing lanthanide ions.5k,22a
that retain the slow relaxation of their magnetization upon As mentioned, metal coordination is highly effective in the
removal of an applied field, acting as magnets below blocking quest to prevent dimerization; however, π-dimerization achieved
temperatures.4 The strong interaction between the spin of the through metal coordination is considerably less explored. The
only example reported to date is the formation of a π-dimer
a. Department
attained by appending two radical moieties on the
of Chemistry and Biomolecular Sciences. University of Ottawa, ON,
Canada K1N 6N5. Email: [email protected]; Tel: + (613) 562 5800 ext. cyclopentadienyl rings of ferrocene, as elegantly demonstrated
2733. by Hicks et al.6 While this represents an intramolecular π-dimer
b. University of Jyväskylä, Department of Chemistry, Nanoscience Centre, P.O. Box

35, FI-40014, University of Jyväskylä, Finland

associated with a metal complex, these π-dimers are not directly
† Electronic Supplementary Information (ESI) available: Experimental details, bound to the metal ion. To date, coordination induced π-
crystallographic data, EPR analysis,magneticstudies and computational
data.CCDC1858838, 1858840 and 1976893. See DOI: 10.1039/x0xx00000x
dimerization or examples of bridging π-dimers between two

This journal is © The Royal Society of Chemistry 20xx J. Name., 2013, 00, 1-3 | 1

Please do not adjust margins

 Please do not
Inorganic adjustFrontiers
Chemistry margins Page 2 of 9

COMMUNICATION Journal Name

metal ions have yet to be reported. This is likely due to the View Article Online
change in electron density of the radical and coupling of the DOI: 10.1039/D0QI00365D
DyIII(TMHD)3 N N N
radical and metal spins upon coordination, thereby decreasing N N
the stabilization effect of dimerization. Furthermore, C6H6/CH3CN N N N

coordination to a metal centre dictates the sterics and orientation

Inorganic Chemistry Frontiers Accepted Manuscript

of the radical moiety and its proximity to neighbouring radicals. N N N 1: = DyIII(TMHD)3
N N
All of these properties inhibit intramolecular dimerization and N N N
minimize the tendency for intermolecular self-association bpytz
between neighbouring radicals. N N
N
To that end, herein we report an unprecedented DyIII(TMHD)3, CoCp 2 N N
N N
intramolecular π-π stacking interaction, also called a pancake C6H6/CH3CN N N
N N N N
bond, in a {Dy2} single-molecule magnet by utilizing a N
bis(pyrazolyl)-tetrazine based ligand framework. More
Published on 16 April 2020. Downloaded by Université de Paris on 4/16/2020 4:57:04 AM.

specifically, the synthesis, extensive computational studies and 2: = DyIII(TMHD)2

detailed magnetic analysis of two structurally related dinuclear Scheme 1 Synthetic route for the isolation of [DyIII2(μ-bpytz)(THMD)6]·4(C6H6)
DyIII SMMs, revealed through an applied dc field, are presented; (1·4(C6H6)) and [DyIII2(μ-(bpytz)2)(THMD)4] (2), where bpytz = 3,6-bis(3,5-
a dinuclear DyIII metal complex [DyIII2(μ- dimethyl-pyrazolyl)-1,2,4,5-tetrazine and TMHD = 2,2,6,6-tetramethyl-3,5-
bpytz)(THMD)6]·4(C6H6) (1·4C6H6; where bpytz = 3,6-bis(3,5- heptanedionate. The dark blue vs. lighter blue bpytz in 2 indicates the above
dimethyl-pyrazolyl)-1,2,4,5-tetrazine; TMHD = 2,2,6,6- and below arrangement of the reduced ligand π-dimer.
tetramethyl-3,5-heptanedionate) with a neutral tetrazine bridging
ligand, alongside [DyIII2(μ-(bpytz)2)(THMD)4] (2), a dinuclear Single-crystal X-ray diffraction analysis reveals that 1·4C6H6
compound containing a unique π-dimerized tetrazine bridge. The and 2 crystallize in the triclinic 𝑃1 and trigonal 𝑃3221 space
yttrium analogue [YIII2(μ-(bpytz)2)(THMD)4] (3), which is groups, respectively. The molecular structures of both metal
isostructural to 2, was also prepared and studied to confirm the complexes are shown in Fig. 1 and Fig. S2-S4, and X-ray data
diamagnetic nature of the bridging π-dimer ligand. This report along with selected distances and angles are given in Tables S1-
represents the first example of a coordination induced tetrazine S3. In 1·4C6H6, the centrosymmetric dinuclear metal complex is
intramolecular π-dimer contained within a single molecule. composed of two DyIII ions bridged by a neutral bpytz ligand;
Preparation of compounds 1·4C6H6, 2 and 3 follow similar close inspection of the N-N distance (1.32(5) Å) in the tetrazine
procedures, beginning with the reaction of one equivalent of core is in good agreement with that of the free ligand, thus
bpytz with one equivalent of M(TMHD)3 (where M = Dy or Y) corroborating the neutral form of the tetrazine moiety. Three
in benzene under aerobic conditions, which affords a dark brown TMHD ligands complete the coordination environment around
solution (for 1·4C6H6, see ESI for more details). Upon vapour the metal centres, affording square antiprismatic geometry as
diffusion of the aforementioned solution with acetonitrile confirmed by SHAPE analysis (Table S4).7 The two metal ions
(CH3CN), red block-like single crystals of [DyIII2(μ- are coordinated in a bidentate fashion in the bipy-like
bpytz)(THMD)6]·4C6H6 (1·4C6H6) suitable for single crystal X- coordination pocket of the bpytz ligand with intramolecular
ray diffraction (SCXRD) were obtained in 85% yield (Scheme DyDy distances of 8.01(4)Å. Four benzene solvent molecules
1). The same product can be isolated if the reaction is performed are also present in the crystal lattice.
under anaerobic conditions (2 and 3), whereas a dark green In the case of 2, the centrosymmetric compound is comprised
solution is obtained if the reaction is carried out in the presence of two DyIII ions bridged by two bpytz ligands, with two TMHD
of one equivalent of cobaltocene (CoCp2). Slow diffusion of coordinated to each metal centre thereby affording a geometry
CH3CN into the latter yields dark green block-like crystals of that can best be described as square antiprism (SHAPE analysis,
[DyIII2(μ-(bpytz)2)(THMD)4] (2) in 80% yield. Alternatively, Table S4).7 Here, the four TMHD co-ligands contribute a total
compound 2 can be prepared from the reaction of 1·4C6H6 with charge of 4, therefore the additional charge to stabilize the 6+
CoCp2 in the same solvolitic conditions, though we found this metal ions must be provided by two reduced bpytz ligands with
resulted in lower yield percentages. This may be attributed to the each having a charge of 1. Reduction of the bpytz ligands in 2
sacrificial nature of the reaction. It is noteworthy that attempts to is thus supported by charge balance considerations. The
isolate the mono-radical anion bridged dinuclear {Dy2} crystallographic changes observed in the tetrazine core through
compound were unsuccessful, as were attempts to prepare the elongation of the azo N-N distances from 1.32(5) Å to 1.39(6)Å
radical anion or π-dimer of bpytz in the absence of metal ions. further endorse the negative charge on the tetrazine moieties.5
Interestingly, compounds 1·4C6H6, 2, and 3 exhibit solid-state The assembly of the two bpytz ligands allows the tetrazine rings
air-stability over long periods of time, as observed via infrared to face each other at a distance of 2.73(5) Å (Fig. S3 and S4); a
(IR) measurements. For example, under aerobic conditions over distance considerably longer than a single bond (ca. 1.43 – 1.54
a period of 20 days, no change was observed in the IR spectra of Å) yet notably shorter than the sum of the van der Waals radii
2 (Fig. S1). (ca. 3.0 – 3.4 Å).8 The packing arrangement displays
intermolecular DyDy distances of 12.11(1)Å, while the
DyDy intramolecular distance is 7.10(8)Å.

2 | J. Name., 2012, 00, 1-3 This journal is © The Royal Society of Chemistry 20xx

Please do not adjust margins

 Page 3 of 9 Inorganic
Please Chemistry
do not adjustFrontiers
margins

Journal Name COMMUNICATION

reduced bpytz moieties and hence π-dimerization ofView theArticle

bridging
Online
ligand. Solution electron paramagnetic resonance (EPR) studies
DOI: 10.1039/D0QI00365D
were also carried out on 3, which exhibit a nine-line pattern
signal attributed to a single bpytz radical anion (i.e., simulated
using a model based on hyperfine coupling of four equivalent

Inorganic Chemistry Frontiers Accepted Manuscript

14N nuclei with a = 0.507 mT; Fig. S8). However, such signals
N
must be taken with caution as 3 is sparingly soluble in common
organic solvents and, under these conditions, its stability is
limited; attempts to probe this interaction through NMR
experiments were inconclusive. As such, the obtained signal is
likely arising from the dissociated compound in solution.
Moreover, a half-field signal arising from the population of the
triplet state was not observed in the EPR studies, indicative of
Published on 16 April 2020. Downloaded by Université de Paris on 4/16/2020 4:57:04 AM.

strong antiferromagnetic coupling between the two bpytz radical

anions.
To further analyse the nature of the pancake bond within
compound 2, broken symmetry density functional theory (BS-
DFT)12 and complete active space self-consistent field
(CASSCF) calculations13 were first carried out for 3 [YIII2(μ-
(bpytz)2)(THMD)4] and its simplified model system 4[YIII2(μ-
(bpytz)2)(PD)4] (PD = propanedionate) using the coordinates
adapted from the crystal structure of 3 and only optimizing the
positions of the hydrogen atoms (see computational details in the
ESI included in Fig. S9). Two spin bearing radicals that strongly
interact can form a triplet or singlet state system depending on
Fig. 1 Molecular structure of 1 (top) and 2 (bottom). Solvent molecules and the ferromagnetic (FM) or antiferromagnetic (AFM) coupling of
hydrogen atoms were omitted for clarity. Color code: Dy (orange), C (gray), N their spins, respectively. In the case of a pancake bonded system,
(blue), O (red). the ground state is typically a singlet.12e Here, the singlet state is
favoured over a triplet one, because the in-phase components of
Although reduction of tetrazine in coordination metal complexes identical singly occupied molecular orbitals (SOMOs) of the
is known to afford tetrazinyl radicals,5 here the observed air- radicals that form the pancake bond strongly overlap with each
stability, close intramolecular contacts and magnetic data (vide other. The overlap of in-phase components of identical SOMOs
infra) indicate spin pairing of the tetrazinyl moieties within the leads to a covalent type interaction between two radicals that
molecule. Despite the electrostatic repulsion expected between automatically favours an AFM interaction.12e,14a
charged radical species, examples of π-dimerized radical cations The wave function of the singlet state pancake bonded
are known as are radical anions, however, there are fewer system usually contains a considerable amount of singlet
examples of the latter (e.g., TCNE and TCNQ).9 While π- diradical character.12e The singlet diradical is a molecular entity
dimerization is quite common among organic radicals, it is rare in which two electrons occupy two (nearly) degenerate
in coordination metal complexes and, when present, tends to lead molecular orbitals.15 The wave function of such a system is
to extended coordination networks.10 In 2, we have a π-dimer that multiconfigurational and cannot be described by the single Slater
acts as an intramolecular bridge between two metal centres in a determinant based methods such as the restricted Hartree-Fock
discrete coordination compound. Here the charge imparted by theory. Therefore, multiconfigurational based approaches like
the cationic lanthanide ions likely alleviate some of the CASSCF are needed. In a strict sense, the basic formalism of
electrostatic repulsion between the radical anions, facilitating the DFT is also a single determinant approach but it is able to treat
formation of the π-dimerized bridging ligand and perhaps small to moderate amounts of the singlet diradical character.
stabilizing self-association. The interaction between the bpytz Because of this, it is an applicable computational method to
ligands in 2, which can be referred to as pancake bonding (i.e., model the pancake bond within compounds 3 and 4. To confirm
multicentered 2-electron bonding; mc-2e),11 is unique to this the ground state multiplicity of 3 and 4, we first calculated the
molecule and such features have yet to be reported. vertical singlet-triplet gap (VSTG) for 4 using a variety of
In an effort to validate the diamagnetic nature of the bridging different exchange-correlation functionals and the Yamaguchi
ligand in 2, the yttrium analogue [YIII2(μ-(bpytz)2)(THMD)4] (3) projection.16 Depending on the functional used, BS-DFT
was synthesized following a similar procedure. SCXRD analysis calculations predicted the triplet state to be ~ 3250–4000 cm-1
of 3 reveals that it crystallizes in the trigonal P3221 space group higher in energy than the singlet state (Table S5). The validity of
and is isostructural with 2, as evidence by the structural overlay the small model system 4 was confirmed by calculating the
(Fig. S5), infrared spectroscopy (Fig. S6) and powder X-ray VSTG for 3 using the LC-ωPBE-D3/def2-TZVP level of
diffraction patterns (Fig. S7). Solid state magnetic studies on 3 theory17a-c,18; very similar values were obtained for 3 (-3228 cm-
reveal its diamagnetic nature, supporting spin pairing of the two 1) and 4 (-3249 cm-1). Small geometrical changes can influence

This journal is © The Royal Society of Chemistry 20xx J. Name., 2013, 00, 1-3 | 3

Please do not adjust margins

 Please do not
Inorganic adjustFrontiers
Chemistry margins Page 4 of 9

COMMUNICATION Journal Name

the value of the STG and it is very likely that 3 does not adopt number of the acceptor orbital nACC (formally the LUMOView Articlein the
Online
the same geometry in the solution and solid state. Thus, we also case of 4) to the reference value of one electron (nACC /1.00) ×
DOI: 10.1039/D0QI00365D
calculated the adiabatic singlet-triplet gaps (ASTG) for the gas- 100%. Despite the size of active space and the geometry
phase optimized geometries of 3 and 4 (only at the LC-ωPBE- employed (i.e., crystal structure or gas-phase optimized), the
D3 level for 3) using the same exchange-correlation functionals investigation of NOONs reveals that ~0.4–0.6 electrons are

Inorganic Chemistry Frontiers Accepted Manuscript

as for the VSTG.14 Geometry optimizations of the HS and LS transferred from the formally HOMO to LUMO, which
states of 3 and 4 revealed that the intramolecular centroid- corresponds to 40–60 % of the singlet diradical character (Tables
centroid (Cnt-Cnt) ring distance of two interacting bpytz•- S8 and S9). Only a small amount of electron density is
radicals for the gas-phase optimized structures are ~0.1–0.3 Å distributed from the other formally occupied π-orbitals to
longer than the intramolecular Cnt-Cnt ring distance of the unoccupied π-orbitals that all have relatively small NOONs.
crystal structure of 3 (Table S6). The best agreement between
experimental and calculated Cnt-Cnt distance is obtained with
the B3LYP-D3/def2-TZVP,17d-f,18 PBE1PBE-D3/def2-
Published on 16 April 2020. Downloaded by Université de Paris on 4/16/2020 4:57:04 AM.

TZVP,17g,h,18 and LC-ωPBE-D3/def2-TZVP17a-c,18 levels of

theory that predict the calculated Cnt-Cnt distance of the ground
LS state to be only ~0.1 Å longer than the experimental value.
Although different projections were used to obtain the VSTGs
and ASTGs, it is evident from the calculated data that the small
increase in the Cnt-Cnt distance has effect on the calculated
singlet-triplet gaps of 3 and 4; the ASTGs are smaller (~-1780 to
-2600 cm-1) than the VSTGs (~ -3250 to -4000 cm-1) (Tables S5
and S7). Nevertheless, such high STGs very likely explain why LUMO
the thermally accessible triplet state is not populated even at the
room temperature, as supported by EPR analysis. Moreover, the
calculated VSTGs and ASTGs fully confirm that the singlet state
is the ground state for 3 and 4 in the solid state and gas-phase.
The highest occupied molecular orbital (HOMO) and lowest
unoccupied molecular orbital (LUMO) obtained at the LC-
ωPBE-D3/def2-TZVP level of theory for the singlet state of 4
are shown in Fig. 2. As can be seen, the bpytz•- radicals within
the metal complex are π-dimerized through an orbital interaction
that resembles covalent-type bonding. The spin density
HOMO
distribution is also presented in Fig. 2, revealing a strong
localization of spin density on the central rings of the two bpytz•-,
as well as (almost) equal distribution for α and β spin density. To
quantify this orbital interaction in 3 and 4, we calculated the
vertical and adiabatic rad-rad coupling constant (Jrad-rad) using
the Yamaguchi and adiabatic projections, respectively, and BS-
DFT formalism.14,16 We evaluated the singlet diradical character,
unpaired electron density,19 and formal bond order (pNO)20 of 4
utilizing natural orbital occupation numbers (NOONs) from the
CASSCF calculations (see ESI for details). The CASSCF
Spin Density
calculations were performed for the frozen and LC-ωPBE-
D3/def2-TZVP optimized ground state gas-phase geometry of 4.
Since the Jrad-rad equals the vertical and adiabatic singlet-triplet Fig. 2 Highest occupied molecular orbitals (HOMO; middle) and lowest
unoccupied molecular orbitals (LUMO; top), as well as the spin density
gaps (see above), the calculated Jrad-rad values indicate a strong
distribution (bottom; blue = α spin density; green = β spin density) for 4.
antiferromagnetic interaction between two bpytz•- in 3 and 4
Similar HOMO, LUMO and spin density distributions are observed for3.
(Tables S5 and S7). These values of Jrad-rad are in line with values
reported for other strongly π-dimerized radical systems.14a
NOONs are the eigenvalues of the one-particle electron The results indicate that the wave function of 4 contains a notable
density matrix, and they converge towards values that they adopt amount of the singlet diradical character, and the formally
in the exact wave function when the level of theory used is high HOMO and LUMO contribute most to the formation of the
enough.21 Because of this, NOONs at the CASSCF level of pancake bond between π-dimerized bpytz•- radicals. NOONs can
theory can be used as a benchmark of the singlet diradical be also used to evaluate the pNO and unpaired electron density
character; in a perfect diradical, two natural orbitals are each between bpytz•- radicals, with the latter measuring the separation
occupied exactly by one electron. Thus, a suitable index for of an electron pair into different spatial regions.19 By using the
diradical character is obtained by comparing the occupation occupation numbers of the frontier natural orbitals (formally the

4 | J. Name., 2012, 00, 1-3 This journal is © The Royal Society of Chemistry 20xx

Please do not adjust margins

 Page 5 of 9 Inorganic
Please Chemistry
do not adjustFrontiers
margins

Journal Name COMMUNICATION

HOMO and LUMO) of 4 from the CASSCF calculations, the pNO View Article Online
value of ~0.4–0.6 is obtained for the frozen and optimized DOI: 10.1039/D0QI00365D
geometry of 4. The unpaired electron density is measured by
calculating the total number of effectively unpaired electrons
(Nu) between bpytz•- ligands. The calculated value of Nu for 4

Inorganic Chemistry Frontiers Accepted Manuscript

deviates between 0.74 and 1.36 for the solid-state geometry and
1.07 and 1.41 for the gas-phase optimized, depending on the size
of active space used in the CASSCF calculations. Most
importantly, such high values reflect the notably diradical
character of compound 4 (Tables S10 and 11). Both the pNO and
Nu values obtained for 4 are in a good agreement with values
reported for other systems containing a single pancake bond.20,22
Overall, these calculations indicate that the interaction between Fig. 3 Variable temperature dc magnetic susceptibility data, where χ = M/H
Published on 16 April 2020. Downloaded by Université de Paris on 4/16/2020 4:57:04 AM.

the bpytz moieties resembles a covalent bond rather than a weak normalized per mole for 1·4C6H6 (blue) and 2 (green) obtained under an
AFM exchange interaction. In this respect, the π-dimerized applied field of 1000 Oe. Experimental data is denoted by circles with the solid
bpytz•- radicals should function as a diamagnetic linker between line representing the fit.
the two DyIII ions within 2.
To validate the nature of the intramolecular π-dimerized Owing to the significant spin orbit coupling associated with
bridging ligand and to probe the static and dynamic magnetic DyIII ions, such compounds often exhibit a slow relaxation of
susceptibility associated with dinuclear DyIII metal complexes, magnetization, indicative of SMM behaviour. To probe this,
the magnetic properties of 1·4C6H6 and 2 were investigated dynamic alternating current (ac) susceptibility measurements
using a SQUID magnetometer. The direct current (dc) were performed on 1·4C6H6 and 2. At low temperatures and zero
susceptibility data obtained at 1000 Oe display room temperature dc field, both metal complexes exhibit ac signals; 1·4C6H6 shows
χT products of 27.83 cm3 K mol-1 and 27.53 cm3 K mol-1 for a small tail while 2 displays a slightly pronounced signal (Fig.
1·4C6H6 and 2, respectively (Fig. 3). These values are in good S11). No clear full peak was observable for either compound
agreement with the theoretical χT values estimated for two non- under these conditions. This indicates that magnetization
interacting DyIII ions (S= 5/2; L=5; 6H15/2; g= 4/3; χTRT= 14.17 relaxation is likely occurring through quantum tunnelling of the
cm3 K mol-1).The similarities between the room temperature magnetization (QTM), thus quenching the SMM behaviour.
values for both compounds further support the absence of any Nonetheless, upon application of a small static field (1000 Oe),
additional spins (i.e., radical ligands) within 2, corroborating the full peaks were observable suggesting that QTM can be
self-association of the bpytz•- ligands and the resulting pancake minimized and relaxation times can be increased upon
bond formation. In the temperature range of 300 – 100 K, the T application of a field. To further probe the effect of the applied
product for both metal complexes remain constant, indicative of dc field, field dependent measurements were carried out at 2 K
the uncoupled nature of the DyIII – DyIII interaction within the with varying magnetic fields up to 1800 Oe for 1·4C6H6 and
molecules. Below 100 K, the decrease of the T product can be 5000 Oe for compound 2 (Fig. S12 and S13). It is noteworthy
associated with depopulation of the Stark sublevels, spin-orbit that two unique “high” and “low” freq. processes can be seen.
coupling and/or weak interactions between the metal ions. Upon This data was fit using a generalized/double Debye model for the
comparing the magnetic susceptibility of 1·4C6H6 vs. 2, the T field dependent ac susceptibility measurements (Tables S12,
product of 2 deviates from linearity at a higher temperature (100 S13). This data confirms QTM can be minimized and the slow
K) than for 1·4C6H6 (50 K). Fitting of the data using the Lines relaxation of the magnetization can be enhanced at 600 Oe for
model23 affords exchange coupling constants of 0.006 cm-1 and 1·4C6H6 and 1200 Oe for 2.
0.016 cm-1 for 1·4C6H6 and 2, respectively, indicating a weak Upon performing temperature dependent (6 to 1.9 K) ac
exchange interaction between the DyIII ions.24 The slightly susceptibility measurements in the presence of a static dc field of
stronger coupling constant observed in 2 is likely due to the 600 Oe, frequency dependent out-of-phase signals were
shorter intramolecular DyIII – DyIII distance of 7.10(8) Å observed in 1·4C6H6, revealing its SMM behaviour (Fig.4 and
compared with 1·4C6H6 (8.01(4) Å). Although weak, this slight S14). This data was fit using the generalized Debye model
variation between compounds may be attributed to the utilizing CC-FIT2 software,25 through which the relaxation times
intramolecular π-dimerized bpytz•- bridging ligand. In addition, (τ) and their respective distributions (α) were extracted (Tables
the field dependence of the magnetization (M vs. H/T) data does S12-S15 for parameters of best fit for each temperature curve).
not exhibit saturation likely due to thermally accessible low- Given the nature of the SMM behaviour, it is vital to consider
lying excited states even at 1.8 K and 7 T (Fig. S10). The not just thermally induced relaxation processes, but also other
isotherm lines do not fully superimpose, suggesting the presence relaxation mechanisms such as Raman, Direct and QTM
of magnetic anisotropy inherent to DyIII ions. processes. Upon plotting τ-1 vs. T on logarithmic axes, a distinct
linear trend can be observed. This is indicative that over the
temperature ranges where values of τ can be observed, the
dominant mechanism of magnetisation relaxation occurs via
Raman processes (τ-1 = CTn; eq. 1). Upon fitting the extracted

This journal is © The Royal Society of Chemistry 20xx J. Name., 2013, 00, 1-3 | 5

Please do not adjust margins

 Please do not
Inorganic adjustFrontiers
Chemistry margins Page 6 of 9

COMMUNICATION Journal Name

relaxation times for 1·4C6H6 using eq. 1, the following terms did not improve the quality of the fit and View did Article
not yield
Online
parameters were obtained: C = 0.457 s-1 K-5.09 and n = 5.09. Fits physically reasonable values further supporting a Raman process
DOI: 10.1039/D0QI00365D
employing terms for Orbach (𝜏 ―1 = 𝜏𝑜―1exp ( ―𝑈𝑒𝑓𝑓 𝐾𝐵𝑇); eq. as the dominant magnetisation relaxation mechanism.
2) and QTM (τ-1QTM) did not improve the quality of the fit, thus In light of the above results, the magnetic properties of the
validating the Raman relaxation mode as the primary contributor centrosymmetric compounds 1·4C6H6 and 2 arise mainly from

Inorganic Chemistry Frontiers Accepted Manuscript

to the slow relaxation of the magnetisation. two non-interacting DyIII ions. This may be attributed to the
shielded core 4f magnetic orbitals of DyIII ions along with the
diamagnetic bridging ligand(s) that link the metal centres in both
metal complexes. To investigate the magnetic properties of
1·4C6H6 and 2 in more detail, the standard CASSCF/SO-RASSI
calculations13 followed by SINGLE_ANISO26 and
POLY_ANISO27 routines were performed (see ESI for details).
The CASSCF/SO-RASSI calculations revealed that the principle
Published on 16 April 2020. Downloaded by Université de Paris on 4/16/2020 4:57:04 AM.

magnetic axes of the ground Kramers doublet (KD) are oriented

to 91° and 86° angle with respect to the line connecting two DyIII
ions in 1 and 2, respectively (Fig. S15). In both compounds, the
angles between the magnetic axes of the ground and excited
doublets vary significantly from ~16° to 170°, neither of which
are colinear to the main magnetic axes of the ground KD (Tables
S16 and S17). Close inspection of the g-tensor of the ground KD
(1: gx = 0.048, gy = 0.084, gz = 19.376; 2: gx = 0.035, gy = 0.037,
gz = 18.667), shows non-negligible transverse components in
both molecules, as they deviate from the ideal values of highly
axial g-tensors (gx = gy = 0.0, gz ≈ 20.0). This likely leads to
mixing of the ground state with the higher excited state, thus
promoting significant QTM as observed experimentally. More
specifically, the percentage composition of the SO-RASSI
wavefunctions of the sixteen lowest states are presented in
Tables S18 and S19 for 1 and 2, respectively. As can be seen, the
ground doublet within 1 is mainly composed of MJ = ±15/2
states, which is common for DyIII SMMs.28 The higher lying
doublets of 1 are considerably more mixed than the ground
doublet and cannot be uniquely defined by a single MJ state. The
ground doublet of 2 is not pure MJ = ±15/2 state but contains
mixing from MJ = ±13/2 (4 %) and MJ = ±11/2 states (12 %), as
well as smaller contributions from several higher lying states. As
expected, the higher lying doublets are strongly mixed within 2.
Taking into account all the above-mentioned data, it can be
concluded that the low symmetry environment of the DyIII ions
effectively diminishes the axiality of KDs and leads to the strong
mixing of states in both metal complexes.
The low axial g-tensors of the ground KDs, as well as the
weak exchange interaction between the metal centres, usually
promotes QTM within the ground KD.24 To further study the
relaxation of magnetisation in both compounds, the qualitive
Fig. 4 Frequency dependence of the out-of-phase susceptibility (χ’’) at variable
temperatures performed at 600 Oe for 1·4C6H6 (top) and 1200 Oe for 2 (middle). The
energy barrier for both were constructed by plotting the energies
solid lines represent best fits obtained from the generalized Debye model using CC-FIT2. of the lowest lying states with respect to their magnetic moments
Plot of the τ-1 vs. T on a log-log scale (bottom) with the fit (red line) using eq. 1. and calculating the transition magnetic moment matrix elements
between the states, i.e., transition probabilities (Fig. S16).26c The
In the case of 2, similar frequency dependent signals were calculated transition probabilities for both metal complexes
observed at 1200 Oe below 8 K, also demonstrating SMM show a rather large value for a matrix element connecting the
behaviour (Fig. 4, middle). Using the same approach as 1·4C6H6, two components of the ground KD: for 1 the value is 0.022 µB,
the data was fit utilizing the generalized Debye model in CC- whereas for 2 it is 0.012. Such high values are usually associated
FIT2, and the relaxation times and distributions were extracted.25 with efficient QTM within the ground KD.24a The computational
The data was further fit using a Raman model (eq. 1), through result is fully in line with experimental findings; 1·4C6H6 and 2
which the following parameters were obtained: C = 0.011 s-1 K- show the relaxation of magnetisation only when the degeneracy
6.48 and n = 6.48. Similar to 1·4C H , adding Orbach or QTM
6 6

6 | J. Name., 2012, 00, 1-3 This journal is © The Royal Society of Chemistry 20xx

Please do not adjust margins

 Page 7 of 9 Inorganic
Please Chemistry
do not adjustFrontiers
margins

Journal Name COMMUNICATION

of the ground KDs are lifted with the application of external dc 14239; (b) S. Demir, I.-R. Jeon, J. R. Long, View T. D. Harris,
Article Online
field. Radical ligand-containing single-molecule magnets, Coord.
DOI: 10.1039/D0QI00365D
Chem. Rev., 2015, 289, 149-176; (c) S. Demir, M. I. Gonzalez,
In conclusion, we report two new tetrazine bridged dinuclear L. E. Darago, W. J. Evans, J. R. Long, Giant coercivity and
DyIII metal complexes exhibiting SMM behaviour revealed high magnetic blocking temperatures for N23- radical bridged
through an applied dc field. In 2, which contains two reduced dilanthanide complexes upon ligand dissociation, Nature

Inorganic Chemistry Frontiers Accepted Manuscript

tetrazine moieties, a unique coordination induced π-dimer Commun., 2017, 8, 2144; (d) B. S. Dolinar, D. I.
connecting the two metal centres is observed. This represents the Alexandropoulos, K. R. Vignesh, T. James, K. R. Dunbar,
Lanthanide triangles supported by radical bridging ligands, J.
first example of an unusual intramolecular pancake bond, which Am. Chem. Soc., 2018, 140, 908-911 (e) H. Miao, M. Li, H.-Q.
is supported experimentally and through computational studies. Li, F.-X. Shen, Y.-Q. Zhang, X.-Y. Wang, Syntheses and
More specifically, the similarity of theT products for 1·4C6H6 magnetic properties of a bis-tridentate nitronyl nitroxide
and 2, as well as the calculated vertical (~-3250 to -4000 cm-1) radical and its metal complexes, Dalton Trans., 2019, 48,
and adiabatic (~-1780 to -2600 cm-1) radical-radical coupling 4774-4778; (f) Z.-X. Xiao, H. Miao, D. Shao, H.-Y. Wei, Y.-
Q. Zhang, X.-Y. Wang, Single-molecule magnet behaviour in
constants (Jrad-rad),along with the EPR studies suggest that the a dysprosium-triradical complex, Chem. Commum., 2018, 54,
Published on 16 April 2020. Downloaded by Université de Paris on 4/16/2020 4:57:04 AM.

two tetrazine rings are strongly antiferromagnetically coupled in 9726-9729; (g) I.-R. Jeon, J. G. Park, D. J. Xiao, T. D. Harris,
2, which makes the (bpytz•-)2 bridge a diamagnetic linker An azophenine radical-bridged Fe2signle-molecule magnet
between two DyIII ions. Under an applied field of 600 Oe for with record magnetic exchange coupling, J. Am. Chem. Soc.,
1·4C6H6 and 1200 Oe for 2, both compounds exhibit slow 2013, 135, 16845-16848.
4 (a) F.-S. Guo, B. M. Day, Y.-C. Chen, M.-L. Tong, A.
relaxation of the magnetisation occurring via Raman process. Mansikkamäki, R. A. Layfield, Magnetic hysteresis up to 80
The results found in this ongoing project will be helpful for kelvin in a dysprosium metallocene single-molecule magnet,
future strategies on designing new lanthanide metal complexes Science, 2018, 362, 1400-14003; (b) C. A. P. Goodwin, F.
containing tetrazinyl-based radicals in the pursuit to exploit Ortu, D. Reta, N. F. Chilton, D. P. Mills, Molecular magnetic
direct exchange coupling. hysteresis at 60 kelvin in dysprosocenium, Nature, 2017, 548,
439-442; (c) G. Christou, D. Gatteschi, D. N. Hendrickson, R.
We thank the University of Ottawa, the CFI, the NSERC and Sessoli, Single-molecule magnets, MRS Bull. 2000, 25, 66-71;
the Academy of Finland (projects 315829, 320015) for their (d) S.-D. Jiang, B.-W. Wang, H.-L. Sun, Z.-M. Wang, S. Gao,
financial support. M. A. L. thanks Conselho Nacional de An organometallic single-ion magnet, J. Am. Chem. Soc.,
Desenvolvimento Científico e Tecnológico (CNPQ; 2011, 133, 4730-4733. (e) K. L. M. Harriman, M. Murugesu,
201395/2014-6) for a PhD scholarship. CSC-IT Centre for An organolanthanide building block approach to single-
molecule magnets, Acc. Chem. Res., 2016, 49, 1158-1167.
Science in Finland, the Finnish Grid and Cloud Infrastructure 5 (a) T. J. Woods, M. F. Ballesteros-Rivas, S. M. Ostrovsky, A.
(persistent identifier urn:nbn:fi:research-infras-2016072533) V. Palii, O. S. Reu, S. I. Klokishner, K. R. Dunbar, Strong
and Prof. H. M. Tuononen (University of Jyväskylä) are direct magnetic coupling in a dinuclear CoII tetrazine radical
acknowledged for providing computational resources for the single-molecule magnet, Chem. Eur. J., 2015, 21, 10302-
project. 10305; (b) M. A. Lemes, G. Brunet, A. Pialat, L. Ungur, I.
Korobkov, M. Murugesu, Strong ferromagnetic exchange
coupling in a {NiII4} cluster mediated through an air-stable
tetrazine-based radical anion, Chem. Commun, 2017, 53, 8660-
References 8663; (c) T. J. Woods, H. D. Stout, B. S. Dolinar, K. R.
1 R.G. Hicks, ed., “Stable Radicals: Fundamentals and Applied Vignesh, M. F. Ballesteros-Rivas, C. Achim, K. Dunbar,
Aspects of Odd-Electron Compounds", John Wiley & Sons, Strong ferromagnetic exchange coupling mediated by a
Ltd.: Wiltshire, 2010 bridging tetrazine radical in a dinuclear nickel complex, Inorg.
2 (a) X. Ma, E. A Suturina, M. Rouzieres, M. Platunov, F. Chem. 2017, 56, 12094-12097; (d) M. Schwach, H. D. Hausen,
Wilhelm, A. Rogalev, R. Clérac, P. Dechambenoit, Using W. Kaim, The first crystal structure of a metal-stabilized
redox-active π bridging ligand as a control switch of tetrazine anion radical: formations of a dicopper complex
intramolecular magnetic interactions, J. Am. Chem. Soc., 2019, through self-assembly in a comproportionation reaction, Inorg.
141, 7721-7725; (b) E. M. Fatila, M. Rouziere, M. C. Jennings, Chem., 1999, 38, 2242-2243; (e) M. Glockle, K. Hubler, H. J.
A. J. Lough, R. Clerac, K. E. Preuss, Fine-tuning the single- Kummerer, G. Denninger, W. Kaim,Dicopper (I) complexes
molecule magnet properties of a [Dy(III)-radical]2 pair, J. Am. with reduced states of 3,6-bis(2’-pyrimidyl)-1,2,4,5-tetrazine:
Chem. Soc., 2013, 135, 9596-9599; (c) S. Fortier, J. J. Le Roy, crystal structures and spectroscopic properties of the free
C.-H. Chen, V. Vieru, M. Murugesu, L. F. Chiboratu, D. J. ligand, a radical species, and a complex of the 1,4-dihydro
Mindiola, K. G. Caulton, A dinuclear cobalt complex featuring form, Inorg. Chem., 2001, 40, 2263-2269; (f) K. Parimal, S.
unprecedented anodic and cathodic redox switches for single- Vyas, C. H. Chen, C. M. Hadad, A. H. Flood, Bond elongation
molecule magnet activity, J. Am. Chem. Soc., 2013, 135, in the anion radical of coordicated tetrazine ligands: a
14670-14678; (d) D. I. Alexandropoulos, B. S. Dolinar, K. R. crystallographic, spectroscopin and computational study of a
Vignesh, K. R. Dunbar, Putting a new spin on supramolecular reduces {Re(CO)3Cl} complex, Inorg. Chim. Acta, 2011, 374,
metallacycles: Co3 triangle and Co4 square bearing tetrazine- 620-626; (g) S. K. Tripathy, M. van der Meer, A. Sahoo, P.
based radicals as bridges, J. Am. Chem. Soc., 2017, 139, Laha, N. Dehury, S. Plebst, B. Sarkar, K. Samanta, S. Patra, A
11040-11043; (e) J. A. DeGayner, I.-R. Jeon, T. D. Harris, A dinuclear [{(p-cym)RuIICl}2(μ-bpytz•-)]+ complex bridged by
series of tetraazalene radical bridged M2 (M = CrIII, MnII, FeII, a radical anion: synthesis, spectrochemical, EPR and
CoII) complexes with strong magnetic exchange coupling, theoretical investigation (bpytz = 3,6-bis(3,5-
Chem. Sci., 2015, 6, 6639-6648. dimethylpyrazolyl)1,2,4,5-tetrazine; p-cym = p-cymene),
3 (a) J. D. Rinehart, M. Fang, W. J. Evans, J. R. Long, A N23- Dalton Trans., 2016, 45, 12532-12538; (h) M. A. Lemes, H.
radical-bridged terbium complex exhibiting magnetic N. Stein, B. Gabidullin, K. Robeyns, R. Clérac, M. Murugesu,
hysteresis at 14 K, J. Am. Chem. Soc., 2011, 133, 14236- Probing Magnetic-Exchange coupling in supramolecular

This journal is © The Royal Society of Chemistry 20xx J. Name., 2013, 00, 1-3 | 7

Please do not adjust margins

 Please do not
Inorganic adjustFrontiers
Chemistry margins Page 8 of 9

COMMUNICATION Journal Name

squares based on reducible tetrazine-derived ligands, Chem. organic compounds.Ab-initio MO calculations ofView theArticle
effective
Online
Eur. J., 2018, 24, 4259-4263; (i) W. Kaim, The coordination exchange integrals for cyclophane-typeDOI:carbene dimers,Chem.
10.1039/D0QI00365D
chemistry of 1,2,4,5-tetrazines, Coord. Chem. Rev., 2002, 230, Lett., 1986, 15, 625. (c) K. Yamaguchi, F. Jensen, A. Dorigo
127-139; (j) G. Brunet, M. Hamwi, M. A. Lemes, B. and K. N. Houk, A spin correction procedure for unrestricted
Gabidullin, M. Murugesu, A tunable lanthanide cubane Hartree-Fock and Møller-Plesset wavefunctions for singlet
platform incorporating air-stable radical ligands for enhanced diradicals and polyradicals,Chem. Phys. Lett., 1988, 149, 537.

Inorganic Chemistry Frontiers Accepted Manuscript

magnetic communication, Commun. Chem. 2018, 1, 88. 17 (a) O. A. Vydrov and G. E. Scuseria, Assessment of a long-
6 B. D. Koivisto, A. S. Ichimura, R. McDonald, M. T. Lemaire, range corrected hybrid functional,J. Chem. Phys., 2006, 125,
L. K. Thompson, R. G. Hicks, Intramolecular pi-dimerization 234109. (b) O. A. Vydrov, J. Heyd, A. V. Krukau and G. E.
in a 1,1′-bis(verdazyl)ferrocene diradical, J. Am. Chem. Soc., Scuseria, Importance of short-range versus long-range
2006, 128, 690-691. Hartree-Fock exchange for the performance of hybrid density
7 D. Casanova, M. Llunell, P. Alemany, S. Alvarez, The rich functionals,J. Chem. Phys., 2006, 125, 074106. (c) O. A.
stereochemistry of eight-vertex polyhedra: a continuous shape Vydrov, G. E. Scuseria and J. P. Perdew, Tests of functionals
measures study, Chem. Eur. J., 2005, 11, 1479-1494. for systems with fractional electron number, J. Chem. Phys.,
8 A. Bondi, van der Waals volumes and radii, J. Phys. Chem., 2007, 126, 154109.(d)C. Lee, W. Yang and R. G. Parr,
1964, 68, 441-451. Development of the Colle-Salvetti correlation-energy formula
Published on 16 April 2020. Downloaded by Université de Paris on 4/16/2020 4:57:04 AM.

9 (a) J. Miller, J. J. Novoa, Four-center carbon-carbon into a functional of the electron density,Phys. Rev. B, 1988, 37,
bonding,Acc. Chem. Res., 2007, 40, 189-196; (b) H. Endres, in 785. (e)A. D. Becke, Density-functional thermochemistry. III.
Extended Linear Chain Compounds, ed. J.S. Miller, Plenum The role of exact exchange, J. Chem. Phys., 1993, 98, 5648. (f)
Press. New York, 1983, vol. 3, ch. 5, 263-317. A. D. Becke,Density-functional exchange-energy
10 (a) D. Gut, A. Rudi, J. Kopilov, I. Goldberg, M. Kol, Pairing approximation with correct asymptotic behavior, Phys. Rev. A,
of propellers: dimerization of octahedral ruthenium(II) and 1988, 38, 3098. (g)M. Ernzerhof and G. E. Scuseria,
osmium(II) complexes of eilatin via π-π stacking featuring Assessment of the Perdew-Burke-Ernzerhof exchange-
heterochiral recognition,J. Am. Chem. Soc., 2002, 124, 5449- correlation functional,J. Chem. Phys., 1999, 110, 5029. (h) C.
5456; (b) J. Yuasa, T. Suenobu, S. Fukuzumi, Highly self- Adamo and V. Barone, Toward reliable density functional
organized electron transfer from an iridium complex to p- methods without adjustable parameters: The PBE0 model,J.
benzoquinone due to formation of a π-dimer radical anion Chem. Phys., 1999, 110, 6158.
complex triply bridged by scandium ions,J. Am. Chem. Soc., 18 (a)F. Weigend and R. Ahlrichs, Balanced basis sets of split
2003, 125, 12090-12091. valence, triple zeta valence and quadruple zeta valence quality
11 K. E. Preuss, Pancake bonds: π-stacked dimers of organic and for H to Rn: Design and assessment of accuracy,Phys. Chem.
light-atom radicals,Polyhedron, 2014, 79, 1-15. Chem. Phys., 2005, 7, 3297. (b) D. Andrae, U. Häußermann,
12 (a) L. Noodleman, Valence bond description of M. Dolg, H. Stoll and H. Preuß, Energy-adjusted ab initio
antiferromangetic coupling in transition metal dimers, J. pseudopotentials for the second and third row transition
Chem. Phys., 1981, 74, 5737. (b) L. Noodleman, E. R. elements,Theor. Chim. Acta, 1990, 77, 123.(c)S. Grimme, J.
Davidson, Ligand spin polarization and antiferromagnetic Antony, S. Ehrlich and H. Krieg, A consistent and accurate ab
coupling in transition metal dimers, Chem. Phys., 1986, 109, initio parametrization of density functional dispersion
131-143; (c) L. Noodleman, J. G. Norman, J. H. Osborne, A. correction (DFT-D) for the 94 elements H-Pu,J. Chem. Phys.,
Aizman, D. A. Case, Models for ferredoxins: electronic 2010, 132, 154104. (d) S. Grimme, S. Ehrlich and L. Goerigk,
structures of iron-sulfur clusters with one, two, and four iron Effect of the damping function in dispersion corrected density
atoms, J. Am. Chem. Soc., 1985, 107, 3418-3426; (d) W. Koch, functional theory,J. Comput. Chem., 2011, 32, 1456.
M. C. Holthausen, A Chemist’s Guide to Density Functional 19 (a) M. Head-Gordon, Characterizing unpaired electrons from
Theory, Wiley-VCH Verlag GmbH, Weinheim, FRG, 2001. the one-particle density matrix,Chem. Phys. Lett., 2003, 372,
(e) M. Kertesz, Pancake bonding: an unusual pi-stacking 508. (b) M. Head-Gordon, Reply to comment on
interaction, Chem. Eur. J., 2019, 25, 400-416 ‘characterizing unpaired electrons from the one-particle
13 (a) P. Siegbahn, A. Heiberg, B. Roos, B. Levy, A comparison matrix’,Chem. Phys. Lett., 2003, 380, 488.
of the super-CI and the Newton-Raphson scheme in the 20 Z. Cui, H. Lischka, H. Z. Beneberu and M. Kertesz, Double
complete active space SCF method, Phys. Scr., 1980, 21, 323- Pancake Bonds: Pushing the Limits of Strong π-π Stacking
327; (b) B. O. Roos, P. R. Taylor, P. E. M. Sigbahn, A Interactions,J. Am. Chem. Soc., 2014, 136, 12958.
complete active space SCF method (CASSCF) using a density 21 M. S. Gordon, M. W. Schmidt, G. M. Chaban, K. R.
matrix formulated super-CI approach, Chem. Phys., 1980, 48, Glaesemann, W. J. Stevens and C. Gonzalez, A natural orbital
157-173; (c) B. O. Roos, R. Lindh, P. Å. Malmqvist, V. diagnostic for multiconfigurational character in correlated
Veryazov and P.-O. Widmark, Multiconfigurational Quantum wave functions,J. Chem. Phys., 1999, 110, 4199.
Chemistry, John Wiley & Sons, Inc., Hoboken, NJ, USA, 22 (a) H. Z. Beneberu, Y.-H. Tian and M. Kertesz, Bonds or not
2016. bonds? Pancake bonding in 1,2,3,5-dithiadiazolyl and 1,2,3,5-
14 (a) A. Mansikkamäki, H. M. Tuononen, The role of orbital diselenadiazolyl radical dimers and their derivatives,Phys.
symmetries in enforcing ferromagnetic ground state in mixed Chem. Chem. Phys., 2012, 14, 10713. (b) Z. Cui, H. Lischka,
radical dimers, J. Phys. Chem. Lett., 2018, 9, 3624-3630; (b) T. Mueller, F. Plasser and M. Kertesz, Study of the
D. Reta Mañeru, A. K. Pal, I. de P. R. Moreira, S. N. Datta, F. Diradicaloid Character in a Prototypical Pancake-Bonded
Illas, The triplet-singlet gap in the m-xylylene radical: a not so Dimer: The Stacked Tetracyanoethylene (TCNE) Anion Dimer
simple one, J. Chem. Theory Comput., 2014, 10, 335-345. and the Neutral K2TCNE2 Complex,ChemPhysChem, 2014,
15 J. Gräfenstein, E. Kraka, M. Filatov and D. Cremer, Can 15, 165.
Unrestricted Density-Functional Theory Describe Open Shell 23 M. E. Lines, Orbital Angular Momentum in the Theory of
Singlet Biradicals?,Int. J. Mol. Sci., 2002, 3, 360. Paramagnetic Clusters,J. Chem. Phys., 1971, 55, 2977.
16 (a) K. Yamaguchi, T. Tsunekawa, Y. Toyoda and T. Fueno, Ab 24 (a) B. S. Dolinar, D. I. Alexandropoulos, K. R. Vignesh, T.
initio molecular orbital calculations of effective exchange James and K. R. Dunbar, Lanthanide Triangles Supported by
integrals between transition metal ions,Chem. Phys. Lett., Radical Bridging Ligands,J. Am. Chem. Soc., 2018, 140, 908–
1988, 143, 371. (b) K. Yamaguchi, H. Fukui and T. Fueno, 911. (b) J. O. Moilanen, A. Mansikkamäki, M. Lahtinen, F.-S.
Molecular orbital (MO) theory for magnetically interacting Guo, E. Kalenius, R. A. Layfield and L. F. Chibotaru, Thermal

8 | J. Name., 2012, 00, 1-3 This journal is © The Royal Society of Chemistry 20xx

Please do not adjust margins

 Page 9 of 9 Inorganic
Please Chemistry
do not adjustFrontiers
margins

Journal Name COMMUNICATION

expansion and magnetic properties of benzoquinone-bridged View Article Online

dinuclear rare-earth complexes,DaltonTrans., 2017, 46, DOI: 10.1039/D0QI00365D
13582.
25 D. Reta and N. F. Chilton, Uncertainty estimates for magnetic
relaxation times and magnetic relaxation parameters, Phys.
Chem. Chem. Phys., 2019, 21, 23567.

Inorganic Chemistry Frontiers Accepted Manuscript

26 (a) L. F. Chibotaru and L. Ungur,Ab initio calculation of
anisotropic magnetic properties of complexes. I. Unique
definition of pseudospin Hamiltonians and their derivatives,J.
Chem. Phys., 2012, 137, 064112. (b) L. Ungur and L. F.
Chibotaru, Ab Initio Crystal Field for Lanthanides,Chem.Eur.
J., 2017, 23, 3708. (c) L. Ungur, M. Thewissen, J.-P. Costes,
W. Wernsdorfer and L. F. Chibotaru, Interplay of Strongly
Anisotropic Metal Ions in Magnetic Blocking of
Complexes,Inorg. Chem., 2013, 52, 6328.
27 (a) L. F. Chibotaru, L. Ungur and A. Soncini, The Origin of
Published on 16 April 2020. Downloaded by Université de Paris on 4/16/2020 4:57:04 AM.

Nonmagnetic Kramers Doublets in the Ground State of

Dysprosium Triangles: Evidence for a Toroidal Magnetic
Moment,Angew. Chemie Int. Ed., 2008, 47, 4126. (b) L.
Ungur, W. Van den Heuvel and L. F. Chibotaru,Ab initio
investigation of the non-collinear magnetic structure and the
lowest magnetic excitations in dysprosium triangles,New J.
Chem., 2009, 33, 1224.
28 (a) F.-S. Guo, B. M. Day, Y.-C. Chen, M.-L. Tong, A.
Mansikkamäki and R. A. Layfield, A Dysprosium Metallocene
Single-Molecule Magnet Functioning at the Axial
Limit,Angew. Chem., Int. Ed., 2017, 56, 11445; (b) S. Demir,
M. I. Gonzalez, L. E. Darago, W. J. Evans and J. R. Long,
Giant coercivity and high magnetic blocking temperatures for
N23- radical-bridged dilanthanide complexes upon ligand
dissociation,Nat. Commun., 2017, 8, 2144; (c) S. Jiang, B.
Wang, H. Sun, Z. Wang and S. Gao, An Organometallic
Single-Ion Magnet,J. Am. Chem. Soc., 2011, 133, 4730; (d) Y.-
S. Meng, Y.-Q. Zhang, Z.-M. Wang, B.-W. Wang and S. Gao,
Weak Ligand-Field Effect from Ancillary Ligands on
Enhancing Single-Ion Magnet Performance, Chem. – Eur. J.,
2016, 22, 12724; (e) C. A. P. Goodwin, F. Ortu, D. Reta, N. F.
Chilton and D. P. Mills, Molecular magnetic hysteresis at 60
kelvin in dysprosocenium,Nature, 2017, 548, 439; (f) C. P.
Burns, B. O. Wilkins, C. M. Dickie, T. P. Latendresse, L.
Vernier, K. R. Vignesh, N. S. Bhuvanesh and M. Nippe, A
comparative study of magnetization dynamics in dinuclear
dysprosium complexes featuring bridging chloride or
trifluoromethanesulfonate ligands,Chem. Commun., 2017, 53,
8419. (g) F.-S. Guo, B. M. Day, Y.-C. Chen, M.-L. Tong, A.
Mansikkamäki and R. A. Layfield, Magnetic hysteresis up to
80 kelvin in a dysprosium metallocene single-molecule
magnet,Science, 2018, 362, 1400.

This journal is © The Royal Society of Chemistry 20xx J. Name., 2013, 00, 1-3 | 9

Please do not adjust margins