Spin-Canted Antiferromagnetic Ordering in Transition Metal-Organic Frameworks Based on Tetranuclear Clusters with Mixed V- and Y-Shaped Ligands

Article abstract of DOI:10.1021/acs.cgd.7b00682

Four transition metal-organic frameworks were solvothermally synthesized with V-shaped 1,3-bis(1-imidazolyl)benzene (bib) and two Y-shaped carboxylate ligands (1,3,5-benzenetricarboxylic acid (H₃btc) and 3,5-pyridinedicarboxylic acid (H₂pydc)), namely, {[M₂(μ₃-OH)(bib)(btc)]·H₂O}_n (M = Co (1) and Fe (2)) and {[M′₂(μ₃-OH)(μ₂-NO₃)(bib)(pydc)]·solvents}_n (M′ = Co (3) and Ni (4)). All of them are characterized by single-crystal X-ray diffraction, infrared spectrosopy, and powder X-ray diffraction. Both complexes 1 and 2 present two-dimensional (3,8)-connected layer structures, and the point symbol is (3.4²)₂(3⁴.4⁶.5⁶.6⁸.7³.8), but Fe2 in 2 is weakly coordinated to O5 as a trigonal bipyramidal geometry compared with the tetrahedral Co2 in 1, while complexes 3 and 4 exhibit three-dimensional pillar-layer structures with (3,8)-connected tfz-d net. Interestingly, nitrate anions with a rare μ₂-η² coordination mode take part in coordination, and rectangular channels along the c axis exist in 3 and 4. Magnetic studies indicate that 1 and 2 present antiferromagnetic behaviors, while 3 and 4 show the coexistence of spin-canting and long-range magnetic ordering.

Full text of DOI:10.1021/acs.cgd.7b00682

Subscriber access provided by UNIV OF NEWCASTLE
Article
Spin-Canted Antiferromagnetic Ordering in Transition
Metal-Organic Frameworks Based on Tetranuclear
Clusters with Mixed V- and Y-Shaped Ligands
Chen Cao, Sui-Jun Liu, Shu-Li Yao, Teng-Fei Zheng, Yong-Qiang Chen, Jing-Lin Chen, and He-Rui Wen
Cryst. Growth Des., Just Accepted Manuscript • DOI: 10.1021/acs.cgd.7b00682 • Publication Date (Web): 19 Jul 2017
Downloaded from http://pubs.acs.org on July 19, 2017
Just Accepted
“Just Accepted” manuscripts have been peer-reviewed and accepted for publication. They are posted
online prior to technical editing, formatting for publication and author proofing. The American Chemical
Society provides “Just Accepted” as a free service to the research community to expedite the
dissemination of scientific material as soon as possible after acceptance. “Just Accepted” manuscripts
appear in full in PDF format accompanied by an HTML abstract. “Just Accepted” manuscripts have been
fully peer reviewed, but should not be considered the official version of record. They are accessible to all
readers and citable by the Digital Object Identifier (DOI®). “Just Accepted” is an optional service offered
to authors. Therefore, the “Just Accepted” Web site may not include all articles that will be published
in the journal. After a manuscript is technically edited and formatted, it will be removed from the “Just
Accepted” Web site and published as an ASAP article. Note that technical editing may introduce minor
changes to the manuscript text and/or graphics which could affect content, and all legal disclaimers
and ethical guidelines that apply to the journal pertain. ACS cannot be held responsible for errors
or consequences arising from the use of information contained in these “Just Accepted” manuscripts.
Crystal Growth & Design is published by the American Chemical Society. 1155
Sixteenth Street N.W., Washington, DC 20036
Published by American Chemical Society. Copyright © American Chemical Society.
However, no copyright claim is made to original U.S. Government works, or works
produced by employees of any Commonwealth realm Crown government in the course
of their duties.

Page 1 of 10
Crystal Growth & Design
1
2
3
4
5
6
SpinꢀCanted Antiferromagnetic Ordering in Transition Metalꢀ
Organic Frameworks Based on Tetranuclear Clusters with Mixed Vꢀ
and YꢀShaped Ligands
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
†
,†
†
†
,‡
†
Chen Cao, SuiꢀJun Liu,* ShuꢀLi Yao, TengꢀFei Zheng, YongꢀQiang Chen,* JingꢀLin Chen, and
,†
HeꢀRui Wen*
†
School of Metallurgy and Chemical Engineering, Jiangxi University of Science and Technology, Ganzhou 341000, Jiangxi
Province, P.R. China
‡College of Chemistry and Chemical Engineering, Jinzhong University, Jinzhong 030619, Shanxi Province, P.R. China
Supporting Information Placeholder
ABSTRACT: Four transition metalꢀorganic frameworks were solvothermally synthesized with Vꢀshaped 1,3ꢀbis(1ꢀ
imidazolyl)benzene (bib) and two Yꢀshaped carboxylate ligands (1,3,5ꢀbenzenetricarboxylic acid (H btc) and 3,5ꢀ
3
pyridinedicarboxylic acid (H pydc)), namely {[M (µ ꢀOH)(bib)(btc)]·H O} (M = Co (1) and Fe (2)) and {[M′ (µ ꢀOH)(µ ꢀNO )
2
2
3
2 n 2 3 2 3
(bib)(pydc)]
·solvents} (M′ = Co (3) and Ni (4)). All of them are characterized by singleꢀcrystal Xꢀray diffraction, infrared spectra
n
and powder Xꢀray diffraction. Both complexes 1 and 2 present a twoꢀdimensional (3,8)ꢀconnected layer and the point symbol is
2
4
6
6
8
3
(3.4 ) (3 .4 .5 .6 .7 .8), but Fe2 in 2 is weakly coordinated to O5 as a trigonal bipyramidal geometry compared with the tetrahedral
2
Co2 in 1. While complexes 3 and 4 exhibit a threeꢀdimensional ‘pillarꢀlayer’ structure with (3,8)ꢀconnected tfzꢀd net. Interestingly,
2
nitrate anions with rare µ ꢀη coordination mode take part in coordination and rectangular channels along the c axis exist in 3 and 4.
2
Magnetic studies indicate 1 and 2 present antiferromagnetic behaviors, while 3 and 4 show the coexistence of spin canting and
longꢀrange magnetic ordering.
INTRODUCTION
As an emerging multifunctional solid crystalline materials
1
ꢀ3
over the last two decades, metalꢀorganic frameworks (MOFs)
have been a hotspot not only the diversity of architectures and
fascinating topologies but also potential applications in gas
4
ꢀ6
7ꢀ8
9ꢀ10
11
storage and separation, catalysis, magnetism,
and chemical sensing.
(
optics
Among them, magnetic MOFs
MMOFs) have received much attention due to the interesting
1
2ꢀ13
magnetic phenomena and great potential applications in high
density information storage, quantum computing and magnetic
14ꢀ20
refrigeration.
To controllable synthesis of MOFs with
definite structures and desired properties, many strategies have
been developed based on the utilization of various organic
ligands with different structures and coordination abilities.
Scheme 1. The ligands bib, H
synthesis of 1–4.
btc and H pydc used for the
2
3
2
1ꢀ24
On account of several advantages, the mixedꢀligand strategy
has been well employed to prepare a large number of classical
A
Vꢀshaped imidazoleꢀcontaining ligand, 1,3ꢀbis(1ꢀ
imidazolyl)benzene (bib) (Scheme 1) with expanded rigid
configuration, may afford MMOFs with attractive framework
and topology. To our best knowledge, bib has rarely been used
to synthesize MOFs because the µ coordinated mode limits
the formation of complicated structures.
the deficiency of bib ligand system, we take full advantage of
the acidꢀbase system of mixed ligands to prepare fascinating
MMOFs. Therefore, two common and similar Yꢀshaped
carboxylate ligands (1,3,5ꢀbenzenetricarboxylic acid (H btc)
and 3,5ꢀpyridinedicarboxylic acid (H pydc)) were utilized as
2
5ꢀ29
and excellent MOF materials.
Generally, the ligands
including multidentate Oꢀ and Nꢀdonors are helpful for the
30
formation of clusterꢀbased or chainꢀbased MOFs. On the
other hand, the use of organic ligands with distinct shapes is
helpful for the control of pores in target MOFs and thus types
2
36ꢀ39
To compensate
3
1ꢀ32
of functional MOFs could be obtained.
In this regard, the
rigid organic ligands with different coordination sites and
shapes are usually used to construct robust MOFs with
3
3ꢀ35
3
permanent porosity.
As such, for rigid Nꢀdonor ligands to
2
prepare porous MOF materials, the acidꢀbase system of mixed
ligands is significant because of its special nature that could
compensate charge balance, coordination deficiency, repulsive
coꢀligands, taking into account the effect of different
carboxylates on the structures in the acidꢀbase system.
Compared with H btc, H pydc has less coordination sites and
25
3
2
vacuum and weakly interaction all at once.
thus more rigidity in configuration is presented. This work
ACS Paragon Plus Environment

Crystal Growth & Design
Page 2 of 10
may provide certain proofs to investigate the effect of the
rigidity of organic coꢀligand on the structures of MMOFs in
mixedꢀligand system.
~60%). Large block of crystalline bib was then obtained by
recrystallization of the white powder in CH Cl /CH OH. Bib
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
2
2
3
crystallizes in the monoclinic P2 /c group and its molecular
1
To prepare desired MMOFs, the suitable choice of
paramagnetic metal ions is another important factor.
Transition metal ions with different valence states are good
candidates because they usually have strong coordination
ability, rich coordination configuration and various magnetic
structure is shown in Figure S1 (SI).
II
II
II
behaviors. Among them, Fe , Co and Ni ions have been well
used to construct transition MMOFs with fascinating
structures and interesting magnetic phenomena.
Scheme 2. The synthetic route to bib.
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
Synthesis of {[Co (µ ꢀOH)(bib)(btc)]·H O} (1):
A
2
3
2
n
Herein, we have successfully synthesized and characterized
four MMOFs, namely {[M (µ ꢀOH)(bib)(btc)]·H O} (M = Co
mixture of Co(NO ) ·6H O (58 mg, 0.2 mmol), bib (21 mg,
3
2
2
2
3
2
n
0.1 mmol) and H btc (21 mg, 0.1 mmol) in 5 mL of
3
(1)
and
Fe
(2))
and
{[M′ (µ ꢀOH)(µ ꢀNO )
2 3 2 3
component solvent (VDMF:Vdeionized water = 4:1) was sealed in a
23 mL Teflonꢀlined autoclave and heated at 120 ℃ for 72 h.
After the autoclave was cooled to RT in 24 h, purple block
crystals were obtained in about 50% yield based on bib.
Elemental analysis (%) calcd for C H Co N O : C, 44.23; H,
(
bib)(pydc)]·solvents} (M′ = Co (3) and Ni (4)). Structural
n
characterization revealed that complexes 1 and 2 show twoꢀ
dimensional (2D) (3,8)ꢀconnected framework based on
tetranuclear clusters with a slight difference. While complexes
3 and 4 present threeꢀdimensional (3D) (3,8)ꢀconnected tfzꢀd
net derived from tetranuclear clusters with rectangular
channels along the c axis, showing a point symbol of
2
1
16
2
4
8
ꢀ
2
.83; N, 9.83. Found: C, 43.72; H, 2.95; N, 9.95. IR (KBr, cm
1
): 3535w, 3426w, 3123m, 1616s, 1566s, 1518s, 1438m,
3
6
18
4
1368s, 1195m, 1112w, 1070m, 998w, 936w, 854m, 773m,
(
4 ) (4 .6 .8 ). Magnetic investigations suggest that 1 and 2
2
7
08s, 653w, 550w, 458m.
display antiferromagnetism, while 3 and 4 show spinꢀcanted
antiferromagnetic ordering.
Synthesis of {[Fe (µ ꢀOH)(bib)(btc)]·H O} (2):
A
2
3
2
n
mixture of Fe(SO ) ·7H O (56 mg, 0.2 mmol), bib (21 mg, 0.1
4
2
2
mmol) and H btc (21 mg, 0.1 mmol) in 8 mL of component
3
EXPERIMENTAL SECTION
solvent (VDMF:Vdeionized water:Vethanol = 4:2:2) was sealed in a 23
mL Teflonꢀlined autoclave and heated at 180 ℃ for 72 h. Then
the autoclave was cooled to RT in 24 h, and yellow block
crystals were obtained in ~25% yield based on bib. Elemental
Materials and Physical Measurements. All reagents were
of analytical grade and used as purchased except the bib ligand.
Elemental analyses (C, H and N) were carried out with a
PerkinꢀElmer 240C analyzer. Powder Xꢀray diffraction
analysis (%) calcd for C H Fe N O : C, 44.72; H, 2.86; N,
21 16
2
4
8
ꢀ
1
9.93. Found: C, 42.53; H, 2.29; N, 9.22. IR (KBr, cm ):
(PXRD) patterns were recorded on an Empyrean
3
1
4
485w, 3124w, 1616s, 1566m, 1516m, 1442w, 1367s, 1282w,
254w, 1113w, 1069w, 931w, 855w, 772w, 740m, 599w,
56w.
diffractometer (PANalytical B.V.) with a Cuꢀtarget tube and a
graphite monochromator. The simulated PXRD spectra were
from the singleꢀcrystal data and the Mercury (Hg) program
obtained free from the website at http://www.iucr.org. The IR
Synthesis
of
{[Co (µ ꢀOH)(µ ꢀNO )
2 3 2 3
(
bib)(pydc)]·solvents}n (3): A mixture of Co(NO ) ·6H O
spectra were obtained on
spectrometer with KBr pellets. Thermogravimetric analyses
TGAs) were carried out on a NETZSCH STA2500 (TG/DTA)
thermal analyser under nitrogen atmosphere at a heating rate
a
Bruker ALPHA FTꢀIR
3 2
2
(
58 mg, 0.2 mmol), bib (21 mg, 0.1 mmol) and H pydc (17
2
mg, 0.1 mmol) in 5 mL of component solvent (VDMF:Vdeionized
(
=
4:1) was sealed in a 23 mL Teflonꢀlined autoclave and
water
ꢀ
1
heated at 160 ℃ for 36 h. And then the autoclave was cooled
to RT in 24 h, red block crystals were obtained in ~40% yield
of 10 ℃ min . Magnetic susceptibility measurements were
performed on a Quantum Design MPMS superconducting
quantum interference device (SQUID). All magnetic data were
corrected for the diamagnetic susceptibility by using Pascal's
constants and for contribution of the sample holder by
experimental measurement.
ꢀ
1
based on bib. IR (KBr, cm ): 3430w, 3104w, 2366w, 1616s,
1517m, 1385s, 1248w, 1121w, 1063w, 935w, 827w, 765w,
655w, 586w, 443w.
Synthesis
of
{[Ni (µ ꢀOH)(µ ꢀNO )(bib)
2 3 2 3
(pydc)]·solvents}n (4): Complex 4 was synthesized by the
similar procedure used for preparation of 3, except that
Co(NO ) ·6H O (58 mg, 0.2 mmol) was replaced by
Synthesis of bib: The synthetic route to bib is shown in
Scheme 2. A mixture of 1,3ꢀdibromobenzene (2.36 g, 10
mmol), imidazole (1.63 g, 24 mmol), 1,10ꢀphenanthroline
monohydrate (0.48 g, 2.4 mmol), K CO (5.53 g, 40 mmol)
3 2
2
Ni(NO ) ·6H O (58 mg, 0.2 mmol). After the autoclave was
3 2
2
2
3
cooled to RT in 24 h, green block crystals were obtained in
and CuI (0.34 g, 1.8 mmol) was dissolved in 100 mL N,Nꢀ
dimethylformamide (DMF) with 250 mL flask and refluxed
ꢀ
1
~
60% yield based on bib. IR (KBr, cm ): 3448w, 3099w,
1
9
620s, 1516m, 1386s, 1300w, 1247w, 1120w, 1062w, 1002w,
35w, 832w, 768w, 740w, 654w, 455w.
under N atmosphere for 72 h. After cooling down to room
2
temperature (RT), the reaction mixture was extracted with
CH Cl for three times and the organic phases were combined.
Xꢀray Data Collection and Structure Determinations.
2
2
All of crystallographic data were collected on Bruker D8
QUEST diffractometer with MoꢀKα radiation ( = 0.71073 Å)
by scan mode. Program SAINT was used for integration of
Then the product was further washed by distilled water for
λ
five times and dried with anhydrous MgSO . Through the
4
filtration and evaporation to dryness under reduced pressure to
remove CH Cl , the reddishꢀbrown crude was obtained. The
ω
40
the diffraction profiles. All structures were solved by direct
method and refined by fullꢀmatrix leastꢀsquares methods
2
2
crude was further purified with a flash chromatography with
V(CH Cl )/V(CH OH) = 20:1, yielding a white power (1.26 g,
4
1
through the SHELXTL program. The nonꢀhydrogen atoms
2
2
3
2
ACS Paragon Plus Environment

Page 3 of 10
Crystal Growth & Design
were identified by successive difference Fourier syntheses and
suitable constrains. The solvent molecules in the channels of 3
and 4 are highly disordered, and removed by SQUEEZE
program in PLATON. A summary of the crystal data and
structure refinements for bib and 1–4 is given in Table 1. The
selected bond lengths and angles of 1–4 are provided in Table
S1 (SI).
2
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
refined with anisotropic thermal parameters on F . The
hydrogen atoms of organic ligands were generated by the
riding mode and refined isotropically with fixed thermal
factors. The hydrogen atoms of water molecules in 1 and 2
were added by the difference Fourier maps and refined with
4
2
Table 1. Crystal data and structure refinements for bib and 1–4
Compound
formula
Mr
bib
1
2
3
4
C H N
C H Co N O
C H Fe N O
C H Co N O
C H Ni N O
12 10
4
21 16
570.24
299(2)
Triclinic
P
2
4
8
21 16
564.08
293(2)
Triclinic
P
2
4
8
19 14
572.22
293(2)
2
6
8
19 14
571.78
293(2)
2
6
8
210.24
293(2)
Monoclinic
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
T (K)
crystal system
space group
a (Å)
b (Å)
c (Å)
Monoclinic
C2/c
Monoclinic
C2/c
P2 /c
1
8.883(3)
13.246(5)
11.332(3)
90
128.672(17)
90
10.3297(9)
10.4480(9)
11.0387(9)
11.1649(9)
109.0524(17)
89.9812(17)
117.1885(12)
1065.56 (15)
2
29.293(11)
11.127(4)
19.674(7)
90.00
95.699(8)
90.00
28.978(4)
10.9548(10)
11.1672(10)
108.744(2)
90.697(2)
117.049(2)
1046.82 (16)
2
11.0040(15)
19.605(3)
90.00
95.042(3)
90.00
α (º)
β (º)
γ (º)
V (Å )
3
1041.0(6)
4
6381(4)
8
6227.4(15)
8
Z
F(000)
440
1.341
0.086
576
1.809
1.645
572
2304
2320
ꢀ
3
Dcalc (g cm )
1.758
1.191
1.220
–
1
µ (mm )
1.421
1.081
1.252
reflections
collected/unique
1
2016/1813
11482/3659
21864/3760
0.0164
15306/5219
0.0951
48000/5476
0.0345
R
0.0775
0.0220
0.0260/0.0634
1.054
int
a
b
R /wR [I2>2σ(I)] 0.0623/0.1443
0.0267/0.0682
1.064
0.1092/0.3101
0.0815/0.2339
1.068
1
2
GOF on F
1.111
1.069
a
b
2
2 2
2 2 1/2
R = ∑||F |ꢀ|F ||/∑|F |, wR = [∑w(F ꢀF ) /∑w(F ) ]
.
1
o
c
o
2
o
c
o
shaped tetranuclear cluster [Co (µ ꢀOH) (CO ) ] (Figure 1b).
4
3
2
2 4
II
RESULTS AND DISCUSSION
The adjacent tetranuclear Co clusters are further linked by
3ꢀ
btc and bib ligands to give the 2D structure. Interestingly, the
role of bib ligands in this structure likes the arch bridge over
the lake. The topology analysis of 1 indicates that a (3,8)ꢀ
Synthesis. By using mixedꢀligand strategy, four tetranuclear
clusters based MMOFs have been successfully produced and
II
2
4
6
6
8
3
the ratio of M salts, bib and corresponding carboxylate
connected net with a point symbol of (3.4 ) (3 .4 .5 .6 .7 .8)
2
44
ligands is 2:1:1. Some differences of synthetic conditions
can be rationalized by TOPOS 4.0 as shown in Figure 1d,
II
indicate that the synthesis of Fe ꢀbased MOFs is more
where Co clusters are considered as eightꢀconnected nodes,
4
3ꢀ
difficulty than that of other transition MOFs, which is resulted
from iron ions exhibiting a strong tendency to undergo
and btc ligands act as threeꢀconnected nodes. In addition, the
3D packing structure (Figure S2a, SI) indicates the existence
of the weak intermolecular CꢀH…O hydrogen bonds due to
the short distances (Table S2, SI). The accessible volume for 1
43
hydrolysis into a stable polymeric hydrated iron oxide.
Crystal Structure of {[Co (µ ꢀOH)(bib)(btc)]·H O} (1)
2
3
2
n
42
3
and {[Fe (µ ꢀOH)(bib)(btc)]·H O}
(2). Complex
1
calculated by PLATON is 69.5 Å (6.6%) per unit cell
volume when the solvent molecules were removed. Complex 2
takes a similar structure with 1 except that Fe2 is weakly
coordinated to O5B as a trigonal bipyramidal geometry
compared with the tetrahedral Co2 in 1 (Figure S2b, SI).
2
3
2
n
crystalizes in the triclinic P space group. The asymmetric uniItI
of 1 consists of two crystallographically independent of Co
3ꢀ
ꢀ
ions, one bib ligand, one btc ligand, one µ ꢀOH and one
3
lattice water molecule. As shown in Figure 1a, Co1 is sixꢀ
coordinated by three carboxylate O atoms (O1, O3A and O5B)
Crystal
Structure
of
{[Co (µ ꢀOH)(µ ꢀNO )
2 3 2 3
3
ꢀ
from three different btc ligands, two O atoms (O7 and O7C)
(bib)(pydc)]·solvents}n (3) and {[Ni (µ ꢀOH)(µ ꢀNO )
2
3
2
3
ꢀ
from distinct OH anions, and one N atom (N1) from bib
(bib)(pydc)]·solvents}n
(4). Complexes
3
and
4
are
ligand, which generate the distorted [CoNO ] octahedral
isostructural, and thus herein the structure of 3 was described
in detail. Complex 3 belongs to the monoclinic C2/c space
group. The asymmetry unit contains two crystallographically
5
geometry [Co1–O = 2.0728(15)–2.1552(15) Å and Co1–N =
2
.108(2) Å]. While Co2 is fourꢀcoordinated with irregular
II
2ꢀ
[
(
(
CoNO ] tetrahedral geometry by two carboxylate O atoms
independent Co ions, one bib ligand, one pydc ligand, one
3
3ꢀ
ꢀ
ꢀ
I
I
O2 and O4D) from two independent btc ligands, one O atom
µ ꢀOH and one NO anion. As shown in Figure 2a, each Co
3 3
ꢀ
O7) from the OH group and one N atom (N4A) from bib
ion presents sixꢀcoordinated irregular octahedral geometry.
Co1 is surrounded by five O atoms (O1, O3C, O5, O5A and
ligand [Co2–O = 1.9414(17)–1.9718(15) Å and Co2—N =
II
ꢀ
2ꢀ
ꢀ
ꢀ
2
.074 Å]. The Co centers are connected by µ ꢀOH and synꢀ
O6) from independent pydc ligands, NO3 and OH anions,
and one N atom (N1) from bib ligand [Co1–O = 2.074(8)–
3
1
1
3ꢀ
synꢀµ ꢀη ꢀη carboxylates of btc ligands to form butterflyꢀ
2
3
ACS Paragon Plus Environment

Crystal Growth & Design
.167(8) Å and Co1–N = 2.097(9) Å]. And Co2 is coordinated
Page 4 of 10
2
topological analysis was performed. If Co4 clusters were
2ꢀ
2ꢀ
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
by four O atoms (O2, O4B, O5 and O6) from different pydc
treated as eightꢀconnected nodes and pydc ligands as threeꢀ
connected nodes, the topology of 3 is a 3D (3,8)ꢀconnected tfzꢀ
d network with a point symbol of (4 )
2d and Figure S2c, SI).
Structural Comparison. Although both 1 and 3 take
tetranuclear clusters based highꢀdimensional structures with
(3,8)ꢀconnected net, their structures are much different. Firstly,
Co2 in 1 is fourꢀcoordinated, and while both Co1 and Co2 in 3
are sixꢀcoordinated, which lead to the complicated 3D
ꢀ
ꢀ
ligands, NO3 and OH anions, and two N atoms (N4D and
2
ꢀ
3
6
18
4
N5C) from bib ligand and pydc ligand [Co2－O = 2.051(7) –
2
(4 .6 .8 ) (see Figure
2.212(8) Å and Co2–N = 2.131(9)–2.213(8) Å]. To our best
ꢀ
1
knowledge, the NO anion in with µ ꢀη coordination mode is
3
2
II
II
45ꢀ48
II
rare in Co and Ni complexes.
are interlinked by four carboxylate groups with synꢀsynꢀµ ꢀη ꢀ
The neighboring Co ions
2 1
1
ꢀ
ꢀ
η
bridging mode, two µ ꢀOH and two NO3 anions,
3
II
generating a tetranuclear Co center with butterfly shape,
namely [Co (µ ꢀOH) (µ ꢀNO ) (CO ) ] (Figure 2b).
structure of 3. Secondly, nitrate anions in 3 take part in
coordination and exhibits rare µ
4
3
2
2
3 2
2 4
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
2
2ꢀ
Meanwhile, the combination of Co centers and pydc ligands
2
ꢀη coordination mode. Last
4
3
−
2ꢀ
form twoꢀdimensional layer. The layers are further bridged by
bib ligands to generate 3D frameworks, accompanying with
oneꢀdimensional rectangular channels (8.5× 13.2 Å in size)
along the c axis. Therefore, the structure can be seen as ‘pillarꢀ
layer’ framework. After the solvent molecules were removed
from the channels, the accessible volume for 3 calculated by
but not the least, the btc in
η :η :η :η :η bridging model (see Figure 3) and both of
them are completely protonated, but one atom in btc is
free. Notably, the btc in
bridging model considering the existence of the weak Feꢀ
O coordination bond. In addition, the rigidity of carboxylate
ligands may favor the construction of higher dimensional
framework.
1
and pydc in
3 reveals µ ꢀ
5
1
1
1
1
1
3−
3−
1
1
1
1
2
2 exhibits µ6ꢀη :η :η :η :η
42
3
PLATON is 2740.2 Å (42.9%) per unit cell volume. To gain
a better visualization and understanding of the structures of 3,
II
Figure 1. Views of (a) the coordination environments and linkage modes of Co in 1 (H atoms omitted for clarity); (b) the butterflyꢀ
shaped Co cluster in 1; (c) the polyhedron representation 2D network of 1; (d) the (3,8)ꢀconnected topology of 1. Symmetry codes: A: 1ꢀ
4
x, 1ꢀy, 1ꢀz; B: ꢀx, ꢀy, 1ꢀz; C: ꢀx, 1ꢀy, 1ꢀz; D: ꢀ1+x, y, z.
4
ACS Paragon Plus Environment

Page 5 of 10
Crystal Growth & Design
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
(
e)
II
Figure 2. Views of (a) the coordination environments and linkage modes of Co in 3 (H atoms omitted for clarity); (b) the 2D network
based on butterflyꢀshaped Co clusters; (c) the 3D pillarꢀlayer framework of 3 showing open 1D channels along the c axis; (d) the 1D
channel running along the c axis; (e) the (3,8)ꢀconnected tfzꢀd topology of 3. Symmetry codes: A: 1/2ꢀx, 1/2ꢀy, 1ꢀz; B: x, 1ꢀy, 1/2+z; C: 1/2ꢀ
x, 1/2+y, 1/2ꢀz; D: 1/2+x, 1/2+y, z.
4
3
ꢀ
2ꢀ
II
II
Figure 3. Views of the bridging model of deprotonated btc and pydc ligands with Co ions (a, c) and Fe ions (b).
5
ACS Paragon Plus Environment

Crystal Growth & Design
Page 6 of 10
PXRD patterns and TGA. To confirm the phase purities of value of 3 gradually decreases down to a minimum value of
3
ꢀ1
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
these complexes, the PXRD patterns were performed on
polycrystalline samples. The PXRD patterns of the asꢀ
synthesized samples are well consistent with their
corresponding simulated ones, indicating the phase purities of
the bulk samples (Figure S3, SI). To study the thermal
stabilities of these complexes, they were carried out for TGA
experiments from 20 to 900 ℃ under nitrogen atmosphere. As
shown in Figure S4 (SI), the results indicate that the lattice
water of 1 and 2 were removed below 286 and 256 ℃ , and
their frameworks finally decomposed at about 380 and 353 ℃ ,
respectively. And the framework of 3 and 4 keep stable until
3.40 cm mol K at 16 K, which is much smaller than the
theoretical values (7.50 cm mol K) of four spinꢀonly Co
ions and indicates antiferromagnetic coupling between Co
3
ꢀ1
II
II
ions. Upon lowering the temperature to 10 K, the χ T abruptly
m
3
ꢀ1
increase to a maximum value (4.21 cm mol K) and then the
3
χ T has a rapid linear drop with a minimum value of 1.53 cm
m
ꢀ1
mol K at 2.0 K. Above mentioned indicates canted
antiferromagnetism exsits in 3. Curie–Weiss fitting in the high
temperatur range leads to C = 13.18 cm mol K and θ =
14
3
−1
3
−1
−78.16 K for 1 and C = 10.49 cm mol K and θ = −43.89 K for
3, respectively. The C values corresponds to g = 2.65 (1) and
2.37 (3), respectively, being normal for the significant spin–
orbit coupling. The strength of the antiferromagnetic exchange
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
3
40 and 390 ℃ , respectively. All above suggest they have
relatively good thermal stabilities.
II
Magnetic Properties. The direct current (dc) magnetic
susceptibilities of 1–4 have been performed on polycrystalline
samples from 2 K to 300 K at an applied field of 1 kOe. In
order to investigate the M4 unit (M = Co, Fe, Ni), the
calculated molecular weights for magnetic data of 1–4 are
interaction caused by spin–orbit coupling of Co at high
49
temperature was estimated based on eq (1).
χ
T = Aexp( − E /kT) + Bexp( − E /kT)
(1)
1
2
In eq (1), A + B equals the curie constant, and E and E
1
2
represent the “activation energies” corresponding to the spinꢀ
orbit coupling and the antiferromagnetic exchange interaction.
The best fitting of the experimental data gives that A + B =
1140.48, 1128.16, 1144.44 and 1143.56, respectively.
3
For 1 and 3, the χ T values at 300 K are 10.19 and 8.95 cm
m
−1
3
−1
mol K, which are significantly larger than that (7.50 cm mol
K) expected for four isolated highꢀspin Co ions (S = 3/2, g =
.0). This is a common phenomenon for Co ions due to its
3
ꢀ1
II
12.40 cm mol K, –E /k = –59.92 K, –E /k = –4.05 K for 1,
1 2
3 ꢀ1
II
and A + B = 10.32 cm mol K, –E /k = –46.43 K, –E /k = –
1 2
2
6
.93 K for 3 (Figures 4a and 4b). The negative values of –E /k
2
strong spin–orbit coupling interactions. For 1, as the
indicate that dominant antiferromagnetic interactions between
temperature decreases, the χ T value slowly decreases down to
m
II
3
−1
Co ions within the Co clusters exist in 1 and 3.
4
a minimum value of 0.33 cm mol K at 2.0 K, indicating the
exsitence of antiferromagnetic behavior. On cooling, the χmT
(a)
(b)
(c)
ꢀ
1
Figure 4. The χ T vs T plots (red lines reprensent for the best fitting) and χM vs T plots (red lines reprensent for the CurieꢀWeiss fitting)
m
of 1 (a), 3 (b) and 4 (c) under applied field of 1kOe.
3
−1
3
−1
For 2, the roomꢀtemperature χ T value is 15.46 cm mol
K
cm mol K and θ = −4.38 K. The negative θ value further
m
II
(
see Figure S5a, SI), which is somewhat larger than the
expected vlaue (12 cm mol K) for four isolated highꢀspin Fe
confirm the antiferromagnetic couplings between adjacent Ni
ions. Therefore, complex 4 exhibits canted antiferromagnetic
3
−1
II
ions (S = 2, g = 2.0). With the temperature decreasing, the χ T
behavior on the whole.
m
3
−1
linearly decreases to a minimum value of 0.31 cm mol K,
indicating strong antiferromagnetic exchange interactions. As
3
−1
for 4, the χ T value at room temperature is 3.51 cm mol K,
m
3
−1
being somewhat smaller than the expected vaule of 4 cm mol
K for four uncoupled Ni ions (S = 1, g = 2.0). On cooling the
II
temperature to 24 K, the χ T value almost remain unchanged
m
above 100 K and gradually decreases down to a minimum
3
ꢀ1
value of 2.75 cm mol K at 24 K, indicating the
II
antiferromagnetic interaction between Ni centers. Upon
Scheme 3. The schematic representation of magnetic mode in 4.
further lowering the temperature to 14 K, the χ T abruptly
m
3
ꢀ1
II
II
increase to a maximum value (3.65 cm mol K) and then the
Taking into account the fact that the Ni ꢀNi interaction
3
χ T has a rapid linear drop with a minimum value of 0.47 cm
between Ni units is expected to be negligibly small, complex
m
4
ꢀ1
II
mol K at 2.0 K. Curie–Weiss fitting above 26 K gives C = 3.57
4 can be simplified as a tetranuclear Ni complex from
6
ACS Paragon Plus Environment

Page 7 of 10
Crystal Growth & Design
II
magnetic point of view (Scheme 3). A quantitative analysis for
4 has been performed on the basis of expression derived from
based Co MOFs, but only 3 exhibits spin canting behavior,
II
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
which suggests that the anisotropy of Co is not the key factor.
the spinꢀonly Hamlitonian, as shown in eq (2) and the
expression is revealed in eq (3).
Hence, in the present case, the existence of inversion centers
between the adjacent spins in 1 forbids the occurrence of
antisymmetric exchange interactions, and due to the fact that
there are no symmetric centers between the neighboring
tetranuclear units, the intercluster magnetic exchanges in 3 and
4 can be antisymmetric.
5
0
ˆ
ˆ ˆ
ˆ ˆ
ˆ ˆ
ˆ ˆ
ˆ ˆ
1A
H = −2J1S S − 2J2(S S + S S + S S + S S ) (2)
1
1A
1
2
1
2A
1A 2A
2
8
b
14b
18b
4a+4b
4a+10b
4a+14b
6a+8b
8a+6b
1
80+84e +30e + 6e +168e
+ 60e
+12e
+ 60e
+ 30e
2
2
8a+10b
10a+8b
Ng
β
+ 6e
+12e
14b
χM
=
×
8b
18b
20b
4a+4b
4a+10b
4a+14b
6a+8b
8a+6b
3kT
9+ 7e + 5e +3e + e +14e
+10e
+ 6e
+10e
+5e
8
a+10b
8a+12b
10a+8b
12a+8b
+
3e
+ e
+ 6e
+ e
where a = –J /kT and b = –J /kT (3)
1
2
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
Leastꢀsquares fitting of the experimental data at 26ꢀ100 K
leads to the following set of parameters: g = 2.00 (fixed), J1
Ni
ꢀ
1
ꢀ1
=
−0.14 cm and J = −2.18 cm (Figure 4c). The negative
2
values of J and J further indicates that antiferromagnetic
1
2
II
interaction exists among the neighboring Ni centers.
The M vs. H plots (at 2 K) for 1–4 are shown in Figure S5b
(SI). The magnetizations of 1–4 increase slowly and reach to
1.80, 3.2, 2.42 and 1.15 Nβ at 70 kOe, which are far from the
saturation values, respectively. The results further suggest
antiferromagnetic couplings between the adjacent metal
◦
centers. The canting angles of 3 and 4 at 2 K are about 4.2 and
◦
3
.7 estimated with the equation sin(γ) = M /M (M obtained
R
S
R
by extrapolating the highꢀfield linear part of the magnetization
5
1
(a)
curve at 2 K to zero field).
To investigate the lowꢀtemperature behaviors of 3 and 4, the
temperature dependencies of fieldꢀcooled (FC) and zeroꢀfieldꢀ
cooled (ZFC) magnetization were performed under a field of 20
Oe upon warming from 2 K (Figure 5). The FC and ZFC curves
of 3 and 4 completely diverge below 11 K and 18.5 K,
respectively, suggesting the onset of longꢀrange ordering at low
temperture. Moreover, no obvious frequencyꢀdependent ac
II
signals appear although anisotropic Co centers exist in 3. Both
the inꢀphase (χ') and outꢀofꢀphase (χ'') signals of 3 and 4 are
consistent with the spinꢀcanted antiferromagnetic ordering
behaviors (Figure S6, SI). Moreover, the obvious peaks of χ''
II
curves in 3 is resulted from the strong anisotropy of Co ions.
II
As shown in Table 2, tetranuclear clusters based Co and
II
Ni MOFs usually contain M (ꢁ ꢀOH) cores and exhibit
4
3
2
antiferromagnetic interactions within the clusters. The reason
may be ascribed to the existence of synꢀsynꢀcarboxylate and
µ3ꢀOH bridges. As is known, spin canting may be ascribed to
(b)
Figure 5. The FC/ZFC curves at low temperature for 3 (a) and 4
two mechanisms: the singleꢀion magnetic anisotropy and the
(b).
52ꢀ54
antisymmetric magnetic exchange.
Although 1–4 all
belong to centrosymmetric space group, only 3ꢀ4 present spinꢀ
canting behaviors. Both 1 and 3 are tetranucluear clusters
II
II
Table 2. Structures and magnetic properties of some selected tetranuclear clusters based Co and Ni MOFs
intraꢀcluster
magnetic
interactions
Bulk Magnetic
behaviour
Compounds
Cluster core
Network
[
(
{
Co (ꢁ ꢀOH)(ꢁ ꢀH O)(pyrazine)(oba)ꢀ
spin canting
slow relaxation
spin canting
spin glass
spin canting
spin glass
2
3
2
2
55
Co
Co
4
4
(ꢁ
(ꢁ
3
3
ꢀOH)
2
2
(ꢁ
2
ꢀH
2
O)
2
8ꢀc
AF
AF
obaH)]n
[Co (ina) (ꢁ ꢀOH) (H O)(EtOH)]ꢀ
4
5
3
2
2
56
ꢀOH)
7ꢀc vmr
9ꢀc bctꢀ9ꢀP2
6ꢀc
·NO ·2EtOH·4H O}
3 2 n
{
[Ni (ina) (ꢁ ꢀOH) (H O)(EtCOO)]·6EtOHꢀ
4
5
3
2
2
56
Ni
Ni
4
(ꢁ
(ꢁ
3
3
ꢀOH)
2
/c AF
1
·2H O}
2 n
{
[Ni (ꢁ ꢀOH) (ina) (dpda) (H O) ]·9H Oꢀ
spin canting
spin glass
4
3
2
2
2
2
3
2
54
n
4
ꢀOH)
2
AF
·3C H O}
[Me NH ][Co (bptc)(ꢁ ꢀOH)(H O) ]
[Me NH ][Ni (bptc)(ꢁ ꢀOH)(H O) ]
2
6
5
7
Co (ꢁ ꢀOH)
2
Ni (ꢁ ꢀOH)
(4,8)ꢀc scu
(4,8)ꢀc scu
AF
F
antiferromagnet
ferromagnet
2
2
2
3
2
2 n
4
3
5
7
2
2
2
3
2
2 n
4 3 2
7
ACS Paragon Plus Environment

Crystal Growth & Design
Page 8 of 10
1
3
4
Co
Co
4
4
(ꢁ
(ꢁ
3
3
ꢀOH)
ꢀOH)
2
(3,8)ꢀc
(3,8)ꢀc tfzꢀd
(3,8)ꢀc tfzꢀd
AF
AF
AF
antiferromagnetism
Spin canting
Spin canting
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
(ꢁ
ꢀNO
ꢀNO
)
2
2
3
2
Ni
(ꢁ
ꢀOH)
(ꢁ
)
2
4
3
2
2
3
oba = 4,4′ꢀoxybis(benzoate), ina = isonicotinate, dpda = 2,6ꢀdimethylꢀpyridineꢀ3,5ꢀdicarboxylate, bptc = 3,3′,4,4′ꢀbiphenyltetracarboxylate AF =
antiferromagnetic and F = ferromagnetic.
CONCLUSION
REFERENCES
By the employment of mixedꢀligand strategy, four new
3,8)ꢀconnected 2D/3D MMOFs have been successfully
synthesized. The bib ligands serve as arch bridges and µ ꢀOH
anions play a key role in the formation of tetranuclear
butterflyꢀshaped clusters, while nitrate anions with rare µ ꢀη
coordination mode take part in coordination in 3 and 4.
1 and 2 exhibit
antiferromagnetic behaviors, while 3 and 4 show the
(1) Li, B.; Wen, H.ꢀM.; Cui, Y.; Zhou, W.; Qian, G.; Chen, B. Adv.
Mater. 2016, 28, 8819ꢀ8860.
(
(
2) Furukawa, H.; Cordova, K. E.; O’Keeffe, M.; Yaghi, O. M.
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
3
Science 2013, 341, 1230444.
2
(3) Bu, X.ꢀH.; Zuo, J.ꢀL. Sci. China Chem. 2016, 59, 927ꢀ928.
4) Kang, Y.ꢀH.; Liu, X.ꢀD.; Yan, N.; Jiang, Y.; Liu, X.ꢀQ.; Sun,
L.ꢀB.; Li, J.ꢀR. J. Am. Chem. Soc. 2016, 138, 6099ꢀ6102.
2
(
Magnetic investigates indicate that
(5) Li, B.; Wen, H.ꢀM.; Wang, H.; Wu, H.; Tyagi, M.; Yildirim, T.;
Zhou, W.; Chen, B. J. Am. Chem. Soc. 2014, 136, 6207−6210.
(6) Zhang, L.; Zou, C.; Zhao, M.; Jiang, K.; Lin, R.; He, Y.; Wu,
C.ꢀD.; Cui, Y.; Chen, B.; Qian, G. Cryst. Growth Des. 2016, 16,
194–7197.
7) Lee, J.; Farha, O. K.; Roberts, J.; Scheidt, K. A.; Nguyen, S. T.;
Hupp, J. T. Chem. Soc. Rev. 2009, 38, 1450−1459.
8) Yoon, M.; Srirambalaji, R.; Kim, K. Chem. Rev. 2012, 112,
196–12317.
9) Biswas, S.; Mondal, A. K.; Konar, S. Inorg. Chem. 2016, 55,
085−2090.
10) Wang, H.ꢀY.; Ge, J.ꢀY.; Hua, C.; Jiao, C.ꢀQ.; Wu, Y.; Leong,
coexistence of spin canting and longꢀrange magnetic ordering.
Further studies of clusterꢀbased MMOFs with interesting
structures and magnetic phenomena are underway in our group.
7
(
ASSOCIATED CONTENT
(
1
2
Supporting Information.
(
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acs.cgd.xxxxxxx.
Supplementary tables, structural figures, PXRD patterns, TGA
curves and magnetic data.
(
C. F.; D’Alessandro, D. M.; Liu, T.; Zuo, J.ꢀL. Angew. Chem. Int. Ed.
2017, 56, 5465–5470.
(
11) Cui, Y.; Yue, Y.; Qian, G.; Chen, B. Chem. Rev. 2012, 112,
Accession Codes
1126–1162.
CCDC 1548660 and 1548330ꢀ1548333 for bib and complexes 1
, respectively, contain the supplementary crystallographic data
for this paper. These data can be obtained free of charge via
www.ccdc.cam.ac.uk/data_request/cif, or by emailing
data_request@ccdc.cam.ac.uk, or by contacting The Cambridge
Crystallographic Data Centre, 12 Union Road, Cambridge CB2
–
(12) Liu, X.ꢀJ.; Zhang, Y.ꢀH.; Chang, Z.; Li, A.ꢀL.; Tian, D.; Yao,
Z.ꢀQ.; Jia, Y.ꢀY.; Bu, X.ꢀH. Inorg. Chem. 2016, 55, 7326–7328.
(13) Kreno, L. E.; Leong, K.; Farha, O. K.; Allendorf, M.; Duyne,
R. P. V.; Hupp, J. T. Chem. Rev. 2012, 112, 1105–11259.
14) Weng, D.ꢀF.; Wang, Z.ꢀM.; Gao, S. Chem. Soc. Rev. 2011, 40,
157–3181.
15) Zhang, X.; Vieru, V.; Feng, X.; Liu, J.ꢀL.; Zhang, Z.; Na, B.;
Shi, W.; Wang, B.ꢀW.; Powell, A. K.; Chibotaru, L. F.; Gao, S.;
Cheng, P.; Long, J. R. Angew. Chem. Int. Ed. 2015, 54, 9861 –9865.
(16) Lorusso, G.; Sharples, J. W.; Palacios, E.; Roubeau, O.;
Brechin, E. K.; Sessoli, R.; Rossin, A.; Tuna, F.; McInnes, E. J. L.;
Collison, D.; Evangelisti, M. Adv. Mater. 2013, 25, 4653–4656.
(17) Han, S.ꢀD.; Zhao, J.ꢀP.; Chen, Y.ꢀQ.; Liu, S.ꢀJ.; Miao, X.ꢀH.;
Hu, T.ꢀL.; Bu, X.ꢀH. Cryst. Growth Des. 2014, 14, 2–5.
(18) Aulakh, D.; Pyser, J. B.; Zhang, X.; A. Yakovenko, A.;
Dunbar, K. R.; Wriedt, M. J. Am. Chem. Soc. 2015, 137, 9254–925.
(19) Wang, H.ꢀY.; Wu, Y.; Leong, C. F.; D’Alessandro, D. M.;
Zuo, J.ꢀL. Inorg. Chem. 2015, 54, 10766ꢀ10775.
4
(
3
(
1
EZ, UK; fax: +44 1223 336033.
AUTHOR INFORMATION
Corresponding Author
*
*
*
Eꢀmail: liusuijun147@163.com. Tel: +86ꢀ797ꢀ8312204.
Eꢀmail: wenherui63@163.com. Tel: +86ꢀ797ꢀ8312553.
Eꢀmail: chenjzxy@126.com.
Notes
The authors declare no competing financial interest.
(
20) Wang, S.ꢀN.; Ma, R.ꢀR.; Chen, Z.ꢀW.; Li, Y.ꢀW.; Cao, T.ꢀT.;
Zhou, C.ꢀH.; Bai, J.ꢀF. Sci. China Chem. 2016, 59, 948ꢀ958.
(21) Stock, N.; Biswas, S. Chem. Rev. 2012, 112, 933–969.
(22) Chen, Q.; Chang, Z.; Song, W.ꢀC.; Song, H.; Song, H.ꢀB.; Hu,
T.ꢀL.; Bu, X.ꢀH. Angew. Chem. Int. Ed. 2013, 52, 11550–11553.
ACKNOWLEDGMENTS
This work was financially supported by the NNSF of China
No. 21501077, 21561013 and 21501078), the China
Postdoctoral Science Foundation (No. 2016M592107), the
Jiangxi Provincial NSF of China (Nos. 20151BAB213003,
0161ACB21013, 20171BCB23066, 20143ACB21017 and
0171BAB203005), the Shanxi Provincial NSF of China (No.
2015011026), the Jiangxi Provincial Postdoctoral Preferred
Project of China (No. 2015KY34), the Jiangxi Provincial
Postdoctoral Daily Project of China (No. 2016RC31), the
Project of Jiangxi Provincial Department of Education (No.
GJJ150634), and the Program for Qingjiang Excellent Young
Talents, JXUST.
(
(
23) Wang, S.ꢀL.; Hu, F.ꢀL.; Zhou, J.ꢀY.; Zhou, Y.; Huang, Q.;
Lang, J.ꢀP. Cryst. Growth Des. 2015, 15, 4087−4097.
(24) Liu, S.ꢀJ.; Cao, C.; Yao, S.ꢀL.; Zheng, T.ꢀF.; Wang, Z.ꢀX.; Liu,
C.; Liao, J.ꢀS.; Chen, J.ꢀL.; Li, Y.ꢀW.; Wen, H.ꢀR. Dalton Trans. 2017,
46, 64–70.
25) Du, M.; Li, C.ꢀP.; Liu, C.ꢀS.; Fang, S.ꢀM. Coord. Chem. Rev.
013, 257, 1282–1305.
26) Qin, J.ꢀS.; Yuan, S.; Wang, Q.; Alsalme, A.; Zhou, H.ꢀC. J.
Mater. Chem. A 2017, 5, 4280–4291.
27) Li, Y.ꢀL.; Zhao Y.; Kang Y.ꢀS.; Liu X.ꢀH.; Sun, W.ꢀY. Cryst.
Growth Des. 2016, 16, 7112–7123.
2
2
(
2
(
(
8
ACS Paragon Plus Environment

Page 9 of 10
Crystal Growth & Design
(
28) Zhang, X.; Liu, P.ꢀF.; Wang, N.; Zhang, D.ꢀS. Polyhedron
(44) Blatov, V. A.; Shevchenko, A. P.; Serezhkin, V. N. J. Appl.
Crystallogr. 2000, 33, 1193.
(45) Sopasis, G. J.; Orfanoudaki M.; Zarmpas, P.; Philippidis A.;
Siczek, M.; Lis T.; O’Brien, J. R.; Milios, C. J. Inorg. Chem. 2012,
51, 1170−1179.
(46) Orfanoudaki, M.; Tamiolakis, I.; Siczek, M.; Lis, T.; Armatas,
G. S.; Pergantis, S. A.; Milios, C. J. Dalton Trans. 2011, 40, 4793–
4796.
(47) Edison, S. E.; Conklin, S. D.; Kaval, N.; Cheruzel, L. E.;
Krause, J. A.; Seliskar, C. J.; Heineman, W. R.; Buchanan, R. M.;
Baldwin, M. J. Inorg. Chim. Acta 2008, 361, 947–955.
(48) Zhang, L.; Yang, W.ꢀB.; Wu, X.ꢀY.; Lu, C.ꢀZ.; Chen, W.ꢀZ.;
Chem. Eur. J. 2016, 22, 11283 – 11290.
(49) Liu, S.ꢀJ.; Xue, L.; Hu, T.ꢀL.; Bu, X.ꢀH. Dalton Trans. 2012,
41, 6813ꢀ6819.
(50) Ginsberg, A. P.; Bertrand, J. A.; Kaplan, R. I.; Kirkwood, C.
E.; Martin, R. L.; Sherwood, R. C. Inorg. Chem. 1971, 10, 240–246.
(51) Li, Y.ꢀW.; Liu, S.ꢀJ.; Hu, T.ꢀL.; Bu, X.ꢀH. Dalton Trans. 2014,
43, 11470–11473.
(52) Li, J.; Li, B.; Huang, P.; Shi, H.ꢀY.; Huang, R.ꢀB.; Zheng, L.ꢀ
S.; Tao J. Inorg. Chem. 2013, 52, 11573−11579.
(53) Li, Z.ꢀY.; Cao, Y.ꢀQ.; Zhang, X.ꢀM.; Xu, Y.ꢀL.; Cao, G.ꢀX.;
Zhang, F.ꢀL.; Li, S.ꢀZ.; Zhang, F.ꢀQ.; Zhai, B. New J. Chem. 2017, 41,
457–461.
(54) Li, J.; Guo, Y.; Fu, H.ꢀR.; Zhang, J.; Huang, R.ꢀB.; Zheng L.ꢀ
S.; Tao, J. Chem. Commun. 2014, 50, 9161–9164.
(55) Mahata, P.; Natarajan, S.; Panissod, P.; Drillon, M. J. Am.
Chem. Soc. 2009, 131, 10140–10150.
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
2017, 126, 83–91.
29) Yin, Z.; Zhou, Y.ꢀL.; Zeng, M.ꢀH.; Kurmoo, M. Dalton Trans.
015, 44, 5258–5275.
30) Liu, S.ꢀJ.; Han, S.ꢀD.; Chang, Z.; Bu, X.ꢀH. New J. Chem.
(
2
2
(
016, 40, 2680–2686.
(31) Han, L.ꢀJ.; Yan, W.; Chen, S.ꢀG.; Shi, Z.ꢀZ.; Zheng, H.ꢀG.
Inorg. Chem. 2017, 56, 2936−2940.
32) He, Y.ꢀF.; Chen, D.ꢀM.; Xu, H.; Cheng, P. CrystEngComm
015, 17, 2471–2478.
33) Xuan, W.ꢀM.; Zhu, C.ꢀF.; Liu, Y.; Cui, Y. Chem. Soc. Rev.
012, 41, 1677−1695.
34) Li, M.; Li, D.; O’Keeffe, M.; Yaghi, O. M. Chem. Rev. 2014,
114, 1343−1370.
35) Chang, Z.; Yang, D.ꢀH.; Xu, J.; Hu, T.ꢀL.; Bu, X.ꢀH. Adv.
Mater. 2015, 27, 5432−5441.
36) Schlechte, L.; Bon, V.; Grünker, R.; Klein, N.; Senkovska, I.;
Kaskel, S. Polyhedron 2012, 44, 179–186.
37) Wu, P.; Xue, Q.; Dong, X.; Zhang, Y.; Liu, B.; Hu, H.; Xue,
G. CrystEngComm 2016, 18, 5320–5326.
38) Zhang, X.ꢀD.; Li, Y.ꢀM.; Fan, L.; Pang, J.ꢀD.; Ju, Z.ꢀF. Inorg.
Chem. Commun. 2015, 53, 4–6.
39) Fan, L.ꢀM.; Gao, Y.; Liu, G.ꢀZ.; Fan, W.ꢀL.; Song, W.ꢀK.;
Sun, L.ꢀM.; Zhao, X.; Zhang , X.ꢀT. CrystEngComm 2014, 16, 7649–
659.
(40) Sheldrick, G. M. SADABS, Program for Empirical
(
2
2
(
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
(
(
(
(
(
(
7
Absorption Correction of Area Detector Data; University of
Göttingen: Germany, 1996.
(
41) Sheldrick, G. M. SHELXL97, Program for Crystal Structure
Refinement; University of Göttingen: Göttingen, Germany, 1997.
42) Spek, A. L. SingleꢀCrystal Structure Validation with the
(56) Chen, Q.; Xue, W.; Lin, J.ꢀB.; Lin, R.ꢀB.; Zeng, M.ꢀH.; Chen,
X.ꢀM. Dalton Trans. 2012, 41, 4199–4206.
(57) Yao, R.ꢀX.; Xu, X.; Zhang, X.ꢀM. Chem. Mater. 2012, 24,
303−310.
(
Program PLATON. J. Appl. Crystallogr. 2003, 36, 7−13.
(43) Li, Y.ꢀW.; Zhao, J.ꢀP.; Wang, L.ꢀF.; Bu, X.ꢀH.
CrystEngComm 2011, 13, 6002–6006.
9
ACS Paragon Plus Environment

Crystal Growth & Design
Page 10 of 10
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
For Table of Contents Use Only
SpinꢀCanted Antiferromagnetic Ordering in Transition MetalꢀOrganic
Frameworks Based on Tetranuclear Clusters with Mixed Vꢀ and Yꢀ
Shaped Ligands
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
Chen Cao, SuiꢀJun Liu,* ShuꢀLi Yao, TengꢀFei Zheng, YongꢀQiang Chen,* JingꢀLin Chen, and HeꢀRui
Wen*
II
II
II
Four Co , Fe and Ni magnetic metalꢀorganic frameworks derived from tetranuclear clusters with
some differences have been synthesized by using mixedꢀligand strategy. Complexes 3 and 4 show the
coexistence of spin canting and longꢀrange magnetic ordering.
10
ACS Paragon Plus Environment