Electronic Supplementary Information
Stepwise assembly of homochiral coordination polymers based on the
precursor of an enantiopure Yb3Mn6 cluster
Yong Zheng, La-Sheng Long,* Rong-Bin Huang, and Lan-Sun Zheng
State Key Laboratory of Physical Chemistry of Solid Surfaces and Department of Chemistry, College of
Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, China.
Email: lslong@xmu.edu.cn
1 Materials and general procedures.
2 Syntheses of 4-6 and their IR data
3 Table S1. Crystal data and structure refinement for 4-6
4 Table S2. Bond valence sum (BVS) calculations for Mn in 4-6
5 Fig. S1. Positive HRESI-MS data of 4 in MeOH : DMF (v:v = 1 : 1) heat at
100℃ for 12 hours and the solution for preparation of 5
6 Fig. S2. TGA curves of 5 and 6
7 Fig. S3. PXRD patterns of 4-6
8 Fig. S4. Solid state CD spectra of 4-6 at room temperature
9 Fig. S5. Two types of connection modes and the packing mode of layers A
and B in 5
10 Fig. S6. Connection mode between clusters 4 in complex 6
11 Fig. S7. Temperature dependence of the mT at 1000 Oe for 4-6
1 Materials and general procedures
All reagents used were commercially available and were used as received. The solvothermal synthesis
was carried out in Teflon lined stainless steel containers under autogenous pressure. The high resolution
electrospray ionization mass spectrometry (HRESI-MS) data were collected on Bruker En Apex ultra 7.0T
FT-MS. And all the HRESI-MS data was processed using the Bruker Daltonics Data Analysis 3.3 software,
while simulated isotope patterns were investigated using Bruker Isotope Pattern software. The C, H, and N
microanalyses were carried out with a CE instruments EA 1110 elemental analyzer. The infrared spectra
(IR) were recorded on a Nicolet AVATAR FT-IR330 Spectrophotometer with pressed KBr pellets. TGA
curves were prepared on a SDT Q600 Thermal Analyzer. The solid circular dichroism spectra were
recorded on a JASCO J-810 spectropolarimeter with pressed KCl pellets at room temperature. Magnetic
measurements were carried out with a Quantum Design SQUID MPMS magnetometer working in the
2-300 K range. The magnetic field was 1000 Gauss. Diamagnetic corrections were made with Pascal's
constants. X-ray powder diffraction studies (PXRD) were performed using a Panalytical X-Pert PRO
diffractometer with Cu-Kα radiation (λ = 0.15418 nm, 40.0 kV, 30.0 mA). The calculated PXRD patterns
were produced using Mercury 2.4 and single crystal reflection data.
Single-crystal X-ray Diffraction
Intensity data of complex 4 were collected using a dark brown, block-shaped crystal, 0.35 x 0.20 x 0.08
mm3, on an Oxford Diffraction Supernova diffractometer with graphite-monochromatized Mo Kα radiation
(λ = 0.71073 nm) at 133 K. Data of complex 5 were collected using a dark brown, block-shaped crystal,
0.30 x 0.20 x 0.05 mm3, on the same diffractometer with graphite-monochromatized Mo Kα radiation (λ =
0.71073 nm) at 123 K. An analytical absorption correction was applied using the CrysAlis RED software.1
Data of complex 6 were collected using a dark brown, rhombic-shaped crystal, 0.08 x 0.05 x 0.05 mm3,
on a Rigaku R-AXIS RAPID Image Plate single-crystal diffractometer with graphite-monochromatized Mo
Kα radiation (λ = 0.71073 nm) at 173 K. Absorption correction was applied by correction of
symmetry-equivalent reflections using the ABSCOR program.2
All the structures were solved by direct methods using SHELXS-973, and further refined by full-matrix
least-squares on F2 with anisotropic displacement parameters for the non-H atoms (except C48, C49, C58,
C75 and O35 in 4, C15, C37, C38, C47, C48, C63, C64, C67, C68, C70, C71, C87, N7 and O37 in 5 and
C4, C5, C11 and O7W in 6) using SHELXL-974 and OLEX2.5 Hydrogen atoms were calculated in ideal
methyl hydrogen atoms). The severely disordered guest molecules in 4 and 5 were removed by SQUEEZE6
Other disordered atoms were refined with commands of ISOR, SIMU and DELU. Totally 25 restraints have
been applied in the structural refinement of 4, 44 restraints for 5 and 13 restraints for 6.
2 Syntheses of complexes 4-6 and their IR data
Complex 4 was prepared as 1 to 3 reported earlier.7 A mixture of LiOH·H2O (0.5 mmol) and
(S)-4-amino-2-hydroxybutanoic acid (0.5 mmol) in methanol (10 ml) was stirred for 20 min, then
2-hydroxybenzaldehyde (0.5 mmol) was added to the solution and stirred for about 1 h at room
temperature. The resulting Schiff-base (H2L-) was added 0.5 mmol of Mn(OAc)2⋅4H2O, 0.25 mmol
Yb(NO3)3⋅6H2O and 1.0 mmol TEA, and stirred again for another 4 h at ambient condition, the resulting
dark brown solution was layered with n-hexane. Block dark crystals were collected in few days. 4 (Yield:
54% based on Mn). Anal. Calcd (%) for C77H109N8Mn6O49Yb3: C, 33.27; H, 3.95; N, 4.03. Found: C,
33.35; H, 4.07; N, 3.87. IR (KBr, cm−1): 3405(b, s), 2924(w), 1601(vs), 1546(m), 1471(w), 1449(m),
1384(vs), 1307(m), 1200(w), 1141(m), 1079(w), 979(w), 910(w), 794(w), 758(w), 633(m), 594(w),
548(m), 515(w), 462(w).
Complex 5 0.08 mmol 4 was resolved in 5 ml MeOH, to which was added 0.2 mmol sodium
isonicotinate and 1.0 mmol TEA, and stirred for 30 minutes at ambient condition, the resulting dark brown
solution was layered with n-hexane. Block dark crystals were collected in few days. 5 (Yield: 35% based
on Mn). Anal. Calcd (%) for C180H244Mn12N18O98Yb6: C, 39.88; H, 4.54; N, 4.65; Found (%): C, 39.54; H,
4.81; N, 4.67. IR (KBr, cm−1): 3377(b, s), 2923(w), 1601(vs), 1546(s), 1471(w), 1449(m), 1394(s),
1308(m), 1202(w), 1140(m), 1134(s), 978(w), 910(w), 793(m), 760(m), 649(w), 633(m), 592(w), 547(m),
513(w), 462(w), 414(w).
Complex 6 0.08 mmol 4 was resolved in 5 ml MeOH and 5 ml DMF, to which was added 0.2 mmol
PbI2 and 0.6 mmol NaI. The mixture was stirred for 30 min, and subsequently sealed in an 18 mL Teflon
lined Parr, heated to 100 ℃ for 12 h, then cooled to room temperature at a rate of 2 ℃·h-1. The dark-brown
rhombic crystals were washed with DMF and MeOH. 6 (Yield: 20% based on Mn). Anal. Calcd (%) for
C75H115IMn6N6NaO53Yb3: C, 30.56; H, 3.93; N, 2.85; Found (%): C,30.29; H, 4.02; N, 2.89. IR (KBr,
cm−1): 3424(b, s), 2924(w), 1600(vs), 1548(s), 1472(m), 1448(m), 1385(s), 1354(m), 1302(s), 1207(w),
1152(m), 1136(s), 1055(w), 908(w), 980(w), 785(m), 764m), 634(m), 589(w), 540(w), 521(w), 463(w).
Synthesis discussion
Step-by-step assembly is useful for the rational design and synthesis of functional materials.8 There are
six terminal ligands (one acetate ion, two aqua molecules and three methanol molecules) around the cluster
4, which may be replaced by other bridging ligands. On the other hand, the six monodentately coordinated
Ophenolic atoms are also expected to bridge a second metal. So, we try to link them with carboxylate salts
that have different coordination modes and lengths. After the successful synthesis of 5, we try to link
cluster 4 using the shorter formate group, which maybe modify the magnetic coupling between clusters of 4
potentially. However, direct synthesis of complex 6 from sodium formate in methanol was failed.
Considering that formate ions can be generated by decomposition of DMF under solvothermal condition as
previous reported by others,9 we are lucky to find the aforementioned procedure for 6 by trial and error. It
should be noted that the presence of Pb(II) salt is necessary for the synthesis of complex 6 which can
improve the yield and quality of the crystal 6 obviously. Only a few crystals were obtained in the absence
of Pb(II) salts.
3 Table S1. Crystal data and structure refinement for 4-6
Complex
4
5
6
Formula
Mr
Crystal system
Space group
a/Å
b/Å
c/Å
V/Å3
Z
Dc/g cm−3
µ/mm−1
Data/parameters
C77H109N8 Mn6O49Yb3
2779.48
Orthorhombic
P21212
28.079(2)
28.134(2)
14.283(1)
11283(1)
4
1.636
3.195
21086/1198
C180H244Mn12N18O98Yb6
5925.45
Trigonal
R32
28.274(1)
28.274(1)
79.473(2)
55020(1)
9
1.610
2.954
22934/1260
C75H115IMn6N6NaO53Yb3
2947.38
Cubic
P213
21.357(3)
21.357(3)
21.357(3)
9741(2)
4
2.010
4.026
5722/437
aR
θ/o
Flack parameters10
Observed
reflections
Goof on F2
3.28-26.0
-0.018(8)
18384
3.27-26.0
-0.039(7)
17836
3.02-25.0
-0.018(17)
3916
1.039
0.999
0.954
R1[I> 2σ(I)]a
0.0435
0.0478
0.0610
wR2(All data)b
0.1020
0.1268
0.1204
1
= ∑||FO| - |FC||/∑|FO|
bwR
2
= {∑[w(FO2 - FC2)2]/∑[w(FO2)2]}1/2
4 Table S2. Bond valence sum (BVS) calculations for Mn atoms in 4-6
4
5
6
Atoms
BVS
Atoms
BVS
Atoms
BVS
Mn1
3.02
Mn1
3.22
Mn1
3.10
Mn2
3.00
Mn2
3.10
Mn2
3.04
Mn3
2.97
Mn3
3.28
Mn4
3.06
Mn4
2.97
Mn5
2.97
Mn5
3.15
Mn6
2.97
Mn6
3.00
5 Fig. S1. Positive HRESI-MS data of 4 in MeOH : DMF (v:v = 1 : 1) heat at
100℃ for 12 hours and the solution for preparation of 5
(a) HRESI-MS data of 4 in MeOH:DMF (v:v = 1:1) heat at 100℃ for 12 hours; (b) HRESI-MS data of the
solution (as prepared in mole ratio of 4:isonicotinate:TEA = 1:2.5:12.5) for the synthesis of 5. The
numerically labelled fragments are assigned as A, [Yb3Mn6(L)6(2-OMe)6]3+ (m/z, 785.30655 for calculated
highest isotopic peak, the same after); B, {[Yb3Mn6(L)6(2-OMe)5(OH)]}3+ (m/z, 780.63466) and C,
{[Yb3Mn6(L)6(2-OMe)6](OH)·(H2O)}2+ (m/z, 1195.46676).
6 Fig. S2. TGA curves of 5 and 6
7 Fig. S3. PXRD patterns of 4-6
8 Fig. S4. Solid state CD spectra of 4-6 at room temperature
9 Fig. S5. Two types of connection modes and the packing mode of layers A
and B in 5
(a) The coordination interaction between subunits of [YbIII3MnIII6(L)6(2-OMe)6(isonicotinate)2(HOMe)2]+
in
layer
A;
(b)
the
hydrogen
bonding
between
subunits
of
[YbIII3MnIII6(L)6(2-OMe)6(isonicotinate)2-(HOMe)4]+ in layer B; (c) packing of layers in an
A1B1A2B2A3B3 mode along c-axis in one unit cell in crystal 5
10 Fig. S6. Connection mode between clusters 4 in complex 6
11 Fig. S7. Temperature dependence of the mT at 1000 Oe for 4-6
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