Electronic Supplementary Information
Trigonal (-3) Symmetry Octahedral Lanthanide(III) Bis-tripodal Complexes
Daron E. Janzen†‡, Michael Juchum,† Tanya K. Ronson,† Wolfgang Mohr,† Rodolphe
Clérac,¶ Humphrey L.C. Feltham,† and Sally Brooker†*
Contents
CSD search results
Table S1
Hydrogen Bonding Tables
Tables S2-S5
List of residual electron density peaks and their environments
Tables S6-S9
Fragments used in CSD search
Figure S1
Unique ligands identified from CSD search
Figure S2
Tautomer Assignment for [TbIII(H3L1)2]Cl3·6MeOH
Figure S3
Tautomer Assignment for [DyIII(H3L1)2]Cl3·6MeOH
Figure S4
Tautomer Assignment for [EuIII(H3L1)2]Cl3·6MeOH
Figure S5
Tautomer Assignment for [TbIII(H3L1)2](NO3)3
Figure S6
Solid-state Emission Spectra of H3L1 and H3L2
Figure S7
Solid-state Emission Spectra of [TbIII (H3L1)2](NO3)3 and[TbIII(H3L2)2](NO3)3∙2MeOH∙H2O
Figure S8
Solid-state Emission Spectra of [DyIII(H3L1)2]Cl3∙6H2O, [HoIII(H3L1)2](NO3)3∙2H2O and
Figure S9
[ErIII(H3L1)2](NO3)3∙H2O
Field Dependence of Magnetisation for [TbIII(H3L1)2](NO3)3, [TbIII(H3L1)2]Cl3∙MeOH∙3H2O,
Figure S10
[DyIII(H3L1)2]Cl3∙6H2O, [HoIII(H3L1)2](NO3)3∙2H2O and [ErIII(H3L1)2](NO3)3∙H2O
Temperature Dependence of ac Susceptibility for [Tb III(H3L1)2](NO3)3,
[TbIII(H3L1)2]Cl3∙MeOH∙3H2O, [DyIII(H3L1)2]Cl3∙6H2O, [HoIII(H3L1)2](NO3)3∙2H2O and
Figure S11
[ErIII(H3L1)2](NO3)3∙H2O
S1
Cambridge Structural Database Search Details
A search of the Cambridge Structural Database (version 5.36 which includes updates through
to February 2015) using the Conquest interface (version 1.17) was performed to find all Xray structures of lanthanide complexes of ligands derived from salicylaldehyde and tren.
Two searches were performed based on the fragments shown in Figure S1.
Figure S1: Fragments used for searches 1 and 2.
These searches included both imine and amine ligands as the CN bond type was set as any
bond type. This search also allowed for substitution at any of the remaining phenyl ring
positions. Search 1 included at least one lanthanide bond to an amine/imine nitrogen and
search 2 included at least one lanthanide bond to the phenol/phenolate oxygen.
The results of these searches were combined to yield a total of 117 structures (106 of which
are unique complexes) encompassing 21 unique ligands. A diagram showing all unique
ligands in this structure set is shown in figure S2.
S2
Figure S2: The 21 unique ligands resulting from the search of the CSD specified in figure S1.
Of this structure set, 36 structures involve cryptate ligands and 81 structures involve noncryptate ligands. Imine ligands are found in the majority of the structures (98 structures)
while amines are far less common (19 structures). A variety of lanthanide/ligand
stoichiometries are found (1:1 78 structures, 1:2 7 structures, 2:1 18 structures, 2:2 4
structures, 3:2 10 structures). All lanthanides are represented in this structure set except Pm.
A detailed list of all the structures of this set with references is presented in table S1.
S3
Table S1: CSD details of structures involved in literature search.
CSD code
ADELAW
ADUPEU
AHICAV
AHICEZ
AHICID
AHICOJ
AHICUP
ATINIA
ATINOG
ATINUM
ATIPAU
BAJJAY
BAJJEC
BAJJIG
CANBAU
CANBOI
CANCAV
CISGIV
CISGOB
DOSVEN
DOSVIR
DOSVOX
DOSVUD
EGIMUC
EGIMUC01
ELUSEJ
ELUSIN
EMEVUN
GACHIC
GACHOI
GACHUO
GACJEA
GACJIE
GANLAK
HELTOH
HELTOH01
HELTUN
HELTUN01
HIBMAI
HIBMAI01
HIBMEM
pub
yr
M
L
2001
Sm
L10
2001
Gd
L10
2002
Gd
L16
2002
Tb
L16
2002 Gd/Cu L16
2002 Lu/Cu L16
2002 Gd/Zn L16
2004
Tb
L8
2004
Dy
L8
2004
Ho
L8
2004
Er
L8
2002 Pr,Zn L16
2002 Yb,Zn L16
2002 Lu,Zn L16
1999
Ce
L16
1999
Nd
L16
1999
Eu
L16
2008
Ce
L9
2008
Ce
L9
2009 La,Ni2 L13
2009 Ce,Ni2 L13
2009
Gd
L15
2009
Ce
L13
2002 Eu,Ni L19
2002 Eu,Ni L19
2003 Eu,Na L4
2003
Dy2
L4
2003
Eu
L21
2003
La
L3
2003
Sm
L3
2003
Tb
L3
2003
Lu
L3
2003
Ce
L3
2012
Sm
L12
1994
La
L6
1997
La
L6
1994
Pr
L6
1997
Pr
L6
2013 Dy2,Zn L15
2013 Dy2,Zn L15
2013 Dy,Zn2 L15
M:L
1:1
1:1
2:1
2:1
2:1
2:1
2:1
1:1
1:1
1:1
1:1
2:1
2:1
2:1
1:1
1:1
1:1
1:1
1:1
3:2
3:2
1:1
2:2
2:1
2:1
2:1
2:1
1:2
1:1
1:1
1:1
1:1
1:1
1:1
1:1
1:1
1:1
1:1
3:2
3:2
3:2
imine/amine
imine
imine
imine
imine
imine
imine
imine
imine
imine
imine
imine
imine
imine
imine
imine
imine
imine
imine
imine
amine
amine
amine
amine
imine
imine
imine
imine
amine
imine
imine
imine
imine
imine
imine
imine
imine
imine
imine
amine
amine
amine
crypt or
no
no
no
crypt
crypt
crypt
crypt
crypt
no
no
no
no
crypt
crypt
crypt
crypt
crypt
crypt
no
no
no
no
no
no
crypt
crypt
no
no
crypt
no
no
no
no
no
no
no
no
no
no
no
no
no
Ref.
[1]
[2]
[3]
[3]
[3]
[3]
[3]
[4]
[4]
[4]
[4]
[5]
[5]
[5]
[6]
[6]
[6]
[7]
[7]
[8]
[8]
[8]
[8]
[9]
[9]
[10]
[10]
[11]
[12]
[12]
[12]
[12]
[12]
[13]
[14]
[15]
[14]
[15]
[16]
[16]
[16]
S4
HOPZER
IPEBIP
IPEBOV
IYOYUQ
KAYMEC
KAYPOP
LECTEU
LIFZOR
MIPTAG
MIPTEK
MIPTIO
MIPTOU
MIPTOU01
MIPTUA
MIPTUA01
MUVZAE
NAKTOK
NALBIL
NALBIL01
NICNIW
NOFLOJ
NUCXOY
NUCXUE
NUNWAU
OGELIV
PALHAL
PERSUA
PERTAH
PIXSAQ
QILREI
QILRIM
REPBOD
SETWIX
TIXNEV
TIXNIZ
TIZSOK
TIZSUQ
TOZNIF
UDUYIB
UMEWEP
UMINAG
UMIPIQ
UMIPOW
UMIPUC
VEDCUC
1999
2011
2011
2004
2000
2000
2012
2013
2001
2001
2001
2001
2011
2001
2004
2002
2010
1996
1998
1997
1998
1997
1997
1996
2002
1992
1993
1993
1998
2001
2001
1997
1997
2014
2014
1996
1996
1996
2002
2011
2011
2010
2010
2010
1998
Lu2
Ce
Ce
Sm
Dy
Dy2
Yb
Gd
Ce
Pr
Nd
Gd
Gd
Yb
Yb
Dy
Ce
La2
La2
Dy
Nd
La,Ni
Gd
Ce
Eu,Cu
Gd2
Pr
Gd
La,Yb
Nd
Sm
Gd
Gd
Er
Er
Pr
Nd
Eu2
Gd,Ni
Eu
Tb
Eu
Gd
Tb
Eu
L16
2:1
L9
1:1
L9
1:1
L1
1:1
L16
1:1
L16
2:1
L14
1:2
L16
1:1
L1
1:1
L1
1:1
L1
1:1
L1
1:1
L1
1:1
L1
1:1
L1
1:1
L19
1:1
L9
1:1
L11
2:2
L11
2:2
L16
1:1
L19
1:1
L6
1:1
L7
1:1
L16
1:1
L19
2:1
L13
2:2
L14
1:2
L14
1:2
L4
2:1
L9
1:1
L9
1:1
L20
1:1
L16
1:1
L5
1:1
L10
1:1
L1
1:1
L1
1:1
L20 1:1 (2:2)
L19
2:1
L2
1:1
L2
1:1
L1
1:2
L1
1:2
L1
1:2
L18
1:1
imine
imine
imine
imine
imine
imine
amine
imine
imine
imine
imine
imine
imine
imine
imine
imine
imine
imine
imine
imine
imine
imine
imine
imine
imine
amine
amine
amine
imine
imine
imine
imine
imine
imine
imine
imine
imine
imine
imine
imine
imine
imine
imine
imine
imine
crypt
no
no
no
crypt
crypt
no
crypt
no
no
no
no
no
no
no
crypt
no
no
no
crypt
crypt
no
no
crypt
crypt
no
no
no
no
no
no
crypt
crypt
no
no
no
no
crypt
crypt
no
no
no
no
no
crypt
[17]
[18]
[18]
[19]
[20]
[20]
[21]
[22]
[23]
[23]
[23]
[23]
[24]
[23]
[19]
[25]
[26]
[27]
[28]
[29]
[30]
[15]
[15]
[31]
[32]
[33]
[34]
[34]
[35]
[36]
[36]
[37]
[38]
[39]
[39]
[40]
[40]
[41]
[42]
[43]
[44]
[45]
[45]
[45]
[46]
S5
VEDDIR
VEQFAY
VEQFEC
VEQFIG
VEQFOM
VEQFOM01
VEQFUS
VEQGAZ
WECQEA
WORZEI
WUXSIR
WUXSOX
WUXSUD
WUXTAK
WUXTEO
XEQMAH
XEQMAH01
XEQMEL
XEQMEL01
XEXJAL
XEXJEP
XEXJIT
XEXJIT01
XIHQIO
XIHQUA
XIHQUA01
XIPGEI
YATHOQ
YONFEM
YONFOW
YONGAJ
1998
Gd
L18
1999
Eu
L1
1999
Gd
L1
1999
Tb
L1
1999
Er
L1
2014
Er
L1
1999
Tm
L1
1999
Lu
L1
2000 Dy,Cu L19
2000
Gd
L19
2003 Sm,Ni2 L13
2003 Lu,Ni2 L13
2003 Pr,Ni2 L13
2003 Tb,Ni2 L13
2003 Er,Ni2 L13
2000
Dy
L1
2011
Dy
L1
2000
Ho
L1
2011
Ho
L1
2000
Sm
L1
2000
Eu
L1
2000
Tb
L1
2011
Tb
L1
2001
Eu
L14
2001
Eu
L14
2001
Eu
L14
2000
Sm
L19
2001
Eu
L19
1995
Gd
L16
1995
Gd
L17
1995
Tb
L17
1:1
1:1
1:1
1:1
1:1
1:1
1:1
1:1
2:1
1:1
3:2
3:2
3:2
3:2
3:2
1:1
1:1
1:1
1:1
1:1
1:1
1:1
1:1
1:1
1:1
1:1
1:1
1:1
1:1
1:1
1:1
imine
imine
imine
imine
imine
imine
imine
imine
imine
imine
amine
amine
amine
amine
amine
imine
imine
imine
imine
imine
imine
imine
imine
amine
amine
amine
imine
imine
imine
imine
imine
crypt
no
no
no
no
no
no
no
crypt
crypt
no
no
no
no
no
no
no
no
no
no
no
no
no
no
no
no
crypt
crypt
crypt
crypt
crypt
[46]
[47]
[47]
[47]
[47]
[39]
[47]
[47]
[48]
[49]
[50]
[50]
[50]
[50]
[50]
[51]
[24]
[51]
[24]
[52]
[52]
[52]
[24]
[53]
[53]
[53]
[54]
[55]
[56]
[56]
[56]
S6
Supplementary Crystallographic data
Table S2: Hydrogen bonds for [TbIII(H3L1)2]Cl3∙6MeOH [Å and °]. Symmetry transformations used to generate
equivalent atoms: #1 = -y+1, x-y, z. Note that hydrogen atoms on nitrogen and oxygen atoms were located from
the difference map and their coordinates fixed, so esd values are not available for distances involving these
hydrogen atoms.
D-H...A
d(D-H)
d(H...A)
d(D...A)
<(DHA)
N2-H2D...O21
0.99
1.83
2.772(5)
157.3
N2-H2C...O1
0.86
2.40
2.858(5)
113.7
N2-H2C...O1#1
0.86
2.32
2.966(5)
131.6
O21-H21...Cl1
0.86
2.26
3.035(4)
148.8
Table S3: Hydrogen bonds for [DyIII(H3L1)2]Cl3∙6MeOH [Å and °]. Symmetry transformations used to
generate equivalent atoms: #1 = -y+1, x-y, z. Note that hydrogen atoms on oxygen atoms were located from the
difference map and their coordinates fixed so esd values are not available for distances involving these hydrogen
atoms. Hydrogen atoms on nitrogen atoms were located from the difference map and freely refined, so esd
values are available for distances involving these hydrogen atoms.
D-H...A
d(D-H)
d(H...A)
d(D...A)
<(DHA)
N2-H2B...O1#1
0.87(4)
2.26(4)
2.950(3)
137(3)
N2-H2A...O21#1
0.91(4)
1.87(4)
2.758(3)
164(3)
O21-H21...Cl1#2
0.84
2.23
3.016(2)
156.7
N2-H2B...O1
0.87(4)
2.28(4)
2.856(3)
124(3)
Table S4: Hydrogen bonds for [EuIII(H3L1)2]Cl3∙6MeOH [Å and °]. Symmetry transformations used to generate
equivalent atoms: #1 = -y+1, x-y, z. Note that hydrogen atoms on oxygen atoms were located from the
difference map and their coordinates fixed so esd values are not available for distances involving these hydrogen
atoms. Hydrogen atoms on nitrogen atoms were located from the difference map and freely refined, so esd
values are available for distances involving these hydrogen atoms.
D-H...A
d(D-H)
d(H...A)
d(D...A)
<(DHA)
O21-H21...Cl1
0.91
2.14
3.0131(17)
160.6
N2-H2D...O21#1
0.81(3)
1.97(3)
2.766(3)
169(3)
N2-H2C...O1
0.88(3)
2.27(3)
2.847(2)
124(2)
N2-H2C...O1#1
0.88(3)
2.27(3)
2.957(2)
135(2)
S7
Table S5: Hydrogen bonds for [TbIII(H3L1)2](NO3)3 [Å and °]. Symmetry transformations used to generate
equivalent atoms: #1 = -y, x-y, z; #2 = -x+y, -x+1, z; #3 = -y+1, x-y+1, z. Hydrogen atoms on nitrogen and
oxygen atoms were located from the difference map and freely refined, so esd values are available for distances
involving these hydrogen atoms.
D-H...A
d(D-H)
d(H...A)
d(D...A)
<(DHA)
N2-H2D...O1#1
0.91(4)
2.08(3)
2.885(3)
147(3)
N2-H2C...O22#2
0.90(4)
1.93(4)
2.769(3)
154(3)
N4-H4C...O4#3
0.89(4)
2.09(4)
2.870(3)
146(3)
N4-H4D...O23
0.92(4)
1.98(4)
2.885(3)
170(4)
S8
Q4
Tb1
Q2
Q6
Q10
Q5
Q7
Q7
N2
Q8
Q1
Q7
Q3
Q7
Q9
3 Q7
Figure S3: [TbIII(H3L1)2]Cl3∙6MeOH structure model before refinement of hydrogens bonded to N2. Green
electron density surface areas and bronze residual electron density peaks overlaid. Image created in Olex2. A
list of the residual electron density peaks and their environments is given in Table S6.
Table S6: List of residual electron density peaks and their environments in the crystal structure of
[TbIII(H3L1)2]Cl3∙6MeOH. See also Figure S3.
Peak
Q1
Q2
Q3
Q4
Q5
Q6
Q7
Q8
Q9
Q10
Frac. x coord.
0.3333
0.6791
-0.0034
0.6651
0.5311
0.6583
0.5681
0.5136
0.0515
0.5356
Frac. y coord
0.6667
0.0124
0.1006
0.3975
0.1549
0.4201
0.2379
0.3154
0.2010
0.0277
Frac z coord.
0.3219
0.4167
0.3455
0.3324
0.3934
0.3556
0.3836
0.3911
0.3719
0.3983
e-/Å3
1.89
1.71
1.01
0.77
0.72
0.63
0.60
0.58
0.54
0.54
S9
Structural Refinement Details for [TbIII(H3L1)2]Cl3·6MeOH
Q5 and Q7 (located in regions of the electron difference map) were refined as the protons of
the N2 ammonium moiety. Q1 and Q3 are in the region detected as void space detected by
SQUEEZE (applied after the RR’NH2 incorporated into the model). Q2 lies on a 2-fold axis
and is likely a ghost peak related to Cl1 (Q2 translated +1/3, 0, 0 from Cl1). Q4 is only 1.14
Å from Tb1, too close to be any atom. Q6 is 1.47 Å from O1 and no evidence is present of
an atom from the electron density difference map. Q8 is 0.96 Å from H2A, Q9 is 1.49A from
H11A, and Q10 is 0.62 Å from O21 and 0.99 Å from C21, all unreasonable for additional
atoms.
After assigning Q5 and Q7 as hydrogen atoms of the ammonium group, residual electron
density remained in void spaces. The SQUEEZE utility in PLATON was applied, the model
was refined with the squeezed .hkl, and peaks formerly assigned as Q1 and Q3 were removed
through this procedure. Void space and residual electron density were consistent with
disordered solvent. A total solvent accessible void space volume of 1338 Å3 per unit cell and
total electron count of 181 electrons per unit cell was calculated. The void spaces large
enough to accommodate solvent can described as 12 isolated areas of 95 Å3 with 15 electrons
per void, each centred on positions with 3-fold symmetry and in close proximity to O2 of the
ester group. Water and methanol are both possibilities based on the volume of these solvent
molecules, the combustion analyses of the air-dried crystals, the existing presence of ordered
methanol in the structure, and the proximity of a hydrogen-bond acceptor group to the voids.
S10
Q5
Tb1
Q6
Q6
Q9
Q7
Q3
Q6
Q8
Q10
Q7
Q6
Q7
Q7
Q6
Q6
Q6
Q7
Q7
Q7
Q4
N2
Q7
Q6
Q7
Q1
Q6
Q7
Q2
Q6
Q7
Q7
Q6
Q7
Figure S4: [DyIII(H3L1)2]Cl3∙6MeOH structure model before refinement of hydrogens bonded to N2. Green
electron density surface areas and bronze residual electron density peaks overlaid. Image created in Olex2. A
list of the residual electron density peaks and their environments is given in Table S7.
Table S7: List of residual electron density peaks and their environments in the crystal structure of
[DyIII(H3L1)2]Cl3∙6MeOH. See also Figure S4.
Peak
Q1
Q2
Q3
Q4
Q5
Q6
Q7
Q8
Q9
Q10
Frac. x coord.
1.0000
0.9879
0.7455
0.4858
0.7057
0.5708
0.5738
0.7120
0.6443
0.6889
Frac. y coord
1.0000
1.0924
0.3882
0.2913
0.2942
0.3384
0.3509
0.3058
0.3574
0.3774
Frac z coord.
0.3461
0.3464
0.3354
0.2728
0.3328
0.2861
0.1853
0.3438
0.3108
0.3095
e-/Å3
1.76
1.19
0.75
0.75
0.75
0.75
0.74
0.60
0.47
0.41
S11
Structural Refinement Details for [DyIII(H3L1)2]Cl3·6MeOH
Q4 and Q6 (located in regions of the electron difference map) were refined as the protons of
the N2 ammonium moiety. Q1, Q2 and Q7 are in the region detected as void space detected
by SQUEEZE (applied after the RR’NH2 incorporated into the model). Q3, Q5, and Q8 all
lie too close to Dy1 and are likely due to Fourier truncation (Dy1-Q distances = 1.22 Å, 1.17
Å, and 1.27 Å, respectively). Q9 and Q10 are located near O1 (O1-Q distances = 1.22 Å, 1.19
Å, respectively) but are too close to Dy1 (Dy1-Q distances = 1.53 Å, 1.59 Å, respectively)
and at unreasonable angles relative to the C5-O1 bond (C5-O1-Q angles = 147°, 174°,
respectively)
After assigning Q4 and Q6 as hydrogen atoms of the ammonium group, residual electron
density remained in void spaces. The SQUEEZE utility in PLATON was applied, the model
was refined with the squeezed .hkl, and peaks formerly assigned as Q1 and Q3 were removed
through this procedure. A total solvent accessible void space volume of 1326 Å3 per unit cell
and total electron count of 177 electrons per unit cell was calculated. The void spaces large
enough to accommodate solvent can described as 12 isolated areas of 95 Å3 with 14 electrons
per void, each centred on positions with 3-fold symmetry and in close proximity to O2 of the
ester group. Water and methanol are both possibilities based on the volume of these solvent
molecules, the combustion analyses of the air-dried crystals, the existing presence of ordered
methanol in the structure, and the proximity of a hydrogen-bond acceptor group to the voids.
S12
Q7
Q6
Q6
Q8
Q7
Q6
Q7
Q4
Q7
N2
Q9
Q5
Q7
Q6
Q10
Q6 Q7
Q6
Q7
Q7
Q6
Q2
Q6
Q7
Q7
Tb1
Q6
Q1
Q7
Q3
Q6
Q6
Q7
Q7
Figure S5: [EuIII(H3L1)2]Cl3∙6MeOH structure model before refinement of hydrogens bonded to N2. Green
electron density surface areas and bronze residual electron density peaks overlaid. Image created in Olex2. A
list of the residual electron density peaks and their environments is given in Table S8.
Table S8: List of residual electron density peaks and their environments in the crystal structure of
[EuIII(H3L1)2]Cl3∙6MeOH. See also Figure S5.
Peak
Q1
Q2
Q3
Q4
Q5
Q6
Q7
Q8
Q9
Q10
Frac. X coord.
-0.6667
0.0236
-0.55640
0.0298
-0.0116
-0.0293
-0.3635
-0.2739
-0.0323
-0.3423
Frac. Y coord
-0.3333
-0.0270
-0.23590
0.1779
0.0901
0.1207
-0.3558
-0.1357
0.1505
0.1483
Frac z coord.
0.5119
0.4909
0.51250
0.4418
0.4529
0.4370
0.4082
0.4229
0.4522
0.4480
e-/Å3
1.59
1.37
0.98
0.80
0.79
0.53
0.48
0.45
0.43
0.42
S13
Structural Refinement Details for [EuIII(H3L1)2]Cl3·6MeOH
Q4 and Q5 (located in regions of the electron difference map) were refined as the protons of
the N2 ammonium moiety. Q1 and Q3 are in the region detected as void space detected by
SQUEEZE (applied after the RR’NH2 incorporated into the model). Q2 lies too close to Eu1
and is likely due to Fourier truncation (Eu1-Q2 = 0.94 Å). Q6 and Q9 are located along the
bond vectors N2-C2 and N2-C3, respectively. Q7 is located 0.84 Å from Cl1, but is not a
hydrogen as anionic chloride is needed for overall structure charge balance and Cl1 already
acts a hydrogen-bond acceptor for two O21-H21 groups along similar vectors. Q8 is located
0.68 Å from O21, but this is too short for a hydrogen atom and is not directed toward a
hydrogen-bond acceptor. Q10 is located 0.91 Å from O2, but this is not a hydrogen atom as
the geometry is inappropriate (C10-O2-Q10 angle = 44°) for an alcohol, and the C10-O2
bond is the appropriate length for an ester C=O (1.201(4) Å).
After assigning Q4 and Q5 as hydrogen atoms of the ammonium group, residual electron
density remained in void spaces. The SQUEEZE utility in PLATON was applied, the model
was refined with the squeezed .hkl, and peaks formerly assigned as Q1 and Q3 were removed
through this procedure. A total solvent accessible void space volume of 1340 Å3 per unit cell
and total electron count of 117 electrons per unit cell was calculated. The void spaces large
enough to accommodate solvent can described as 12 isolated areas of 96 Å3 with 10 electrons
per void, each centred on positions with 3-fold symmetry and in close proximity to O2 of the
ester group. Water and methanol are both possibilities based on the volume of these solvent
molecules, the combustion analyses of the air-dried crystals, the existing presence of ordered
methanol in the structure, and the proximity of a hydrogen-bond acceptor group to the voids.
S14
Tb2
Q6
Q6
Q5
Q9
Q7
0
Q6
Q6
Q1
N4
O4
Q7
Q6
Q7
Q6
Q6
Q7
Q7
Q7
Q6
Q7
Q7
Q6
Q7
Q4
N2Q6
Q3
Q6
Q7
Q7
Q6
Q7
Tb1
Q8
Q6
Q2
Q6
Q7
Q6
Q7
Q7
Q1
Q6
Figure S6: [TbIII(H3L1)2](NO3)3 structure model before refinement
of hydrogens bonded to N2 and N4. Green
Q7
electron density surface areas and bronze residual electron density peaks overlaid. Image created in Olex2. A
list of the residual electron density peaks and their environments is given in Table S9.
Table S9: List of residual electron density peaks and their environments in the crystal structure of
[TbIII(H3L1)2](NO3)3. See also Figure S6.
Peak
Q1
Q2
Q3
Q4
Q5
Q6
Q7
Q8
Q9
Q10
Frac. X coord.
0.5628
0.5298
0.0234
0.0109
0.5144
0.4239
0.6316
0.3514
0.5929
0.3425
Frac. Y coord
0.1952
0.2442
0.1148
0.1825
0.6755
0.6491
0.6641
0.2435
0.7059
0.6253
Frac Z coord.
0.6453
0.6338
0.5528
0.5650
0.5987
0.6136
0.6071
0.6155
0.5708
0.6442
e-/Å3
1.07
0.99
0.80
0.78
0.71
0.68
0.54
0.50
0.50
0.46
S15
Structural Refinement Details for [TbIII(H3L1)2](NO3)3
Q3, Q4 and Q5, Q6 (located in regions of the electron difference map) were refined as the
protons of the N2 and N4 ammonium moieties, respectively. Q1 and Q2 are located directly
between two well-modeled orientations of disorder of the coordinated ligand bonded to Tb2,
near C27 and C28. Q7 and Q9 (distances from N20 = 1.46 Å, 1.39 Å, respectively) are in a
region too near N20 to refine as any atom. Q8 is located directly between two well-modeled
orientations of disorder of the coordinated ligand bonded to Tb2, near O6 (O6-Q8 and O6’Q8 distances =0.70 Å, 0.68 Å, respectively) in a region too crowded to refine as any atom.
Q10 is located near O4 (O1-Q10 distances = 1.10) but are too close to Tb2 (Tb2-Q10
distance = 1.41 Å) and at unreasonable angles relative to the C19-O4 bond (C19-O4-Q10
angle = 145°).
S16
Supplementary spectroscopic data
Figure S7: Normalized solid-state emission spectra of H3L1 and H3L2 (exc = 360 nm).
S17
Figure S8: Normalized solid-state emission spectra of [TbIII(H3L1)2](NO3)3 and
[TbIII(H3L2)2](NO3)3∙2MeOH∙2H2O (exc = 360 nm) at room temperature. The spectrum of
[TbIII(H3L2)2](NO3)3∙2MeOH∙2H2O is shown as normalized relative to the intra-ligand peak at 466 nm, rather
than the actual intensity maximum at 488 nm for ease of display.
S18
Figure S9: Normalized solid-state emission spectra of [DyIII(H3L1)2]Cl3∙6H2O, [HoIII(H3L1)2](NO3)3∙2H2O, and
[ErIII(H3L1)2](NO3)3∙H2O (exc = 360 nm) at room temperature.
S19
Supplementary magnetic data
Figure S10: Field dependence of magnetisation for [TbIII(H3L1)2](NO3)3, [TbIII(H3L1)2]Cl3·MeOH·3H2O,
[DyIII(H3L1)2]Cl3·6H2O, [HoIII(H3L1)2](NO3)3·2H2O and [ErIII(H3L1)2]·H2O at 2 K between 0 and 70 kOe. The
solid lines are not a fit but are merely a guide for the eye.
S20
Figure S11: Temperature dependence of the molar ac susceptibility of [TbIII(H3L1)2] ](NO3)3,
[TbIII(H3L1)2]Cl3·MeOH·3H2O, [DyIII(H3L1)2]Cl3·6H2O, [HoIII(H3L1)2](NO3)3·2H2O and [ErIII(H3L1)2]·H2O in a
3 Oe ac field oscillating at 1500 Hz, and zero applied dc field, showing the in- (χacʹ) and out-of-phase (χacʺ)
components. The solid lines are not a fit, but merely a guide for the eye. Other frequencies are similarly
featureless to the 1500 Hz mode so are not shown.
S21
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S24