Sandwich-type mixed tetrapyrrole rare-earth triple-decker compounds. Effect of the coordination geometry on the single-molecule-magnet nature

Article abstract of DOI:10.1021/ic400485y

Employment of the raise-by-one step method starting from M(TClPP)(acac) (acac = monoanion of acetylacetone) and [Pc(OPh)₈]M′[Pc(OPh) ₈] led to the isolation and free modulation of the two rare-earth ions in the series of four mixed tetrapyrrole dysprosium sandwich complexes {(TClPP)M[Pc(OPh)₈]M′[Pc(OPh)₈]} [1-4; TClPP = dianion of meso-tetrakis(4-chlorophenyl)porphyrin; Pc(OPh)₈ = dianion of 2,3,9,10,16,17,23,24-octa(phenoxyl)phthalocyanine; M-M′ = Dy-Dy, Y-Dy, Dy-Y, and Y-Y]. Single-crystal X-ray diffraction analysis reveals different octacoordination geometries for the two metal ions in terms of the twist angle (defined as the rotation angle of one coordination square away from the eclipsed conformation with the other) between the two neighboring tetrapyrrole rings for the three dysprosium-containing isostructural triple-decker compounds, with the metal ion locating between an inner phthalocyanine ligand and an outer porphyrin ligand with a twist angle of 9.64-9.90 and the one between two phthalocyanine ligands of 25.12-25.30. Systematic and comparative studies over the magnetic properties reveal magnetic-field-induced single-molecule magnet (SMM), SMM, and non-SMM nature for 1-3, respectively, indicating the dominant effect of the coordination geometry of the spin carrier, instead of the f-f interaction, on the magnetic properties. The present result will be helpful for the future design and synthesis of tetrapyrrole lanthanide SMMs with sandwich molecular structures.

Full text of DOI:10.1021/ic400485y

Article
pubs.acs.org/IC
Sandwich-Type Mixed Tetrapyrrole Rare-Earth Triple-Decker
Compounds. Effect of the Coordination Geometry on the Single-
Molecule-Magnet Nature
Jinglan Kan,† Hailong Wang,† Wei Sun,† Wei Cao,† Jun Tao,‡ and Jianzhuang Jiang*,†
†Beijing Key Laboratory for Science and Application of Functional Molecular and Crystalline Materials, Department of Chemistry,
University of Science and Technology Beijing, Beijing, China
‡State Key Laboratory of Physical Chemistry of Solid Surfaces and Department of Chemistry, College of Chemistry and Chemical
Engineering, Xiamen University, Xiamen, China
S
* Supporting Information
ABSTRACT: Employment of the raise-by-one step method starting from
M(TClPP)(acac) (acac = monoanion of acetylacetone) and [Pc(OPh)8]-
M′[Pc(OPh)8] led to the isolation and free modulation of the two rare-
earth ions in the series of four mixed tetrapyrrole dysprosium sandwich
complexes {(TClPP)M[Pc(OPh)8]M′[Pc(OPh)8]} [1−4; TClPP =
dianion of meso-tetrakis(4-chlorophenyl)porphyrin; Pc(OPh)8 = dianion
of 2,3,9,10,16,17,23,24-octa(phenoxyl)phthalocyanine; M−M′ = Dy−Dy,
Y−Dy, Dy−Y, and Y−Y]. Single-crystal X-ray diffraction analysis reveals different octacoordination geometries for the two metal
ions in terms of the twist angle (defined as the rotation angle of one coordination square away from the eclipsed conformation
with the other) between the two neighboring tetrapyrrole rings for the three dysprosium-containing isostructural triple-decker
compounds, with the metal ion locating between an inner phthalocyanine ligand and an outer porphyrin ligand with a twist angle
of 9.64−9.90° and the one between two phthalocyanine ligands of 25.12−25.30°. Systematic and comparative studies over the
magnetic properties reveal magnetic-field-induced single-molecule magnet (SMM), SMM, and non-SMM nature for 1−3,
respectively, indicating the dominant effect of the coordination geometry of the spin carrier, instead of the f−f interaction, on the
magnetic properties. The present result will be helpful for the future design and synthesis of tetrapyrrole lanthanide SMMs with
sandwich molecular structures.
tetrapyrrole rings provides a good chance to work for this target
owing to the inherent advantage in modulating the rare-earth
ions and tuning the coordination geometry for lanthanide ions
and f−f magnetic interaction.5 In the present paper, a series of
four sandwich-type mixed (phthalocyaninato)(porphyrinato)
di-rare-earth complexes with isostructural triple-decker molec-
ular structure {(TClPP)M[Pc(OPh)8]M′[Pc(OPh)8]} (1−4;
M−M′ = Dy−Dy, Y−Dy, Dy−Y, and Y−Y) have been
designed, synthesized, and structurally characterized [TClPP
= dianion of 5,10,15,20-tetrakis(4-chlorophenyl)porphyrin and
Pc(OPh)8 = dianion of 2,3,9,10,16,17,23,24-octa(phenoxyl)-
phthalocyanine] (Scheme 1). Free modulation in the two
shortly separated rare-earth ions between dysprosium and
yttrium in combination with their different octacoordination
geometries (in terms of the twist angle defined as the rotation
angle of one coordination square from tetrapyrrole away from
the eclipsed conformation with the other) renders it possible
toward clarifying the effect of the coordination geometry of the
spin carrier and/or the f−f interaction on their magnetic
properties. Systematic and comparative studies over the
magnetic properties revealed magnetic-field-induced SMM,
INTRODUCTION
■
Both lanthanide- and transition-metal-based single-molecule
magnets (SMMs) have attracted increasing research interest
because of their potential applications in magnetic storage and
molecular spintronics associated with the magnetic bistability.1
Investigations clearly revealed the relationship of the energy
barrier in reversing magnetization for most polynuclear
transition-metal-based SMMs with the magnetic anisotropy
projected on the ground exchange and the multiplet projection
of the total spin on the symmetry axis due to the much larger
exchange coupling than the zero-field-splitting effect on an
individual metal.2 In good contrast, origination of the height of
the barrier in reversing magnetization for lanthanide-based
analogues was only proposed to be associated with the larger
zero-field-splitting effect on the spin carrier and/or the weak
interionic exchange interaction.3 Limited studies conducted
thus far suggest the magnetic exchange interaction on the SMM
behavior of the lanthanide-based complexes without concerning
the contribution from the coordination geometry of an
individual lanthanide ion and vice versa.4 Obviously, suitable
polylanthanide SMM systems that allow studies toward
clarifying the contribution of the coordination geometry and/
or f−f magnetic interaction are highly desired. The availability
of sandwich-type multinuclear rare-earth complexes with mixed
Received: February 24, 2013
© XXXX American Chemical Society
A
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Scheme 1. Synthesis of the Sandwich-Type Mixed (Phthalocyaninato)(porphyrinato) Di-Rare-Earth Triple-Decker Complexes
with M−M′ = Dy−Dy, Y−Dy, Dy−Y, and Y−Y for 1−4
SMM, and non-SMM nature for the Dy−Dy, Y−Dy, and Dy−Y
systems, respectively, indicating the dominant effect of the
coordination geometry of the spin carrier, instead of the f−f
interaction, on the magnetic properties of the sandwich-type
tetrapyrrole lanthanide triple-decker systems.
Supporting Information, the two singlet signals at δ 9.44 and
8.50 in the diyttrium triple-decker compound 4 are attributed
to the nonperipheral protons of the Pcin(OPh)8 and
Pcout(OPh)8 rings, respectively. Replacement of one of the
two diamagnetic yttrium ions by a paramagnetic dysprosium
ion leads to an obvious upfield shift of the nonperipheral
proton signals of the Pcin(OPh)8 and Pcout(OPh)8 rings to δ
−44.65 and −38.97 for 2 as well as δ −4.42 and 12.14 for 3
(Figures S4 and S5 in the Supporting Information), revealing
the long-distance lanthanide-induced shift of the dysprosium-
(III) ion to the whole triple-decker molecular skeleton.7 A
further change in the remaining diamagnetic yttrium ion in 2
and 3 to a paramagnetic dysprosium ion in 1 induces a further
shift of the nonperipheral proton signals of the Pcin(OPh)8 and
Pcout(OPh)8 rings to δ −59.66 and −35.58 (Figures 1 and S3 in
the Supporting Information), suggesting the presence of f−f
interaction between the two shortly separated dysprosium ions
in this didysprosium triple-decker compound 1.7
RESULTS AND DISCUSSION
■
Treatment of the half-sandwich porphyrinato rare-earth
complex M(TClPP)(acac), generated in situ from the reaction
between [M(acac)3]·nH2O (acac = monoanion of acetylace-
tone) and H2TClPP, with bis(phthalocyaninato) rare-earth
complex [Pc(OPh)8]M′[Pc(OPh)8] in refluxing 1,2,4-trichlor-
obenzene (TCB) for 4 h led to isolation of the sandwich-type
mixed (phthalocyaninato)(porphyrinato) di-rare-earth com-
plexes 1−3.6 For the purpose of a comparative study, 4 was
also obtained with the half-sandwich porphyrinatoyttrium
complex and the bis(phthalocyaninato)yttrium double-decker
compound as starting materials. It is worth noting that
employment of such a kind of raise-by-one step synthesis
method allows free modulation on the two rare-earth species
between dysprosium and yttrium in the triple-decker structure.
In addition to elemental analysis, these four triple-decker
compounds have also been characterized by a series of
spectroscopic methods including matrix-assisted laser desorp-
tion ionization time-of-flight (MALDI-TOF) mass and NMR
spectroscopy (Figure 1 and Figures S1−S6 and Table S1 in the
Supporting Information). The MALDI-TOF mass spectra of
these four compounds clearly showed intense signals for
molecular ion [M + H]+ (Figure S1 in the Supporting
Information). As is clearly shown in Figure S2 in the
Supporting Information and summarized in Table S1 in the
The mixed tetrapyrrole nature with sandwich-type triple-
decker molecular structures for 1−3 was clearly revealed by
single-crystal X-ray diffraction analysis. Single crystals of all of
the three triple-decker compounds suitable for X-ray diffraction
analysis were obtained by diffusion of methanol onto the
solution of a corresponding compound in chloroform. The
isostructural compounds crystallize in the tetragonal system
with the space group P4nc, and each unit cell contains two
sandwich-type triple-decker molecules of 1−3 (Table S2 in the
Supporting Information). The structural data of 1−3 are
summarized in Table S3 in the Supporting Information. As
shown in Figure 2A,B, the outer phthalocyanine and porphyrin
ligands are connected by two rare-earth ions sharing a common
phthalocyanine ligand, forming the isostructural triple-decker
molecular structure for 1. This is also true for the analogous
triple-decker complexes 2 and 3 (Figures S7 and S8 in the
Supporting Information). The two rare-earth ions M and M′ in
these three compounds are separated by a short distance of
3.586(3)−3.605(3) Å, leading to magnetic−dipolar interac-
tion.5f,8 The rare-earth ion sandwiched between the inner
phthalocyanine and outer porphyrin ligands adopts a more
distorted square-antiprism (SAP) geometry comprised of four
isoindole nitrogen atoms of the phthalocyanine ligand and four
pyrrole nitrogen atoms of the porphyrin ligand with a twist
angle ϕ1 of 9.64−9.90°, and the other between two
phthalocyanine ligands employs a distorted SAP octacoordina-
tion geometry constructed from eight isoindole nitrogen atoms
with a twist angle ϕ2 of 25.12−25.30° (Figure 2C).
Figure 1. 1H NMR spectra for triple-decker complexes 1−3 in CDCl3,
showing the singals of the nonperipheral protons of the Pcin(OPh)8 (i)
and Pcout(OPh)8 (ii) rings.
To evaluate the effect of the coordination geometry around
the dysprosium ion and the f−f interaction between the two
dysprosium ions in the didysprosium triple-decker compound
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μB for the former triple-decker compound and 5.48−7.61 μB for
the latter two compounds at 5 T without reaching the
theoretical magnetization saturation [20.00 and 10.00 μB4for
5
two and one dysprosium(III) (6H15/2, S = /2, L = 5, g = /3)
ions, respectively], revealing the crystal-field effect on the
dysprosium ion.9b−d As also can be seen in this figure, the
nonsuperposition field-dependent magnetization curves ob-
tained at 2.0, 3.0, and 5.0 K for the di- and monodysprosium
involved triple-decker compounds 1−3 indicate the presence of
crystal-field effects, thus leading to magnetic anisotropy for the
dysprosium(III) ion in these triple-decker complexes.
Figure 4 shows the temperature dependence of the
alternating-current (ac) magnetic susceptibility of 1−3 under
Figure 2. Molecular structure of 1 in a side view (A) and a top view
(B), with all of the hydrogen atoms, benzene rings of phenoxy groups,
and solvent molecules omitted for clarity. The twist angles ϕ1 and ϕ2
are defined as the twist angles around M and M′ for 1−3, respectively
(C).
on the magnetic properties, the static magnetic properties of
the whole series of three complexes 1−3 have been
systematically and comparatively investigated. As can be seen
in Figure S2 in the Supporting Information, the curve of the
magnetic susceptibility χMT for 1−3 shows a temperature-
dependent character. The χMT value of 28.09 cm3 K mol−1 for
1 at 300 K is consistent with the value of 28.34 cm3 K mol−1 for
two dysprosium(III) ions [6H15/2, S = 5/2, L = 5, g = 4/3], while
those of 14.77 and 14.32 cm3 K mol−1 for 2 and 3 are
consistent with the expected value of 14.17 cm3 K mol−1 for
one dysprosium(III) ion.9 When the temperature is lowered,
the χMT values of these three compounds decrease slowly until
about 15 K, then decreasing to minimum values of 15.06, 8.84,
and 7.69 cm3 K mol−1 for 1−3 at 2 K, respectively. The overall
magnetic behavior of all of these three compounds can be
attributed mainly to the crystal-field effects such as thermal
depopulation of the dysprosium(III) Stark sublevels and
intramolecular magnetic interaction.9b−d Actually, the intra-
molecular Dy−Dy interaction in 1 could be analyzed in a
qualitative manner according to the ΔχMT tendency by
subtracting the χMT values of the monodysprosium triple-
decker compounds 2 and 3 from that of 1.9d As shown in
Figure 3, the increase of ΔχMT for 1 following a decrease of the
temperature indicates the ferromagnetic interaction between
the two dysprosium(III) ions in this compound.9d In addition,
as shown in Figure S9 in the Supporting Information, the three
nonsuperposition curves for 1−3 display a rapid increase at low
field and eventually achieve the maximum value of 12.40−12.61
Figure 4. Plots for the temperature dependence of the in-phase (χ′)
and out-of-phase (χ″) ac susceptibilities of 1−3 under a zero applied
dc magnetic field.
a zero direct-current (dc) magnetic field oscillating at 10−997
Hz. As can be seen, only monodysprosium triple-decker
compound 2 with a conformation of {(TClPP)Y[Pc(OPh)8]-
Dy[Pc(OPh)8]} exhibits a frequency-dependent character in
the in-phase (χ′) and out-of-phase (χ″) signals, indicating the
slow relaxation of magnetization and revealing the SMM nature
for this complex. However, the relaxation time of magnetization
cannot be deduced for this compound most probably because
of the location of the relaxation mode at higher frequency than
997 Hz associated with the fast quantum tunneling. In contrast,
the other monodysprosium triple-decker compound 3 with a
conformation of {(TClPP)Dy[Pc(OPh)8]Y[Pc(OPh)8]} does
not show a frequency-dependent character in the in-phase (χ′)
and out-of-phase (χ″) signals (Figure 4), revealing its non-
Figure 3. Temperature dependence of χMT for 1−3 (A) as well as that
of ΔχMT = [χM(1) − χM(2) − χM(3)]T (B).
C
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SMM nature under a zero applied dc magnetic field.
Unexpectedly, this is also true for the didysprosium triple-
decker compound 1 despite involvement of the same
[Pc(OPh)8]Dy[Pc(OPh)8]} fragment as that in analogous 2
(Figure 4). Anyway, these results suggest the more significant
effect of the coordination geometry of a lanthanide ion relative
to the magnetic interaction between the lanthanide ions on the
magnetic properties of sandwich-type tetrapyrrole rare-earth
triple-decker complexes.
For the purpose of further understanding the magnetic
behavior of these sandwich-type tetrapyrrole dysprosium triple-
decker complexes, dynamic magnetic measurements over 1−3
have been conducted under an external dc, 2000 Oe magnetic
field. As expected, the frequency-dependent character in the in-
phase (χ′) and out-of-phase (χ″) signals still exists for 2 (Figure
5), confirming the SMM nature of this compound. In addition,
Ueff = 17.3 cm−1 (24.9 K) and τ0 = 1.52 × 10−7 s with R =
0.9989, suggesting the presence of one thermally activated
relaxation process.9d Not surprisingly, typical slow relaxation of
magnetization behavior could still not be observed for the other
monodysprosium 3 involving (TClPP)Dy[Pc(OPh)8] instead
of the [Pc(OPh)8]Dy[Pc(OPh)8] fragment. However, under an
external dc, 2000 Oe magnetic field, the didysprosium triple-
decker compound 1 starts to show a frequency-dependent
character in the in-phase (χ′) and out-of-phase (χ″) signals in
the whole oscillating range of 10−1488 Hz employed,
indicating the field-induced SMM nature of this compound.10
Comparative inspection over the magnetic properties in
association with the detailed molecular conformations of 1−3
seems to reveal the significant role of the bis-
(phthalocyaninato)dysprosium fragment [Pc(OPh)8]Dy[Pc-
(OPh)8] over the (phthalocyaninato)(porphyrinato)-
dysprosium fragment (TClPP)Dy[Pc(OPh)8] in a triple-decker
molecule in contributing to the SMM nature of the mixed
tetrapyrrole rare-earth complexes most probably because of the
less significant deviation of the coordination geometry of the
dysprosium ion sandwiched between two phthalocyanine
ligands, in comparison with the one between one porphyrin
and one phthalocyanine ligands, from the SAP in terms of the
twist angle between two tetrapyrrole rings, as detailed above.
This appears in line with that derived from previous studies
over the magnetic properties of sandwich-type tetrapyrrole
dysprosium compounds with double-, triple-, and quadruple-
decker molecular structures to the point that the degree of
suppression of the QTM was revealed to increase along with a
decrease in the deviation of the twist angle from 45° despite the
typical slow relaxation of magnetization behavior, as revealed
for all of the thus-far-reported tetrapyrrole dysprosium
sandwich complexes with the twist angle between two
tetrapyrrole rings ranging from 18 to 43°.8,9c,d,11 Nevertheless,
the non-SMM nature revealed for the triple-decker compound
3 with (TClPP)Dy[Pc(OPh)8] as the sole spin-carrier
fragment, in which the twist angle between two tetrapyrrole
rings amounts to less than 10°, actually 9.68°, appears to give
an obvious hint for the future design and synthesis of
tetrapyrrole dysprosium SMMs with sandwich molecular
structure. Additional support for this point comes from the
non-SMM character of the didysprosium triple-decker com-
pound 1 under a zero applied dc magnetic field despite
involvement of the better spin-carrier fragment [Pc(OPh)8]-
Dy[Pc(OPh)8]} in addition to (TClPP)Dy[Pc(OPh)8].
CONCLUSIONS
■
In conclusion, three sandwich-type mixed tetrapyrrole di-rare-
earth complexes with dysprosium as spin carrier(s) and an
isostructural triple-decker conformation have been designed
and synthesized. Free modulation in the two shortly separated
rare-earth ions between dysprosium and yttrium in combina-
tion with their different octacoordination geometry in terms of
the twist angle for the dysprosium ion between the two
neighboring tetrapyrrole rings in the triple-decker molecule
renders it possible toward clarifying the effect of the
coordination geometry of the spin carrier and/or the f−f
interaction on the magnetic properties for these sandwich
systems. The magnetic-field-induced SMM, SMM, and non-
SMM nature revealed for the Dy−Dy, Y−Dy, and Dy−Y
systems, respectively, indicate the dominant effect of the
coordination geometry of the spin carrier, instead of the f−f
interaction, on the magnetic properties.
Figure 5. Plots for the temperature dependence of the in-phase (χ′)
and out-of-phase (χ″) ac susceptibilities of 1−3 under a 2000 Oe
applied dc magnetic field.
the peak of the out-of-phase signal (χ″) for this compound
could be observed until a frequency as low as 330 Hz,
indicating the effective suppression of quantum tunneling of
magnetization (QTM) under an external dc, 2000 Oe magnetic
field. On the basis of a thermally activated mechanism, τ = τ0
exp(Ueff/kT) and τ = 1/2πν, the Arrhenius law fitting for the
data under a 2000 Oe magnetic field was carried out. As shown
in Figure S10 in the Supporting Information, a linear
relationship exists between ln(τ) and 1/T in the temperature
range of 2.26−2.80 K for 2, which, in turn, results in a barrier
D
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7.25 (Por-Hβ), 7.12−7.18 (m, 28H, Por-Ph-H, Pcout-Ph-Hp and Pcout
-
EXPERIMENTAL SECTION
■
Ph-Hm), 6.32−6.34 (d, 4H, Por-Ph-H). 13C NMR (400 MHz, CDCl3,
δ): 157.87, 156.69, 156.57, 154.20, 152.34, 149.89, 148.98, 140.08,
133.68, 133.51, 132.96, 132.73, 132.53, 130.74, 129.94, 127.77, 127.16,
126.24, 124.97, 123.23, 120.29, 119.93, 117.50, 114.69, 112.59.
MALDI-TOF MS: an isotopic cluster peaking at m/z 3429.1. Calcd
for C204H120Cl4N20O16Y2: m/z 3427.9 ([M + H]+). Anal. Calcd for
C204H120Cl4N20O16Y2: C, 71.50; H, 3.53; N, 8.17. Found: C, 71.40; H,
3.49; N, 7.99.
Measurements. H, H−1H COSY, and 13C NMR spectra were
recorded on a Bruker DPX 400 spectrometer in CDCl3. Spectra were
referenced internally using the residual solvent resonance (δ 7.26 for
1H NMR) relative to SiMe4. Electronic absorption spectra were
1
1
recorded with a Hitachi U-4100 spectrophotometer. MALDI-TOF
mass spectra were taken on a Bruker BIFLEX III ultrahigh-resolution
Fourier transform ion cyclotron resonance (FT-ICR) mass spec-
trometer with α-cyano-4-hydroxycinnamic acid as the matrix.
Elemental analysis was performed on an Elementar Vario El III.
Chemicals. All reagents and solvents were used as received. The
compounds of M(acac)3·H2O (M = Dy and Y)12 and H2TClPP13 and
the homoleptic bis(phthalocyaninato) rare-earth(III) complexes
M′[Pc(OPh)8]2 [Pc(OPh)8 = 2,3,9,10,16,17,23,24-octaphenoxyphtha-
locyaninate]14 were prepared according to literature methods.
General Procedure for the Synthesis of {(TClPP)M[Pc(OPh)8]-
M′[Pc(OPh)8]} (1−4; M−M′ = Dy−Dy, Y−Dy, Dy−Y, and Y−Y). A
mixture of H2(TClPP) (0.03 mmol) and [M(acac)3]·nH2O (ca. 0.04
mmol) in TCB (2 mL) was refluxed for 4 h under a slow stream of
nitrogen. The resulting dark-cherry-red solution was cooled, then
M′[Pc(OPh)8]2 (0.02 mmol) was added, and the mixture was refluxed
for a further 4 h. After cooling to room temperature, 10 mL of n-
hexane was added to the mixture. The precipitate was filtered off and
washed with n-hexane and methanol. The residue left was chromato-
graphed on a silica gel column with CH2Cl2 as the eluent. Repeated
chromatography followed by recrystallization from CHCl3 and
methanol gave pure compound as a dark powder. In a similar manner,
4 was also isolated. Single crystals of 1−3 suitable for X-ray diffraction
analysis were obtained by diffusion of methanol onto a solution of the
corresponding compound in chloroform.
X-ray Crystallographic Analysis of 1−3. Single crystals suitable
for X-ray diffraction analysis were grown by diffusing MeOH into the
CHCl3 solutions of these compounds. The details of the structure
refinement are given in Table S2 in the Supporting Information, and
structural data of 1−3 are summarized in Table S3 in the Supporting
Information. Crystal data for 1−3 were determined by X-ray
diffraction analysis at 100−126 K using an Oxford Diffraction Gemini
E system with Cu Kα radiation (λ = 1.5418 Å), using a ω scan mode
with an increment of 1°. The preliminary unit cell parameters were
obtained from 30 frames. The final unit cell parameters were obtained
by global refinement of reflections obtained from integration of all of
the frame data. The collected frames were integrated using the
preliminary cell-orientation matrix. SMART software was used for data
collection and processing, ABSpack for absorption correction,15 and
SHELXL for space group and structure determination, refinement,
graphics, and structure reporting.16 CCDC 902562−902564 for 1−3,
respectively, containing the supplementary crystallographic data for
this paper can be obtained free of charge from the Cambridge
Crystallographic Data Centre via www.ccdc.cam.ac.uk/data_request/
cif.
ASSOCIATED CONTENT
■
{(TClPP)Dy[Pc(OPh)8]Dy[Pc(OPh)8]} (1). Yield: ca. 36 mg (50%).
UV−vis [CHCl3; λmax, nm (log(ε), M−1 cm−1)]: 364 (5.30), 412
(5.16), 625 (4.91), 752 (4.58). 1H NMR (400 MHz, CDCl3, δ): 34.66
S
* Supporting Information
MS and 1H NMR spectra for 1−4, 1H−1H COSY NMR spectra
for 2−4, 13C NMR spectrum of 4, χMT and ΔχMT, M vs H/T,
ln(τ) vs 1/T for 2, NMR data and assignments for 1−4, details
of the structure refinement and structural data of 1−3, and CIF
file of 1−3. This material is available free of charge via the
Internet at http://pubs.acs.org.
(s, Por-Ph-H), 12.46 (s, Por-Ph-H), 3.21 (s, Por-Ph-H), 1.74 (s, Pcout
-
Ph-Hp), 1.21 (s, Pcout-Ph-Hm), −4.27 (s, Pcout-Ph-Ho), −5.28 (s, Pcin-
Ph-Hp), −5.90 (s, Pcin-Ph-Hm), −15.03 (s, Por-Ph-H), −16.48 (s, Pcin-
Ph-Ho), −35.58 (s, Pcout-Hα), −59.66 (s, Pcin-Hα). MALDI-TOF MS:
an isotopic cluster peaking at m/z 3575.5. Calcd for
C204H120Cl4Dy2N20O16: m/z 3575.1 ([M + H]+). Anal. Calcd for
C204H120Cl4Dy2N20O16: C, 68.55; H, 3.38; N, 7.84. Found: C, 68.76;
H, 3.46; N, 7.73.
AUTHOR INFORMATION
■
{(TClPP)Y[Pc(OPh)8]Dy[Pc(OPh)8]} (2). Yield: ca. 30 mg (43%).
UV−vis [CHCl3; λmax, nm (log(ε), M−1 cm−1)]: 364 (5.22), 410
(5.08), 625 (4.83), 752 (4.47). 1H NMR (400 MHz, CDCl3, δ): 31.73
(s, Por-Ph-H), 28.01 (s, Por-Ph-H), 14.95 (s, Por-Ph-H), 1.62 (s,
Pcout-Ph-Hm), 2.07 (s, Pcout-Ph-Hp), −0.99 (s, Pcin-Ph-Hp), −2.23 (s,
Pcin-Ph-Hm), −4.39 (s, Por-Ph-H), −5.25 (s, Pcout-Ph-Ho), −10.38 (s,
Pcin-Ph-Ho), −38.97 (s, Pcout-Hα), −44.65 (s, Pcin-Hα). MALDI-TOF
MS: an isotopic cluster peaking at m/z 3501.9. Calcd for
C204H120Cl4DyN20O16Y: m/z 3501.5 ([M + H]+). Anal. Calcd for
C204H120Cl4Y2N20O16: C, 70.00; H, 3.46; N, 8.00. Found: C, 70.07; H,
3.41; N, 7.89.
Corresponding Author
*E-mail: jianzhuang@ustb.edu.cn.
Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
■
Financial support from the National Key Basic Research
Program of China (Grants 2013CB933402 and
2012CB224801), Natural Science Foundation of China, Beijing
Municipal Commission of Education, and State Key Laboratory
of Physical Chemistry of Solid Surfaces is gratefully acknowl-
edged.
{(TClPP)Dy[Pc(OPh)8]Y[Pc(OPh)8]} (3). Yield: ca. 52 mg (75%).
UV−vis [CHCl3; λmax, nm (log(ε), M−1 cm−1)]: 362 (5.20), 412
(5.06), 625 (4.82), 753 (4.50). 1H NMR (400 MHz, CDCl3, δ): 12.14
(s, Pcout-Hα), 8.56 (s, Por-Ph-H), 7.26 (s, Pcout-Ph-Hp), 7.03 (s, Pcout
-
Ph-Hm), 6.89 (s, Pcout-Ph-Ho), 4.76 (s, Por-Ph-H), 4.75 (s, Pcin-Ph-
Hp), 4.57 (s, Pcin-Ph-Hm), 2.33 (s, Pcin-Ph-Ho), −2.23 (s, Por-Hβ),
−4.42 (s, Pcin-Hα), −19.33 (s, Por-Ph-H). MALDI-TOF MS: an
isotopic cluster peaking at m/z 3502.0. Calcd for
C204H120Cl4DyN20O16Y: m/z 3501.5 ([M + H]+). Anal. Calcd for
C204H120Cl4Dy2N20O16: C, 70.00; H, 3.46; N, 8.00. Found: C, 70.28;
H, 3.40; N, 7.93.
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