Rare Earth pcu Metal-Organic Framework Platform Based on RE4(μ3-OH)4(COO)62+ Clusters: Rational Design, Directed Synthesis, and Deliberate Tuning of Excitation Wavelengths

Article abstract of DOI:10.1021/jacs.7b04532

The T_d point group symmetry of rare earth (RE³⁺) metal clusters RE₄(μ₃-OH)₄(COO)₆²⁺ makes them attractive building blocks for creating metal-organic frameworks (MOFs) with controllable topologies. Herein, we describe the design and synthesis of a series of isoreticular MOFs featuring pcu topology [MOF-1114(RE) and MOF-1115(RE)] with variable rare earth metal ions (RE³⁺ = Y³⁺, Sm³⁺, Eu³⁺, Gd³⁺, Tb³⁺, Dy³⁺, Ho³⁺, Er³⁺, Tm³⁺, Yb³⁺) and linear amino-functionalized dicarboxylate linkers of different lengths. In total, we report 22 MOFs that vary in both composition and structure yet share the same RE₄(μ₃-OH)₄ cluster motif. We demonstrate that these pcu MOFs are cationic and that anion exchange can be used to affect the MOF properties. We also investigate the luminescence properties of a representative member of this MOF series [MOF-1114(Yb)] that exhibits near-infrared emission. We show that the excitation energy for Yb³⁺ sensitization can be carefully adjusted to lower energy via covalent postsynthetic modification at the amino group sites within the MOF.

Full text of DOI:10.1021/jacs.7b04532

Article
Rare Earth pcu MOF Platform Based on RE4(µ3-
OH)4(COO)62+ Clusters: Rational Design, Directed
Synthesis, and Deliberate Tuning of Excitation Wavelengths
Tian-Yi Luo, Chong Liu, Svetlana V Eliseeva, Patrick Flynn Muldoon, Stephane Petoud, and Nathaniel L Rosi
J. Am. Chem. Soc., Just Accepted Manuscript • Publication Date (Web): 15 Jun 2017
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Rare Earth pcu MOF Platform Based on RE
4
(μ
3
-OH)
4
(COO)
6
Clusters:
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Rational Design, Directed Synthesis, and Deliberate Tuning of Exci-
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‡
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‡*
Tian-Yi Luo, Chong Liu, Svetlana V. Eliseeva, Patrick F. Muldoon, Stéphane Petoud,
*
and Nathaniel L. Rosi
†
†
Department of Chemistry, University of Pittsburgh, Pittsburgh, PA 15260, United States
Centre de Biophysique Moléculaire, CNRS UPR 4301, 45071 Orléans, France
‡
3
+
2+
ABSTRACT: The T
d
point group symmetry of rare earth (RE ) metal clusters RE
4
(μ
3
-OH)
4
(COO)
6
makes them attractive building blocks
for creating metal-organic frameworks (MOFs) with controllable topologies. Herein, we describe the design and synthesis of a series of iso-
3
+
3+
3+
3+
reticular MOFs featuring pcu topology [MOF-1114(RE) and MOF-1115(RE)] with variable rare earth metal ions (RE = Y , Sm , Eu ,
3
+
3+
3+
3+
3+
3+
3+
Gd , Tb , Dy , Ho , Er , Tm , Yb ) and linear amino-functionalized dicarboxylate linkers of different lengths. In total, we report 22 MOFs
that vary in both composition and structure yet share the same RE (μ -OH)
cluster motif. We demonstrate that these pcu MOFs are cationic
4
3
4
and that anion exchange can be used to affect the MOF properties. We also investigate the luminescence properties of a representative member
3+
of this MOF series [MOF-1114(Yb)] that exhibits near-infrared emission. We show that the excitation energy for Yb sensitization can be
carefully adjusted to lower energy via covalent postsynthetic modification at the amino group sites within the MOF.
3
+
10-12
RE -based metal-organic frameworks (MOFs) are highly prom-
INTRODUCTION
We have a long-standing interest in creating rare earth (RE )-based
1,13,14
3+
RE -MOFs can be de-
ising for biological imaging applications.
3
+
signed to incorporate a high density of both chromophoric ligands
1
-4
3+
emissive materials, with a focus on tuning their excitation proper-
and RE , which renders them sufficiently bright. Further, different
3
+
3+
ties for optical biological imaging applications. RE emitters have
several inherent features that make them attractive for biological im-
aging: i) sharp, non-overlapping emission bands that range from the
visible to the near infrared (NIR); ii) long luminescence lifetimes
that allow for temporal discrimination from background autofluo-
rescence, which leads to enhanced signal-to-noise ratios and im-
proved sensitivity of detection; iii) continuous, stable emission sig-
nals that are highly resistant to photobleaching; and iv) the positions
of their emission bands, based on atomic fàf transitions, are inde-
pendent of solution or environmental conditions, such as pH, sol-
vent, etc. However, fàf transitions are Laporte forbidden, causing
direct excitation to be prohibitively inefficient. Further, overtones of
C-H, O-H, and N-H vibrations from solvent or other neighboring
RE can be incorporated into a single MOF, enabling the creation
3
of luminescent ‘barcoded’ materials that would be uniquely attrac-
tive for multiplex measurements. To date, we have prepared numer-
4
ous NIR-emitting MOFs and shown for the first time that they can
1
be used for biological imaging in living cells. Having demonstrated
3
+
the applicability of NIR-emitting RE -MOFs, we are now motivated
3
+
to design RE -MOF platform materials that will allow for systematic
control over structure and careful optimization of photophysical
properties. In particular, an ideal MOF platform would accommo-
3
+
date a wide range of RE , would be easily postsynthetically modified
3
+
to tune the RE environment and the photophysical properties, and
would serve as the basis for myriad structure-property studies.
Salient features of prototypical MOF platforms include: i) high sym-
metry and predictable topology imparted by rigid, well-defined sec-
3
+
molecules can quench RE emission. To overcome these chal-
3
+
lenges, RE excited states must be indirectly sensitized by appropri-
ate chromophores that have large molar absorption coefficients and
are capable of converting the excitation light into energy to feed the
15
ondary building units (SBUs); ii) ease of structural modification
and formation of isoreticular analogues by employing different metal
and ligand precursors; and iii) amenability to functionalization. Mul-
tiple MOF platforms have been developed using transition metal
3
+
electronic structures of RE . This process is called the ‘antenna ef-
5
,6
fect’. Many examples of classical molecular antennae are typically
ion-based
Zr (OH)
SBUs,
(COO)
including
-based MOFs.
Zn
4
O(COO)
6
-
While numerous RE -
and
3+
3
+
coordinated to the RE , providing efficient sensitization and protec-
16-19
6
4
O
4
n
3
+
tion to the RE from sources of non-radiative deactivation. For bio-
logical imaging applications, especially in vivo, it is crucial that the
antennae absorb low energy visible or NIR light: biological tissues
possess low autofluorescence and have much lower absorption in
10-12
3+
RE -based plat-
based MOFs have been reported and studied,
forms suitable for systematic modification and study are scarce, with
20-22
notable exceptions,
3+
despite the presence of many well-defined
23-28
discrete RE -carboxylate clusters in the literature.
RE
cubane-like
4
3
(μ -
7-9
this region known as the biological window (650 - 1450 nm),
2+
OH)
4
(COO)
6
clusters exhibiting the RE
4
(μ
3
-OH)
4
which allows for enhanced sensitivity of detection and deeper pene-
tration of the excitation radiation.
core (Figure 1) are particularly attractive building blocks due to their
symmetry, connectivity, and similarity to the ubiquitous
2
+
Zn
4
O(COO)
6
SBU. Like Zn
4
O(COO)
6
, RE
4
(μ
3
-OH)
4
(COO)
6
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can be viewed as an octahedral SBU which can theoretically lead to conditions and suitable supporting ligands play essential roles. Sev-
2
9
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1
1
1
1
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1
1
1
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1
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2
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3
3
4
4
4
4
4
4
4
4
4
4
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6
a wide variety of network topologies through rational design. For
eral studies
have reported the formation and crystallization of
(μ -OH) cores from aqueous or alco-
2
+
example, connecting RE
4
(μ
3
-OH)
4
(COO)
6
with linear linkers
. However, it has been difficult
(μ -OH)
core, in part because the RE can accommodate varying numbers of
carboxylate ligands and coordinating solvent molecules. Further,
syntheses are dependent on solvent, temperature, and pH, as well as
on the nature of carboxylate ligands employed. Although a few
various complexes with RE
4
3
4
should afford the pcu net
(
Figure 1
)
holic solutions in the presence of a variety of α-amino acids as sup-
porting ligands. In these examples, the α-amino groups in proximity
to the coordinating carboxylates may play an important role in regu-
to carefully control carboxylate coordination to the RE
4
3
4
3
+
2
7
3+
lating the RE hydrolysis/alcoholysis processes by temporarily co-
3
+
ordinating the RE centers at intermediate stages of reaction and/or
2
7
by affecting the local pH environment surrounding the cluster. We
therefore hypothesized that target MOFs based on the RE (μ
cluster should require carboxylate linkers having a
MOFs containing RE
4
(μ
3
-OH)
4
(ligand)
n
clusters have been discov-
constructing a MOF platform through deliberate and pre-
4
3
-
3
0-33
2+
0
1
2
3
4
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0
1
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0
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8
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0
1
2
3
4
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0
ered,
dictable formation of the RE
been achieved
OH)
4
(COO)
6
2
+
4
(μ
3
-OH)
4
(COO)
to
6
cluster has not
date.
primary amino group located at the ortho position to the coordinat-
ing carboxylate. To implement this design strategy, we reacted 2-
amino-1,4-benzenedicarboxylic acid (H
GdCl ∙6H O in mixed dimethylformamide (DMF) and water solu-
tion at 100 ˚C. This reaction yielded clear, colorless cubic crystals,
2
-NH
2
-BDC) with
3
2
3
5
MOF-1114(Gd)
.
Single crystal X-ray diffraction (SCXRD) of MOF-1114(Gd) re-
vealed that it crystallizes in the cubic space group Fm-3m with the
unit cell dimensions a = b = c = 27.860 Å. The inorganic SBU has the
distorted cubane Gd
(Figure 2A and Figure S2.1). The four Gd ions located at the ver-
tices of the tetrahedron (shown in green in Figure 2A) are bridged
-OH which protrude slightly from the four triangular faces.
Each Gd pair is bridged by one carboxylate group along each edge
of the tetrahedron. In addition, two other O atoms are bound to each
Gd ; one is located on the 3-fold axis and the other is disordered
among 3 symmetry equivalent positions around the 3-fold axis with
equal 1/3 occupancy (Figure S2.1). We speculate that these O at-
4
(μ
3
-OH)
4
polymetallic core with T symmetry
d
3
+
by four µ
3
3
+
3
+
3
+
oms could be either water molecules or μ
ions. The inorganic SBUs, formulated as [Gd
1
-OH coordinating to Gd
(μ
, are connected by the linear
4
3
-
(
2-x)+
OH)
4
(COO)
6
(H
2
O)8-x(μ
1
-OH) ]
x
aminophenylene linkers into a pcu 3-D framework (Figure 2A-C).
Interconnected ~10 Å × 10 Å 1-D channels run along the a, b, and c
crystallographic axes. In addition to Gd , isoreticular MOFs were
prepared using Y , Tb , Dy , Ho , Er , Tm , and Yb , as evi-
denced by comparing their powder X-ray diffraction (PXRD) pat-
terns to that collected for MOF-1114(Gd) and that simulated from
single crystal diffraction data (Figure 2D and Figures S2.3 to S2.10).
3
+
2+
Figure 1. Structure of the RE
4
(μ
3
-OH)
4
(COO)
6
SBU and construc-
tion of the pcu net (RE , green spheres; C, grey spheres; O, red spheres;
green tetrahedron defines RE core; H atoms omitted for clarity; teal
3+
3+
3+
3+
3+
3+
3+
3+
3+
octahedron defines structure of SBU).
Herein, we present the rational design and synthesis of a new porous
Attempts to make isoreticular MOFs by reacting RECl
1,4-benzenedicarboxylic acid (H -BDC) or other functionalized
variants of H -BDC (e.g. -Br, -NO , -OH) yielded MOFs containing
3
∙6H
2
O with
2
+
pcu MOF platform based on the RE
4
(μ
3
-OH)
4
(COO)
6
cluster. We
2
determine strategies for constructing an isoreticular family of MOFs
based on this SBU and present, in total, 22 new MOF materials with
varying structures and compositions. Finally, we demonstrate that
these materials are amenable to postsynthetic modification (PSM)
via both ion exchange and covalent chemistry. In one representa-
tive example, we show for the first time that covalent PSM can be
used to systematically optimize the photophysical properties of an
2
2
3
+
infinite RE -carboxylate SBUs, pointing toward the potential im-
portance of the primary amino group in influencing SBU formation.
Collectively, this series of new MOFs represents a platform for dif-
ferent studies and applications based on the unique optical, mag-
34
3+
netic, and catalytic properties of RE .
MOF-1114 could be charged depending on x, the number of μ
-OH
groups per SBU. For example, if x is less than 2, the framework
would be positively charged. The positive charges would likely be
1
3+
Yb -based MOF in this series. More specifically, we shift the excita-
tion wavelengths of this MOF towards lower energy in order to cre-
ate more biologically adapted luminescent probes that would pos-
sess excitation and emission wavelengths within the biological win-
-
balanced by anions, such as Cl , randomly disordered in the MOF
cavities. Qualitative scanning electron microscopy energy-dispersive
X-ray spectroscopy (SEM/EDS) analysis on the as-synthesized
MOF-1114(Tb) (Figures S2.11 to S2.16) reveal the presence of Cl
in the MOF crystals, likely in the form of mobile Cl ions, as con-
firmed by ion exchange experiments. MOF-1114(Tb) was soaked in
a 0.1 M DMF
7-9
dow.
RESULTS AND DISCUSSION
-
Formation of RE
4
(μ
3
-OH)
4
-related complexes relies on well-
controlled hydrolysis or alcoholysis of RE where both solution
3+
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Figure 2. Construction of a MOF series based on the RE
4
(μ
of MOF-1114 (RE , green spheres; C, grey spheres; O, red spheres; RE
dinated water molecules, μ -OH groups, and H atoms have been omitted for clarity; only one of the possible positions is illustrated for each disordered
NH
group); (C) 1-D ~10 Å × 10 Å channels along the a, b, and c crystallographic axes in MOF-1114; (D) PXRD patterns of MOF-1114 synthesized
3
-OH)
4
motif. (A) Organic linker and inorganic SBU in MOF-1114; (B) crystal structure
3
+
4
(μ -OH) , green tetrahedra; teal octahedron defines structure of SBU; coor-
3
4
1
–
2
3
+
3+
3+
3+
3+
3+
3+
3+
3+
with different RE (front to back: simulated, Y , Gd , Tb , Dy , Ho , Er , Tm , Yb ); (E) organic linkers and inorganic SBU in MOF-1130 and
MOF-1131 (light-orange spheres highlight O atoms on chelating carboxylates); (F) crystal structure of MOF-1130 (for clarity, the identical interpen-
etrating framework is omitted; only one of the possible positions is illustrated for each disordered –NH
for clarity, the identical interpenetrating framework is omitted; only one of the possible positions is illustrated for each disordered –NH
organic linker and inorganic SBU in MOF-1115; (I) crystal structure of MOF-1115 (only one of the possible positions is illustrated for each disordered
2
group); (G) crystal structure of MOF-1131
(
2
group); (H)
3+
3+
3+
3+
3+
3+
3+
3+
–
NH
group); (J) PXRD patterns of MOF-1115 synthesized with different RE (front to back: simulated, Sm , Eu , Gd , Tb , Dy , Ho , Er ).
2
solution of NMe
4
BF
4
for 5 days. Thereafter, the crystalline material
anions per formula unit in MOF-1114 was quantified by solution nu-
clear magnetic resonance (NMR) spectroscopy. An ion-exchanged
was thoroughly washed with fresh DMF and analyzed using
-
SEM/EDS, which shows nearly complete removal of Cl and appear-
MOF-1114(Tb) sample was digested with acidified DMSO-d
analyzed using both solution H and F NMR with the internal
6
and
-
1
19
ance of F from BF
4
(Figures S2.17 to S2.20). The number of mobile
+
standard α,α,α-trifluorotoluene (Figures S2.21 to S2.22). NMe
4
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1
-
was not observed via H NMR, while 0.5 BF
4
per NH
2
-BDC, were
If the crosslinking ligands in MOF-1130 and MOF-1131 were re-
1
9
-
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
observed via F NMR, indicating 1.5 Cl per SBU in the as-synthe-
sized MOF-1114(Tb). The as-synthesized MOF-1114 is therefore
moved and replaced with terminal aqua ligands, the resulting struc-
tures would be isoreticular to MOF-1114. In MOF-1114, the posi-
2
+
formulated
as
[RE
4
(μ
3
-OH)
4
(NH
2
-BDC)
3
(H
2
O)7.5(μ
1
-
tive charges of the RE
4
(μ
3
-OH)
4
(COO)
6
cluster are balanced by
3
+
-
OH)0.5]·1.5Cl,10DMF according to elemental microanalysis (see
page S13 in Supporting Information for details) and solution H
μ
1
-OH groups bound to the RE centers and Cl ions in the cavities.
1
MOF-1130 and MOF-1131 have a different means to achieve charge
balance: two additional carboxylates bind to the inorganic SBUs.
The longer biphenyl and terphenyl struts in MOF-1130 and MOF-
1131 may yield void space that is sufficient to accommodate the ad-
ditional diagonal crosslinking ligands that provide charge balance.
We postulated that a sterically bulky ligand, such as 4,4'-(9,10-an-
NMR (Figure S2.23). We note that each MOF analogue may have
elemental compositions that deviate slightly from this formula.
These data indicate that: i) the framework is cationic, and ii) the an-
ions are mobile and can be readily exchanged without loss of frame-
work crystallinity (Figure S2.24). Therefore, ion exchange could ad-
vantageously be used to tailor the MOF pore space and adjust MOF
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
thracenediyl)bis(2-aminobenzoate) (NH -ABB) (Figure 2H), may
2
properties. Thermogravimetric analyses of both as-synthesized and
prevent the incorporation of the diagonal crosslinker and lead to the
target expanded version of the pcu net. Using similar reaction condi-
-
BF
4
anion-exchanged MOF-1114(Tb) samples (Figure S2.25)
show a steep weight loss corresponding to solvent removal between
25 ˚C and ~150 ˚C followed by a steady gradual weight loss up to
650 ˚C. We have not yet determined the experimental conditions for
tions that produced MOF-1114
,
MOF-1130, and MOF-1131, H
-
2
NH -ABB and RECl ∙6H
2
3
2
O were reacted to yield MOF-1115, which
crystallizes in the cubic space group Fd-3m with the unit cell dimen-
sions a = b = c = 44.8598 Å. MOF-1115 consists of two maximally
displaced interpenetrated frameworks that are isoreticular to MOF-
activating the as-synthesized MOF to obtain permanent porosity.
-
However, after anion exchange with BF
4
,
MOF-1114(Tb) can be
adsorp-
3
+
3+
3+
3+
3+
3+
activated. Despite a loss of crystallinity after activation, N
2
1114 (Figure 2I). Seven different RE (Sm , Eu , Gd , Tb , Dy ,
3
+
3+
tion analysis (77 K) yields a type I isotherm (Figure S2.26), charac-
teristic of a microporous material.
Ho , Er ) can form MOF-1115, as confirmed by comparing their
PXRD patterns with that simulated from crystal structure data of
MOF-1115(Tb) (Figure 2J and Figures S4.2 to S4.8). MOF-1115 is
Having successfully prepared MOF-1114 via deliberate design and
directed synthesis, we next sought to build a family of isoreticular an-
alogues using biphenyl- and terphenyl-based amino-functionalized
carboxylate linkers: 3,3'-diamino-1,1'-biphenyl-4,4'-dicarboxylate
formulated as [RE
(
4
(μ
3
-OH)
4
(NH
2
-ABB)
3
(H
2
O) ]·2Cl,11.5DEF
8
1
19
DEF = diethylformamide) based on solution H and F NMR
spectra of anion-exchanged MOF-1115(Tb) (Figure S4.9 and
S4.10) and CHN elemental microanalysis of as-synthesized
MOF-1115(Tb) (see page S56 in Supporting Information for
details). In this example, we demonstrate the importance of ligand
steric demand in influencing MOF topology. In summary, we have
(NH
ylate (NH
tions that yielded MOF-1114 but substituting either H
or H -NH -TPDC for H -NH -BDC, two new twofold interpene-
trated MOF structures were formed: MOF-1130(Y Gd Tb Dy Ho)
and MOF-1131(Er Yb) MOF-1130 and MOF-1131 are isoreticu-
lar. MOF-1130 crystallizes in the monoclinic space group P2
/n (a
18.0453 Å, b = 18.1800 Å, c = 32.5984 Å; α = 90º, β = 95.864º, γ =
0º); MOF-1131 crystallizes in the same space group with different
2
-BPDC) and 3,3''-diamino-1,1':4',1''-terphenyl-4,4''-dicarbox-
-TPDC) (Figure 2E). Using similar solvothermal condi-
-NH -BPDC
2
2
2
2
2
2
2
achieved, via design and rational, directed syntheses, a family of new
,
,
,
,
2+
pcu MOFs based on the RE
4
(μ
3
-OH)
4
(COO)
6
cluster.
,
.
An ideal material for optical biological imaging should have excita-
tion and emitting wavelengths within the biological window (vide
1
=
9
3
+
supra). Many RE emit in the NIR, yet typical MOF ligands that
serve as the antennae absorb in the UV or high energy visible re-
unit cell demensions (a = 23.6058 Å, b = 22.2824 Å, c = 37.1223 Å;
α = 90º, β = 90.222º, γ = 90º) (Figure 2F,G, Figures S3.1 to S3.10).
The inorganic SBU for both MOF-1130 and MOF-1131 (Figure
3
6
gions. In order to lower the excitation energy, ligands having ex-
4
tended π systems are often used. One common consequence of this
3
+
approach is formation of lower density MOFs that have fewer RE
emitters per unit volume. We suggest that covalent postsynthetic
2
E) consists of the RE
4
(µ
3
-OH) polymetallic core observed in
4
MOF-1114. This result confirms our hypothesis that the primary
amino group adjacent to the carboxylate facilitates formation of
3
7
modification (CPSM) of MOF linkers (antennae) is one way to
systematically shift their excitation wavelengths to lower energy
RE
4
(µ
3
-OH) . However, in addition to the six carboxylates that
4
3
+
3
+
while maintaining a high density of RE emitters.
bridge the edges of the RE tetrahedron, two additional carboxylate
3
+
groups coordinate in a chelating mode to two of the RE in the clus-
ter, resulting in a total of eight carboxyates per SBU present in two
different coordination modes (Figure 2E; O on chelating carbox-
The MOF-1114 platform is ideal for investigating this approach: i)
the amino groups can serve as sites for CPSM reactions used to ex-
tend the π system, and ii) the pore space is sufficient for facile diffu-
sion of precursor molecules for CPSM and for accommodating the
product extended antennae. MOF-1114(Yb) was selected because
ylates highlighted in orange). This new SBU, formulated as [RE
OH) (COO) (solvent) ] (solvent = DMF or H O) according to
4
3
(µ -
4
8
4
2
3
+
SCXRD data, should be a neutral moiety, which is supported by the
absence of Cl peaks in the SEM/EDS spectra (Figures S3.11 to
S3.21). To visualize the crystal structures of MOF-1130 and MOF-
Yb emits exclusively in the NIR range (λem = 940 - 1100 nm). We
hypothesized that condensation reactions between primary amines
of NH -BDC and aromatic aldehydes would result in the expansion
2
1
131, a single, non-interpenetrated framework is shown for each
of the conjugated π system, leading to a red-shift of the excitation
band. To test this hypothesis, colorless as-synthesized MOF-
1114(Yb) crystals were soaked in DMF solutions of either salicylal-
dehyde or 3-hydroxynaphthalene-2-carboxaldehyde to yield orange
MOF in Figure 2F and 2G, respectively (the interpenetrated frame-
works are shown in Figure S3.1). Cages within the MOF are defined
by eight neighboring inorganic SBUs that no longer sit at the corners
of a cube, as in MOF-1114. Instead, the cages are distorted with two
parallel faces along (010), each having one additional ligand cross-
linking two SBUs on the face diagonal. The carboxylates from these
MOF-1114(Yb)
tively (Scheme 1). PXRD patterns after CPSM reactions indicate
that both MOF-1114(Yb) and MOF-1114(Yb)
retain their origi-
1
crystals and red MOF-1114(Yb)
crystals, respec-
2
1
2
3+
1
diagonal crosslinkers coordinate to the single RE , while the carbox-
nal crystallinity after modification (Figures S5.1 and S5.2). H NMR
of acid digested MOF samples suggested the inclusion of approxi-
3+
ylates on the linkers on the edges of the cage all bridge two RE ions.
mately 1 equivalent of salicylaldehyde in MOF-1114(Yb)
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Journal of the American Chemical Society
equivalent of 3-hydroxynaphthalene-2-carboxaldehyde in MOF-
1114(Yb)
per NH -BDC ligand (Figures S5.3 and S5.4). To con-
firm covalent attachment of the aldehydes to the framework prior to
acid digestion, NaBH in ethanol was used to reduce the imine to the
in MOF-1114(Yb) can only be excited by light with wavelengths
shorter than 460 nm. In contrast, the excitation spectra are signifi-
cantly red-shifted after CPSM to 570 nm for MOF-1114(Yb)
and
to 670 nm for MOF-1114(Yb)
. This red-shift of excitation bands
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
1
4
2
stable C-N single bond. The reduced MOF samples were then di-
can be attributed to sensitizers with large conjugated π systems upon
1
3+
gested for H NMR analysis and liquid chromatography-mass spec-
CPSM of RE -MOFs. It is worth mentioning that for MOF-
trometry (LC-MS), which showed that ~70% of the NH
MOF-1114(Yb)
were converted into the Schiff base product. Re-
duced alcohol product from salicylaldehyde and unmodified NH
2
-BDC in
1114(Yb)
2
, the longest edge of the excitation wavelengths lies within
1
the biological window (650 - 1450 nm). This advantage in combina-
3
+
2
-
tion with Yb emission in the NIR range makes MOF-1114(Yb)
a
2
BDC were also observed, indicating the presence of free salicylalde-
hyde trapped in MOF pores after CPSM (Figures S5.5 and S5.6).
promising candidate for biological applications including in vivo im-
aging.
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
Similarly, for MOF-1114(Yb)
verted to a Schiff base product. Again, reduced alcohol product and
unmodified NH -BDC were observed, indicating free 3-hy-
2
, 22% of the NH -BDC were con-
2
2
droxynaphthalene-2-carboxaldehyde trapped in the pore after
CPSM (Figures S5.7 and S5.8).
Scheme 1. CPSM reactions in MOF-1114(Yb).
Scale bars represent 100 μm in length.
Figure 3. (A) Corrected and normalized absorption spectra of single
Absorption spectra collected on single crystalline samples of
crystalline MOF-1114(Yb) (black), MOF-1114(Yb)
1
(navy) and
MOF-1114(Yb)
quentially red-shifted. The as-synthesized MOF-1114(Yb) only ab-
sorbs below 450 nm, while the absorption bands of MOF-1114(Yb)
and MOF-1114(Yb)
extend to 550 nm and 650 nm, respectively
Figure 3A). To rule out the possibility that the red-shift of absorp-
,
MOF-1114(Yb)
1
, and MOF-1114(Yb)
2
are se-
MOF-1114(Yb)
2
(red); (B) normalized absorption spectra of salic-
ylaldehyde (green) and 3-hydroxy-naphthalene-2-carboxaldehyde
(grey) in solution (10 µM in dichloromethane); corrected and nor-
malized (C) emission spectra (λex = 380 nm) and (D) excitation
1
2
(
spectra (λem = 980 nm) of MOF-1114(Yb)
,
MOF-1114(Yb)
and
1
tion bands is caused by the presence of free aldehyde molecules in
the pores, solution UV-Vis spectra were collected for each of the free
aldehydes (Figure 3B). Both molecules only absorb at wavelengths
below 500 nm. Therefore, the red-shift of absorption spectra and the
crystal color change after CPSM reactions can be ascribed to the
imine products featuring extended conjugated π systems.
MOF-1114(Yb)
2
; (E) Luminescence lifetimes (τobs) and quantum
yields (QYb) of MOFs at room temperature (crystals under DMF; 2σ
values between parentheses; lifetimes measured under excitation at
3
55 nm).
3+
Quantum yields of NIR Yb emission (QYb) were determined under
excitation at 380 and 500 nm (Figure 2E). QYb values for MOF-
Photoluminescence studies were then performed. The characteristic
1
114(Yb)
1
and MOF-1114(Yb)
under 380 nm excitation were
2
3
+
2
Yb NIR emission band in the range 940 - 1100 nm due to the F5/2
found to be similar to that of unmodified MOF-1114(Yb). On the
2
® F7/2 transition can be observed for MOF-1114(Yb)
1114(Yb) and MOF-1114(Yb)
upon excitation through the lig-
ands’ bands at 380 nm (Figure 3C). This is an indication that an ‘an-
tenna effect’ is operating between the organic sensitizers and Yb for
all samples: because Yb does not possess an electronic level in the
,
MOF-
3+
other hand, CPSM significantly improves Yb quantum yields un-
1
2
der higher excitation wavelength, resulting in up to 4.4 times in-
crease compared to the unmodified MOF-1114(Yb). Luminescence
3
+
3+
2
2
lifetimes of Yb MOFs upon monitoring the F5/2 ® F7/2 transition
3
+
lie in the range 620 - 670 ns, indicating that CPSM does not signifi-
3
+
UV or in the visible, the sensitization of Yb has to occur through
the electronic levels of the chromophoric entities. The excitation
3+
cantly affect the coordination environment around Yb .
spectra of MOF-1114(Yb)
upon monitoring the Yb emission show sequential red-shifts, con-
.
sistent with the absorption spectra (Figure 3A vs 3D). Yb emission
,
MOF-1114(Yb)
1
, and MOF-1114(Yb)
2
CONCLUSION
We successfully designed and synthesized a new class of MOFs
3
+
3
+
based on the RE
4
(μ
3
-OH)
cluster motif. A new pcu MOF platform
4
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Journal of the American Chemical Society
Page 6 of 8
2
+
was created using the highly symmetric RE
4
(μ
3
-OH)
4
(COO)
6
was measured several times under comparable experimental condi-
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
cluster as the inorganic SBU. We demonstrated that this MOF plat-
tions, varying the position of samples. Estimated experimental error
for the quantum yield determination is ~10 %.
General synthesis of MOF-1114. 2-amino-1,4-benzenedicarboxylic
3
+
form is highly tunable in terms of RE composition and structure
metrics. It can be systematically modified via either postsynthetic an-
ion exchange or covalent modification. Finally, CPSM was used to
deliberately red-shift the excitation wavelengths of a representative
NIR-emitting MOF, MOF-1114(Yb), into the range suitable for bi-
ological imaging applications.
acid (1 equiv) and RECl
3
∙6H O (3 or 4 equiv) were dissolved by
2
DMF in a 20 mL Pyrex vial. To the DMF solution, a certain amount
of nanopure water was added. The vial was then capped and placed
in a 100 ºC oven for 12 h to yield cubic block crystals. Once the re-
action cooled to room temperature, the mother liquor was decanted.
The crystals were then washed with fresh DMF (3x). The detailed
EXPERIMENTAL DETAILS
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
General Methods. All purchased chemicals were used without
further purification except where otherwise noted. Nanopure water
syntheses using different RECl
ing Information.
3
∙6H O can be found in the Support-
2
TM
(18.1 MΩ) was obtained from a Barnstead Diamond water puri-
General synthesis of MOF-1130. 3,3'-diamino-1,1'-biphenyl-4,4'-di-
fication system. Powder X-ray diffraction patterns were collected
using a Bruker AXS D8 Discover powder diffractometer at 40 kV,
40 mA for Cu Kα, (λ = 1.5406 Å) with a scan speed of 0.10 sec/step
from 3 to 45º at a step size of 0.02º. The data were analyzed using
the EVA program from the Bruker Powder Analysis Software pack-
age. The simulated powder patterns were calculated using Mercury
carboxylate (1 equiv) and RECl ∙6H O (4 equiv) were dissolved by
3
2
DMF in a 20 mL Pyrex vial. To the DMF solution, a certain amount
of nanopure water was added. The vial was then capped and placed
in a 100 ˚C oven for 12 h to yield colorless crystals. Once the reac-
tion cooled to room temperature, the mother liquor was decanted.
Crystals were then washed with fresh DMF (3x). The detailed syn-
3
.8 based on crystal structures of corresponding MOFs. Single crys-
theses using different RECl ∙6H O can be found in the Supporting
3
2
tal X-ray diffraction experiments were performed on a Bruker X8
Prospector Ultra diffractometer equipped with an Apex II CCD de-
tector and an IµS micro-focus Cu Kα X-ray source (λ = 1.54178 Å).
Information.
General synthesis of MOF-1131. 3,3''-diamino-1,1':4',1''-terphenyl-
,4''-dicarboxylic acid (1 equiv) and RECl ∙6H O (2 equiv) were dis-
4
3
2
Data were collected at 230 K or 240 K under N
2
flow and processed
solved by DMF in a 20 mL Pyrex vial. To the DMF solution, a certain
amount of nanopure water was added. The vial was then capped and
placed in an 85 or 100 ˚C oven for 12 h to yield light yellow crystals.
Once the reaction cooled to room temperature, the mother liquor
was decanted. Crystals were then washed with fresh DMF (3x). The
using the Bruker APEX II software package and refined with Olex2
3
8,39 1
13
19
program.
H, C and F NMR spectra were obtained using
Bruker Avance III 300/400/500 MHz spectrometers. Chemical
shifts are in parts per million (ppm) using the residual solvent peak
(
CDCl
analyses (TGA) were performed using a TGA Q500 thermal analy-
sis system under a N atmosphere from room temperature to 650
C at a ramping rate of 5 °C/min. LC-MS analyses were performed
3
, D
2
O, or DMSO-d
6
) as references. Thermogravimetric
detailed syntheses using different RECl
Supporting Information.
3
∙6H O can be found in the
2
2
General synthesis of MOF-1115. 4,4'-(9,10-anthracendiyl)bis(2-
aminobenzoic acid) (1 equiv) and RECl ∙6H O (5 equiv) were dis-
°
3
2
on a Shimadzu LCMS-2020 instrument using a 6 minute running
time with a constant 1:1 ratio of acetonitrile : water at a constant
flow rate of 0.2 mL/min without passing through a column.
SEM/EDS analyses were conducted using ZEISS Sigma 500 VP
SEM with Oxford Aztec X-EDS. The crystal samples were washed
with ethanol and drop cast on silicon wafers and dried under ambi-
ent condition before SEM/EDS analyses. Soluiton UV−Vis absorp-
tion spectra were collected using an Agilent 8453 UV−Vis spec-
trometer equipped with deuterium and tungsten lamps. Solid state
UV-Vis absorption spectra were collected on individual crystals on
glass slide using a CRAIC QDI 2010 microspectrophotometer in
solved in DEF in a 20 mL Pyrex vial. To the DEF solution, a certain
amount of nanopure water was added. The vial was then capped and
placed in a 100 ˚C oven for 24 h to yield light yellow crystals. Once
the reaction cooled to room temperature, the mother liquor was de-
canted. The crystals were washed with fresh DEF (3x). The detailed
syntheses using different RECl
ing Information.
3
∙6H O can be found in the Support-
2
Anion exchange of MOF-1114(Tb) with NMe
100 mg of as-synthesized MOF-1114(Tb) crystals were soaked in 10
mL of a 0.1 M DMF solution of NMe BF in a vial. The NMe BF
solution was removed and the crystals were washed with fresh DMF
(3x) every 24 h before the vial was replenished with fresh NMe BF
solution. After 5 days, the crystals were copiously washed with DMF
4
BF .
Approximately
4
4
4
4
4
2
transmission mode. The sampling area was fixed at 37 × 37 µm .
The photoluminescence properties were measured in an integra-
tion sphere using a Horiba Jobin-Yvon Fluorolog-3 spectrofluo-
rometer equipped with a 450 W xenon excitation source and a visi-
ble photomultiplier tube (PMT) (220 - 800 nm, R928P; Hamama-
tsu), and a NIR PMT (950 - 1650 nm, H10330-75; Hamamatsu)
on solid MOF samples stored under DMF in quartz capillary tubes.
All spectra were corrected for the instrumental functions. Lumines-
cence lifetimes were determined under 355 nm excitation provided
by the third harmonic of a YG 980 Quantel Nd-YAG laser; emis-
sion signals were selected using a Horiba Scientific iHR-320 mono-
chromator, detected using a Hamamatsu H10330-75 NIR PMT,
fed into a 500 MHz bandpass digital oscilloscope (TDS 754C; Tek-
tronix), transferred to a PC in which data were processed with the
Origin 8® program. Quantum yields were determined with a Horiba
Scientific Fluorolog-3 spectrofluorimeter based on an absolute
method (Model G8, GMP SA, Renens, Switzerland). Each sample
4
4
1
19
and dried on a Schlenk line before solution H and F NMR analysis.
About 5 mg of crystals were dissolved in 500 μL of DMSO-d and 15
μL of DCl in D O (36%). 1 μL of α,α,α-trifluorotoluene was added
as internal standard in the sample before H and F NMR.
adsorption at 77 K. After anion exchange, ~50 mg of MOF-
114(Tb) crystals were exchanged in dry EtOH for 3 days in a 20
6
2
1
19
N
2
1
mL vial. EtOH was removed every 24 h followed by replenishment
1
with fresh EtOH until no DMF peak was observed by solution H
NMR of an acid digested MOF sample. The crystals were then
transferred to the activation chamber of a Tousimis SAMDRI-PVT-
3
B supercritical drier where supercritical CO activation experiment
2
was performed. During the entire transfer process, all the crystals
were soaked under dry EtOH. After cooling to 0 ˚C, the chamber
was filled with liquid CO
2
. Every 30 min, the chamber was purged
for 5 min while the CO filling rate was kept above the purge rate to
2
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Journal of the American Chemical Society
ensure that the MOF sample remains soaked under liquid CO
chamber temperature was kept between 0 - 10 ˚C. After 6 h, the
chamber filled with liquid CO was heated to 40 ˚C to transform
CO from liquid state to supercritical state. The chamber was then
vented slowly for the next 18 h until the pressure dropped down to 1
atm. The MOF sample was then degassed at 50 ˚C under dynamic
2
. The
Svetlana V. Eliseeva: 0000-0002-1768-8513
Patrick F. Muldoon: 0000-0001-5241-1694
Stéphane Petoud: 0000-0003-4659-4505
Nathaniel L. Rosi: 0000-0001-8025-8906
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
vacuum for 24 h before the N
formed on a Quantachrome Autosorb-1 instrument at 77 K.
Preparation and characterization of MOF-1114(Yb)
5 mg of as-
2
adsorption experiment was per-
Notes
1
.
The authors declare no competing financial interest.
synthesized MOF-1114(Yb) were soaked in 1 mL 0.5 M DMF solu-
tion of salicylaldehyde for 48 h at room temperature to yield orange
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
ACKNOWLEDGMENT
MOF-1114(Yb)
crystals. The orange crystals were then copiously
1
This project received partial support from the Defense Threat Reduc-
tion Agency-Joint Science and Technology Office for Chemical and Bi-
ological Defense Basic Research (Grant no. HDTRA1-16-1-0044,
NLR). In addition, this work is partially supported by La Ligue Contre
le Cancer, La Region Centre, Agence Nationale de la Recherche (Lu-
miphage ANR-13-BSV5-009 and Lumzif ANR-12-BS07-0012). S.P.
acknowledges support from the Institut National de la Santé et de la Re-
cherche Médicale (INSERM). The authors thank the Petersen Nano
Fabrication and Characterization Facility at the University of Pittsburgh
for access to PXRD, SEM/EDS and microspectrophotometry instru-
mentation.
washed with anhydrous DMF (5x). The MOF crystals were dried
under vacuum for 10 min and dissolved in a mixture of 500 μL
DMSO-d
6
and 15 μL 36% D
2
O solution of DCl. The solution was
used for H NMR experiment. To confirm the formation of imine
bond, MOF-1114(Yb)
was then reacted with 1 mL of 0.3 M ethanol
solution of NaBH in a 4 mL vial. After 24 h, the solid sample was
washed with MeOH (3x) and dried under a Schlenk line vacuum for
10 min. To the dried crystal sample were added 500 μL D O and 10
μL 10% D O solution of NaOD. The mixture was sonicated for 30
min and centrifuged. The supernatant was used for H NMR. 3 mg
of the reduced product from MOF-1114(Yb)
were dissolved in 1
O. The solution was used
1
1
4
2
2
1
1
REFERENCES
mL MeOH and 15 μL of 36 % HCl in H
2
(
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for LC-MS experiment.
Collet, G.; Kieda, C.; Li, T.; Geib, S. J.; Rosi, N. L.; Petoud, S. Proc. Natl.
Acad. Sci. 2013, 110, 17199-17204.
(2) An, J.; Shade, C. M.; Chengelis-Czegan, D. A.; Petoud, S.; Rosi, N. L. J.
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Petoud, S. J. Am. Chem. Soc. 2009, 131, 18069-18071.
Preparation and characterization of MOF-1114(Yb)
. 5 mg of as-
2
synthesized compound MOF-1114(Yb) were soaked in 1 mL 0.5 M
DMF solution of 3-hydroxynaphthalene-2-carboxaldehyde for 48 h
at room temperature to yield red MOF-1114(Yb)
2
crystals. The red
crystals were copiously washed with anhydrous DMF (5x) and dried
under Schlenk line vacuum for 10 min. the sample was then dis-
(
4) White, K. A.; Chengelis, D. A.; Zeller, M.; Geib, S. J.; Szakos, J.; Petoud,
S.; Rosi, N. L. Chem. Commun. 2009, 4506-4508.
solved with 500 μL DMSO-d
DCl. The solution was used for H NMR experiment. To confirm
the formation of imine bond, MOF-1114(Yb)
was then reacted
with 1 mL 0.3 M ethanol solution of NaBH . After 24 h, the solid
6
and 15 μL of 36% D O solution of
2
(
(
(
(
5) Weissman, S. I. J. Chem. Phy. 1942, 10, 214-217.
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AUTHOR INFORMATION
Corresponding Authors
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*
*
stephane.petoud@inserm.fr
nrosi@pitt.edu
D'Elia, V.; WojtasŁukasz; Adil, K.; Eddaoudi, M. Nat. Chem. 2014, 6, 673-
680.
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ORCID
Belmabkhout, Y.; Cairns, A. J.; Chen, Z.; Wojtas, Ł.; Eddaoudi, M. J. Am.
Chem. Soc. 2015, 137, 5421-5430.
Tian-Yi Luo: 0000-0002-9973-9328
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23) Wu, Y.; Morton, S.; Kong, X.; Nichol, G. S.; Zheng, Z. Dalton Trans.
Chong Liu: 0000-0002-9780-9062
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011, 40, 1041-1046.
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