Article

pubs.acs.org/JPCC

Fluorescence of A100 MOF and Adsorption of Water, Indole, and

Naphthalene on A100 by the Spectroscopic, Kinetic, and DFT Studies
Jun Dai,† Michael L. McKee,‡ and Alexander Samokhvalov*,†
†
Department of Chemistry, Rutgers University, Camden, New Jersey 08102, United States
‡
Department of Chemistry and Biochemistry, Auburn University, Auburn, Alabama 36849, United States
*
S Supporting Information

ABSTRACT: Metal−organic frameworks (MOFs) are promising materials for

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adsorption and separations. It is important to understand the details of chemical bonding

between the adsorbate and structural units in the MOFs. In A100 MOF, the near-UV−
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visible fluorescence is found to be the intralinker fluorescence. Naphthalene and indole

form the stoichiometric “host-guest” π−π adsorption complexes with A100 that contain
one adsorbate molecule per two BDC linkers, and adsorption of indole causes a strong
quenching of the intralinker fluorescence. The excitation wavelength dependent steady-
state fluorescence spectra, the nanosecond time-resolved fluorescence spectra, and DFT
calculations indicate the strong π−π interactions between adsorbed indole and
naphthalene and aromatic ring of the BDC linker, as well as hydrogen bonding between
adsorbed indole and COO group of the linker. Activated A100 adsorbs up to four water molecules per BDC linker. Kinetic study
of adsorption of naphthalene and indole from n-alkane on hydrated A100 yields the preferential adsorption of indole as
determined by the in-situ time-dependent fluorescence spectroscopy and complementary ex-situ UV−vis absorption
spectroscopy.

1. INTRODUCTION The high microporosity of MIL-53(Al) results in the Langmuir

Aromatic N-heterocyclic compounds are abundantly present in
petroleum1 and other fossils, in refinery streams,2 and in certain
commercial fuels.3 Upon combustion of nitrogen-containing
fuels, toxic nitrogen oxides are released that cause air pollution.
The adsorption of aromatic N-heterocyclic compounds from
liquid fuels was studied on zeolites, activated carbons,4 and
novel sorbents such as ionic liquids.5 Metal−organic frame-
works (MOFs) have a very high surface area and pore volume
and are well suited for adsorption. Adsorption of many
industrially important gases such as hydrogen,6 acetylene,7
and carbon dioxide8 on the MOFs has been studied quite
extensively, and an excellent review has recently been published
on the topic,9 while adsorption in the liquid phase was studied
much less. Many MOFs have a moderate to high stability to
elevated temperatures and oxygen, but the majority of the
MOFs undergo hydrolysis, e.g., ref 10. Many Al-containing
MOFs11 with linkers of aromatic acids are water stable
including microporous MIL-53(M), where M = Al,12 Cr,13
Fe,14 In,15 Sc.16 The 3D framework of MIL-53(Al) is built by
the infinite 1D chains of repeating corner-sharing octahedral
AlO4(OH)2 units, and the chains are interconnected by the
COO groups of organic linker, the anion of 1,4-benzenedi-
carboxylic acid (BDC).17 MIL-53(Al) is synthesized hydro-
thermally, and in its as-synthesized form, rhombic-shaped
micropores ca. 7.3 × 7.7 Å are filled with an excess of 1,4-
benzenedicarboxylic acid (BDCH2) used in the synthesis.12
Upon thermal “activation”, MIL-53(Al) desorbs the BDCH2
impurity and water and changes to its large-pore (lp) form aka
the high-temperature (ht) form Al(OH)[O2C−C6H4−CO2].
surface area up to 1600 m2/g. In the lp form, micropores are
free of adsorbate and have the dimensions ca. 8.5 × 8.5 Å. The
lp form of MIL-53(Al) can adsorb water vapor at room
temperature, yielding the narrow pore (np) form12 with
formula Al(OH)[O2C−C6H4−CO2] H2O. The hydrogen
bonds are formed between the H atoms of adsorbed water
molecule and the O atoms of the COO groups of the linker.
The np MIL-53(Al) can reversibly lose adsorbed water upon
heating, and the lp form is formed. The reversible change
between two forms of MIL-53 aka “breathing” has been utilized
for selective separations, e.g., the np MIL-53(Cr) features
selective adsorption of CO2 in the presence of methane.13 MIL-
53(Al) has a commercially available equivalent A100 Basolite
MOF18 with specific surface area 1084 m2/g, total pore volume
0.51 cm3/g, and similar XRD pattern.19
Indole (IND) is the smallest molecule with fused
heteroaromatic and aromatic rings; IND and alkyl-substituted
indoles are present in petroleum, tar sands and bitumen,
streams of petroleum refineries,2 and commercial liquid fossil
fuels. The functional group of indole is present in amino acid
tryptophan and proteins containing tryptophan and in many
biologically active natural and synthetic compounds: metabo-
lites, e.g., tryptamine, natural pigments, e.g., eumelanin,20
medicinal drugs for treatment of many diseases including HIV21
and cancer,22 in food supplements, e.g., melatonin, etc.
Received: October 11, 2014
Revised: January 9, 2015
Published: January 9, 2015

© 2015 American Chemical Society 2491 DOI: 10.1021/jp510272s

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The Journal of Physical Chemistry C
Naphthalene (NAP) is the smallest hydrocarbon with a fused-
ring aromatic system, and fused-ring aromatic hydrocarbons are
the common chemical components of all fossils and liquid fossil
fuels. Adsorption of IND, pyridine, pyrrole, and quinoline was
studied from n-octane23 on activated MIL-53(Al), but the
adsorbed amount of IND was not reported.23 Adsorption of
IND and quinoline on activated MIL-53(Al) was tentatively
assigned to the π−π interactions, but no experimental proof
was provided.23 To our knowledge, no direct spectroscopic
characterization of the nature of chemical bonds between the
aromatic and the heteroaromatic adsorbate and adsorption sites
in MIL-53 or A100 MOF was reported. The mechanism of
adsorption of the smallest fused-ring aromatic hydrocarbon
naphthalene on mesoporous F300 MOF was reported by our
group.24 Adsorption of naphthalene on microporous MOF
[Cu2(BDC)2(dabco)] was reported,25 but its mechanism was
not determined. Adsorption of the fused-ring hydrocarbons on
MIL-53(Al) and A100 MOF was not reported, to our
knowledge.
Fluorescence spectroscopy is a convenient nondestructive
method for studies of adsorption.26 However, there are very few
papers on characterization of adsorption of aromatic and
heterocyclic compounds in solution27 or titration of adsorbate
in solution with the use of fluorescence spectroscopy.28 Direct
experimental determination of the type of chemical bonding in
the “host−guest” adsorption complexes of the MOFs and
aromatic hydrocarbons or aromatic N-heterocyclic compounds
was not reported by fluorescence spectroscopy, to our
knowledge. Further, fluorescence spectroscopy is well suited
to study the MOFs29,30 and mechanisms of adsorption on the
MOFs, but the origin of the fluorescence from many MOFs is
not known. The origin of the fluorescence from MIL-53(Al)
was tentatively assigned to emission due to the LMCT,31 while
it was noted in a recent critical review that the LMCT
fluorescence of MIL-53(Al) is unlikely for thermodynamic
reasons.32
Density functional theory (DFT) is an ab initio technique of
quantum chemistry that is commonly used to calculate the
energies and geometries of adsorption sites and adsorption
complexes. Due to a high requirement on the CPU, DFT
calculations are usually performed on the small clusters
containing one metal site and one or a few linker units.15
The DFT calculations of the small clusters of HKUST-1 are
rather abundant,33,34 while calculations of adsorption on MIL-
53 are rare. Small clusters of MIL-53(Ga) and MIL-53(Al)
containing one metal site and two BDC linkers were utilized in
the quantum chemical study of “breathing” upon adsorption
and desorption of water.15 To our knowledge, calculations of
the structure and binding energy in the host−guest adsorption
complexes formed by either aromatic or heteroaromatic
compounds with the cluster of MIL-53 were not reported.
Recently, we reported a study of reactive adsorption of H2S
on Cu(II) sites in Cu−ZnO/SiO2 sorbents by the comple-
mentary UV−vis diffuse reflectance spectroscopy (UV−vis
DRS), electron spin resonance (ESR) spectroscopy, and DFT
computations.35 Most recently, we reported the mechanism of
adsorption of aromatic sulfur compounds on C300 MOF33 and
mechanisms of adsorption of N-heterocyclic compound IND vs
fused-ring aromatic hydrocarbon NAP on F300 MOF.24
Herein, we report the following: (i) direct experimental proof
of the origin of the near-UV and visible fluorescence from
A100; (ii) the stoichiometry of adsorption complexes formed
by activated A100 with water, IND, and NAP; (iii)
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spectroscopic characterization of the host−guest adsorption
complexes of IND, NAP, and water with activated A100 using
the complementary wavelength-dependent and nanosecond
time-resolved fluorescence spectroscopy; (iv) complementary
DFT calculations of interactions of water, IND, and NAP with
binding sites in the cluster of MIL-53(Al) due to the π−π
interactions and hydrogen bonding, and (v) the spectroscopic
study of kinetics and stoichiometry of adsorption of IND vs
NAP on hydrated A100 by the complementary in-situ time-
dependent fluorescence spectroscopy and ex-situ UV−vis
spectroscopy.
2. EXPERIMENTAL AND THEORETICAL METHODS
2.1. Chemicals. Naphthalene (NAP), indole (IND), 1,4-
benzenedicarboxylic acid (BDCH2), and A100 Basolite MOF
were from Sigma; DMF and n-heptane of spectroscopic purity
were from Fisher.
2.2. Activation and Hydration of A100. The as-received
A100 Basolite termed asA100 was activated at 150 °C and <1 ×
10−3 Torr for 24 h36 and kept isolated from moisture in
ambient air; the obtained activated A100 (actA100) has the Hill
formula C8H5AlO5. Upon activation, actA100 was placed inside
the desiccator with liquid water to be in contact with water
vapor at relative humidity (RH) ≈ 100% at 25 °C. The
desiccator was kept closed for 2 or 7 days, and obtained
hydrated A100 MOFs were termed 2hydA100 and 7hydA100,
respectively.
2.3. Preparation of the Stoichiometric Adsorption
Complexes of A100 with IND or NAP. The sample of 0.024
g asA100 was thermally activated in a 0.5 cc quartz fluorescence
cuvette, and 0.5 cc of 0.08 M solution of IND or NAP in n-
heptane was added under argon. The cuvette was promptly
closed with a PTFE (polytetrafluoroethylene) stopper, shaken
for 1 h on a rotary shaker (Roto-Shake Genie), opened under
argon, and placed into the high-vacuum system, and n-heptane
solvent was slowly evaporated at 100−1000 mTorr. The turbo
pump was turned on until pressure < 1 mTorr; then the
vacuum system was vented with argon; the cuvette was closed
with a PTFE stopper and sealed with Parafilm tape.
2.4. Steady-State Fluorescence Spectroscopy. Steady-
state fluorescence spectroscopy experiments were conducted
using a Cary Eclipse spectrometer equipped with a custom-
designed angular fluorescence accessory from Quantum
Northwest Inc. The angle of incidence of the excitation beam
was set at 30° from the normal to the surface of the cuvette to
minimize spectral artifacts due to primary and secondary
reabsorption of light.37 Visualization of the cross-section of the
photoexcitation beam reaching the surface of the cuvette
allowed the conclusion that the excitation beam was completely
absorbed by the specimen. Wavelength-dependent steady-state
fluorescence measurements were conducted at λexc = 260, 280,
310, and 372 nm, and bandwidths of excitation and emission
slits were chosen at 5 and 5 nm to avoid spectral saturation.
2.5. Nanosecond Time-Resolved Fluorescence Spec-
troscopy. Nanosecond time-resolved fluorescence spectrosco-
py measurements were conducted using the Fluorolog-3
spectrometer from Horiba Scientific. The sample in the
fluorescence cuvette was oriented at 30° from the normal to
the front surface of the cuvette. The light source was pulsed
NanoLED with λexc = 366 nm and pulse duration < 1 ns. Time-
resolved emission was collected at the center wavelength 440
nm and bandwidth 8 nm.
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2.6. Kinetics of Adsorption by in-Situ Time-Depend- Scheme 1. Changes of Mass and Chemical Formula of
ent Fluorescence Spectroscopy in Suspension. A Cary Activated and Hydrated A100 MOF
Eclipse fluorescence spectrometer was equipped with a custom-
designed angular fluorescence accessory that had a ministirrer
that can rotate the PTFE-coated magnetic ministir bar inside
the sealed fluorescence cuvette. This accessory allowed
maintaining the 3.5 cc quartz fluorescence cuvette at a constant
temperature of 20 °C. The sample of 0.144 g of hydrated
2hydA100 was placed in the cuvette, the PTFE-coated
magnetic ministir bar was added under argon, 3.5 cc of 0.08
M solution of IND or NAP in n-heptane was added under
argon, and the cuvette was closed. The suspension in the
cuvette was continuously stirred, and the time-dependent
fluorescence spectra were continuously measured at λexc = 310
nm.
2.7. Kinetics of Adsorption by ex-Situ UV−Vis
Absorption Spectroscopy. Chemical analysis of the liquid
phase of the suspension with A100 was conducted in parallel
with the in-situ time-dependent fluorescence spectroscopic
measurements (above). Periodically, the stirrer was stopped,
the MOF was allowed to settle, an aliquot of 6 μL of liquid 3.2. Fluorescence Spectra of A100 MOF. The
phase was collected from the top of the cuvette, and a clear fluorescence spectra obtained with an empty quartz cuvette
supernatant was diluted with n-heptane by a factor of 500 and using angular accessory (see Experimental and Theoretical
analyzed by UV−vis spectroscopy. Molar concentrations were Methods) had no peaks as expected. Figure 1A shows the
determined by the Bougert−Lambert−Beer method. normalized fluorescence spectra of actA100 (solid black line)
2.8. Quantum Chemical Calculations.38,39 All calcu- and 7hydA100 (solid blue line) at λexc = 260 nm.
lations were conducted with the Gaussian 09 program,40 and
geometries were calculated at the M06-2X/LANL2DZ level.

3. RESULTS AND DISCUSSION

3.1. Preparation of hydA100 by Water Adsorption.
Prior to spectroscopic measurements, we determined the
change of mass of asA100 after its thermal activation to form
actA100; the decrease of mass was 4.8 wt % due to the loss of
“free” BDCH2 and adsorbed water. Next, we determined the
increase of the mass of actA100 due to subsequent adsorption
of water after prolonged exposure (up to 7 days) in water vapor
at RH ≈ 100% and 25 °C (see Experimental and Theoretical
Methods); 7hydA100 was kept in a closed vessel while
weighing. Each structural unit of MIL-53(Al) and A100
contains four BDC linkers; each linker is shared between two
neighboring units; thus, each unit contains two BDC linkers,
(AlOH)2−[BDC]2. The 7hydA100 obtained by us has the
formula (AlOH)2−[BDC]2−(H2O)8, Scheme 1.
Next, we thermally activated 7hydA100 following the same
procedure as for the activation of asA100 (see Experimental
and Theoretical Methods). The decrease of mass of 7hydA100 Figure 1. Fluorescence spectra of actA100 (solid black line) and
7hydA100 (solid blue line): (A) at λexc = 260 nm and (B) at λexc = 310
due to the loss of water was 24 wt %; thus, within the error, nm.
actA100 with formula (AlOH)2−[BDC]2 was formed again.
When hydration of actA100 in water vapors was conducted for
2 days, the increase of mass of actA100 corresponds to the
formula (AlOH)2−[BDC]2−(H2O)3 of obtained 2hydA100, The spectra are nearly of the same shape and intensity; thus,
Scheme 1. hydration of actA100 does not cause quenching or increase the
Adsorbed amounts of water on A100 (Scheme 1) are higher fluorescence. For both actA100 and 7hydA100 MOFs, there is a
than those reported12 for MIL-53(Al). We note the following large fluorescence peak centered at ca. 380 nm and a much
major differences. First, this is a controlled high relative smaller peak at 320 nm. The fluorescence spectra obtained at
humidity (RH ≈ 100%) in our experiments (see Experimental λexc = 280 nm (not shown) show the same spectral position and
and Theoretical Methods). Second, this is a long adsorption shapes of the peaks. Figure 1B shows the fluorescence spectra
time in our experiments (2−7 days) vs brief exposure of MIL- of actA100 (solid black line) and 7hydA100 (solid blue line) at
53(Al) to air in reported study.12 We believe that studies of λexc = 310 nm; there is only one fluorescence peak at ca. 380
water adsorption under controlled high humidity and nm. The spectra of actA100 and 7hydA100 are nearly of the
prolonged adsorption times are useful for understanding the same shape and intensity; thus, hydration of actA100 does not
behavior of MOFs. cause any quenching or increase of the fluorescence at λexc =
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310 nm. The fluorescence spectra in Figure 1 imply the energy
level diagram as in Scheme 2.
Scheme 2. Proposed Energy Levels and Excitation and
Fluorescence Transitions in A100 MOF
The proposed energy level diagram is consistent with the
Kasha rule:41 photoexcitation at 260 nm proceeds from the S0
to the S2 level, and then a weak emission at 320 nm occurs due
to the transition from the S2 to the S0 level. However, the main
relaxation pathway is via internal conversion (IC) from the S2
to the S1 level and the subsequent high intensity emission from
the S1 to the S0 level with the peak at 380 nm. Both transitions
shown in Scheme 2 can be observed in Figure 1A as
fluorescence bands centered at 320 and 380 nm. The excitation
at 310 nm causes an excitation from the S0 to the S1 level and
the subsequent high-intensity emission from S1 to S0 centered
at 380 nm, Scheme 2.
The proposed scheme of radiative transitions (Scheme 2) is
also consistent with reported fluorescence spectra of certain
nonsubstituted and substituted aromatic hydrocarbons. For
example, fluorescence spectra of naphthalene and several 1-
substituted naphthalenes in solution at room temperature were
reported to contain both S2 → S0 and S1 → S0 transitions,42
with rate constants for radiative decay and internal conversion.
Interestingly, both S2 → S0 and S1 → S0 transitions in
naphthalene and associated internal conversion were also
reported in the fluorescence spectra of naphthalene vapor.43
This indicates that the basic energy level diagram and radiative
transitions may be the same for certain aromatic compounds in
the vapor and condensed phase. Further, the appearance of
both S2 → S0 and S1 → S0 transitions in fluorescence spectra of
naphthalene and substituted naphthalenes was supported by
the UV−vis absorption spectra in solution, where two
respective absorption bands S0 → S2 and S0 → S1 have been
found.42 The BDC linker in A100 MOF contains an aromatic
benzene ring that has structural similarity with the aromatic
system of fused-ring aromatic hydrocarbon naphthalene. The
origin of two fluorescence transitions in A100 MOF from
excited S1 and S2 states (Scheme 2) was investigated by us
using the UV−vis absorption spectra of solution of the linker of
A100 MOF, see Figure 2.
3.3. Origin of the Fluorescence from A100 MOF.
Recent reviews on the luminescent MOFs29,30 summarize the
origin of the known mechanisms of the fluorescence: (i) from
the adsorbate, (ii) from the linker in the MOF (the intralinker
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Figure 2. UV absorption spectra of 0.0007 M solution of BDCH2 in
aqueous 0.1 M HCl (dashed line) and 0.002 M solution of BDCH2 in
phosphate buffer at pH = 8.5 (solid line).
fluorescence), (iii) due to energy transfer from one linker to
another (the interlinker fluorescence) aka the ligand-to-ligand
charge transfer, LLCT, (iv) the ligand-to-metal charge transfer
(LMCT) fluorescence due to the transfer of electron density
from the linker to the metal cation in the MOF, (v) from
cations of f metals in the MOFs. It was speculated that the
fluorescence from MIL-53(Al) centered at ca. 410 nm may
originate from the LMCT;31 however, no experimental or
computational evidence was provided. To our knowledge, no
experimental proof of the origin of the fluorescence spectra of
Al-MOFs was reported.
We decided to determine the origin of the fluorescence from
electronic levels in A100 MOF shown in Scheme 2. Electronic
transitions in solids are determined by UV−vis diffuse
reflectance spectroscopy (UV−vis DRS). The UV-DRS of
A100 MOF at ∼260 nm could not be obtained using the
available instrument; hence, we investigated the model system:
a solution of the neutral form of aromatic linker in A100, 1,4-
benzenedicarboxylic acid BDCH2 in water. For BDCH2, acidity
constants44 are pKa1 = 3.51 and pKa2 = 4.82. Therefore, at pH =
8.5, both carboxylic groups are dissociated to form (BDC)2−
anion, while at pH = 1 both carboxylic groups are not
dissociated to form the “free” acid BDCH2. The solubility of
BDCH2 in 0.1 M HCl to obtain pH = 1 is significantly lower
than that in phosphate buffer to obtain pH = 8.5. Figure 2
shows the UV spectra of 0.0007 M solution of BDCH2 in
aqueous 0.1 M HCl (dashed line) and 0.002 M solution of
BDCH2 present as anion (BDC)2− in the buffer at pH = 8.5
(solid line).
Buffer solution at pH = 8.5 containing (BDC)2− is a model
system for A100 MOF where BDC linker is present as the
(BDC)2− anion connected to Al(OH)2+ cationic units. In
Figure 2, two absorption bands are present: at 240 and 295 nm
that correspond to transitions S0 → S2 and S0 → S1 (HOMO
→ LUMO), respectively, in neutral form BDCH2 and anionic
form BDC2−. Thus, for both BDCH2 and its anion BDC2− the
energy gap between the HOMO and the LUMO electronic
levels is ca. 295 nm or 4.2 eV. This value of the HOMO−
LUMO energy gap is close to that at 4.1 eV or 302 nm reported
recently for the adsorbed monolayer of terephthalic acid.45
One can see in Figure 2 that the UV spectra of BDC in
neutral BDCH2 form and anionic form (BDC)2− with both
COOH groups dissociated are very similar that implies the
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excitation of the π → π* transitions involving molecular orbitals
(MOs) of aromatic system of benzene ring. On the other hand,
the spectral position and intensity of the n → π* transition
involving the lone electron pair of the O atom of the COO
group in BDCH2 would be dependent on dissociation of the
COO group that is not the case. Thus, the fluorescence from
A100 MOF (Scheme 2) is due to an intralinker emission from
the aromatic system of benzene ring of the BDC linker.
Further, it is known that adsorbed water in MIL-53(Al) is H
bonded to the COO group of the BDC linker.12 A100 MOFs is
similar19 to MIL-53(Al), and fluorescence spectra of actA100
(without adsorbed water) and hydA100 (with adsorbed water
coordinated to COO group) are essentially the same, Figure 1.
This finding further indicates that the fluorescence from A100
MOF is independent of chemical bonds involving the COO
group, i.e., the fluorescence in Figure 1 originates from the
MOs of benzene ring. We checked the origin of the
fluorescence of A100 MOF by comparing the fluorescence
spectra from A100 MOF and solutions of model compound
BDCH2 in water at different pH.
Figure 3A shows the normalized fluorescence spectra at λexc =
260 nm obtained from BDCH2 in its anionic (BDC)2− form as
Figure 3. Normalized fluorescence spectra at λexc = 260 nm of (A)
0.002 M solution of BDCH2 in phosphate buffer at pH = 8.5 (solid
line) and 0.0007 M solution of BDCH2 in 0.1 M HCl (dotted line)
and (B) A100 MOF (solid line) and neat BDCH2 (dotted line).
0.002 M solution in phosphate buffer at pH = 8.5 (solid line) vs
neutral BDCH2 as 0.0007 M solution in 0.1 M HCl (dotted
line).
The spectra have nearly the same position of spectral
maximum and shape that indicates that the fluorescence
emission is not dependent on whether the COOH group is
dissociated. These data are consistent with absorption spectra
of BDCH2 vs (BDC)2− in solution (Figure 2) that are also
independent of the pH. Therefore, the fluorescence from BDC
originates from electronic states of the aromatic system of the
phenyl ring in the BDC linker. The fluorescence from either
BDC2− or BDCH2 in Figure 3A appears as a broad peak
centered at 380 nm when excited at λexc = 260 nm. Thus, the
fluorescence from BDC2− or BDCH2 is strongly “red shifted”
from the excitation wavelength that can be explained by the
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excitation to the higher vibrational states. The first mechanism
of excitation to the higher vibrational states can be realized via
vibrational overtones in the anharmonic oscillator with
selection rule Δv = ±2 for vibrational quantum number v,
compared to the selection rule for harmonic oscillator Δv = ±1.
The second mechanism for a large red shift of the fluorescence
is via exciting combination frequencies. In our recent paper,24
the set of combination frequencies due to vibrations in the
naphthalene molecule was detected as vibronic shoulders in the
fluorescence spectrum of naphthalene in diluted solution. In
addition, the reported experimental FTIR spectrum of model
compound 2-aminoterephthalic acid46 that is structurally
similar to BDCH2 contains a very intense set of overtone and
combination modes. Therefore, the strong red shift of the
fluorescence from the monomer of BDC in Figure 3A is
consistent with the excitation and emission from electronic
states of the aromatic system of the benzene ring in BDC
involving vibrational overtones and/or combination frequen-
cies. Further, the fluorescence spectrum of diluted 5 × 10−4 M
water solution of another model compound, benzoic acid,47
appears at 310−390 nm when excited with λexc = 250 nm. Thus,
both benzoic acid47 and terephthalic acid BDCH2 (Figure 3A)
in diluted solution undergo a significant red shift of the
fluorescence when excited close to the maximum of absorption,
and hence, the origin of the fluorescence is the same, namely,
excitation of aromatic system of benzene ring.
Figure 3B shows the fluorescence spectra at λexc = 260 nm
from A100 MOF that contains BDC linker in its anionic
(BDC)2− form (solid line) vs neat solid BDCH2 present as
molecular form (dotted line). One can see that the presence of
Al(III) cation in A100 MOF does not significantly change the
fluorescence spectrum compared to neat BDCH2. Therefore,
the fluorescence from A100 in Figure 3B is unlikely to be the
LMCT fluorescence involving Al(III) cation. This conclusion is
consistent with the recent critical review:32 “given the
extraordinary energetic difficulty of accomplishing one electron
reduction of Al(III)... Presumably emission is instead occurring
from a linker-localized excited state”. Further, positions of the
fluorescence spectral maxima and spectral widths in Figure 3
are about the same for solid A100 MOF, solid BDCH2,
(BDC)2− in diluted 0.002 M solution, and BDCH2 in diluted
0.0007 M solution. This is a standard method in fluorescence
spectroscopy to use diluted solutions with concentration
∼<10−3 M to observe only the emission from the monomers
but not from excimers or complexes. Indeed, in 0.002 M
solution of (BDC)2− at pH = 8.5 (Figure 3) there are 0.002 mol
of anion (BDC)2− present per 55.6 mol of water solvent, i.e.,
one anion (BDC)2− is surrounded with 27 800 water molecules,
on average. In such diluted solution, the observed fluorescence
(Figure 3A) is the intramolecular fluorescence from electronic
states of (BDC)2− monomer rather than the fluorescence from
any molecular associate involving more than one molecular unit
of BDC. In addition, electrically charged (BDC)2− anions in
solution at pH = 8.5 would electrostatically repel each other,
thus making formation of any excimers or other clusters highly
unlikely. Two conclusions can be made by comparing Figure
3A and 3B. First, the fluorescence spectra are essentially the
same for BDC monomers in diluted solutions in Figure 3A and
BDC linker in A100 MOF (Figure 3B). Therefore, in all cases
the fluorescence originates from the monomer of the BDC unit
rather than from some associated form of BDC units, e.g.,
excimers or the LLCT excited state in A100. This conclusion is
consistent with the relative position of neighboring BDC linker
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units in activated A100 and MIL-53(Al): BDC linkers are
positioned at ca. 90° to each other;12 therefore, any interlinker
energy transfer (LLCT) from one BDC unit to another is
unlikely for sterical reasons. Second, in all cases, the
fluorescence at 380 nm originates from the S1 → S0 or
LUMO → HOMO transition within the aromatic system in the
BDC monomer. In summary, as shown by combination of the
wavelength-dependent fluorescence spectra in the solid phase
and diluted solutions of model systems and the complementary
UV−vis absorption spectroscopy in solution, the fluorescence
from A100 MOF originates in the intralinker transitions of
BDC. Therefore, one can expect that binding of the adsorbate
molecule to the aromatic system of the BDC linker would
modify the fluorescence. We test this hypothesis below by
comparing the fluorescence spectra of A100 MOF and its
host−guest adsorption complexes with indole and naphthalene.
3.4. Fluorescence Spectra of the Host−Guest Adsorp-
tion Complexes of NAP and IND with actA100 at λexc =
260 and 310 nm. Prior to spectroscopic measurements, we
determined the increase of mass of actA100 after the formation
of the host−guest adsorption complex with naphthalene (NAP)
or indole (IND). The increase of mass corresponds to the
formulas of the host−guest adsorption complexes
(AlOH)2−[BDC]2−[NAP]1 and (AlOH)2−[BDC]2−[IND]1,
respectively. In other words, one NAP or IND molecule is
adsorbed per structural unit in A100 MOF. The kinetic
diameter of indole at 5.4 Å23 is comparable to the micropore
size36 in A100 MOF at 5.3 Å. On the other hand, the kinetic
diameter of the naphthalene molecule at 6.57 Å48 is larger than
the micropore size. We speculate that “breathing” of A100
occurs to admit one naphthalene molecule to the structural unit
(AlOH)2−[BDC]2 to form the stoichiometric host−guest
adsorption complex (AlOH)2−[BDC]2−[NAP]1.
Figure 4A shows the fluorescence spectra at λexc = 260 nm
obtained with actA100 with formula (AlOH)2−[BDC]2 (solid
black line) and host−guest adsorption complexes formed by
actA100 with naphthalene (AlOH)2−[BDC]2−[NAP]1 (solid
Figure 4. Fluorescence spectra of (AlOH)2−[BDC]2 (black line),
complex (AlOH)2−[BDC]2−[NAP]1 (green line), and (AlOH)2−
[BDC]2−[IND]1 (red line) at (A) λexc = 260 nm and (B) λexc = 310
nm.
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green line) and indole (AlOH)2−[BDC]2−[IND]1 (solid red
line).
There is a decrease of the fluorescence in the complex
(AlOH)2−[BDC]2−[NAP]1 by ca. 50% in the spectral range
ca. 350−400 nm after adsorption of naphthalene, compared to
A100, Figure 4A. This emission range surrounds the emission
maximum of A100 MOF at ca. 380 nm, see also Figure 1A.
Therefore, quenching of emission from A100 occurs after
adsorption of naphthalene. Further, there is an increase of
emission at ca. 410−480 nm after adsorption of naphthalene,
Figure 4A. Such an “extra” fluorescence signal corresponds to
emission from adsorbed highly fluorescent49 NAP molecule in
the complex with A100 that appears in the spectrum in addition
to the intralinker fluorescence from the BDC linker. This is
further commented in the discussion of Figure 4B below. On
the other hand, the fluorescence intensity in the spectrum of
adsorption complex with indole (AlOH)2−[BDC]2−[IND]1 is
a factor of ∼10 lower than that of actA100 (AlOH)2−[BDC]2.
Therefore, there is a strong quenching of the fluorescence from
the BDC linker in A100 MOF upon the formation of the host−
guest adsorption complex with indole. The absence of emission
from adsorbed indole is attributed to an efficient intersystem
crossing to the triplet state due to the significant spin−orbit
coupling in the aromatic heterocyclic compounds, compared to
aromatic hydrocarbons.50 We propose that in the host−guest
adsorption complex (AlOH)2−[BDC]2−[IND]1 an adsorbed
indole molecule accepts the energy of the photoexcited states of
the BDC linker and transfers it to the triplet state and/or
vibrations. Such mechanism is consistent with the proposed
interlinker fluorescence of BDC in A100 MOF, namely, in the
adsorption complex with indole, the excitation energy of BDC
linker is transferred not to another BDC linker but to the
weakly fluorescent adsorbed molecules of indole that causes the
observed quenching of the fluorescence in the adsorption
complex. In solution, the fluorescence quenching of the excited
state of the π−π complex containing indole and benzene has
been reported.51 We propose that in the host−guest adsorption
complex of indole and A100 MOF, the bonding is between the
π system of adsorbed indole and the π system of the BDC
linker. We will further investigate this interaction using the
DFT calculations, section 3.8.
Figure 4B shows the fluorescence spectra of (AlOH)2−
[BDC]2 (solid black line) and the host−guest adsorption
complexes with naphthalene (AlOH)2 −[BDC]2−[NAP]1
(solid green line) and indole (AlOH)2−[BDC]2−[IND]1
(solid red line). λexc = 310 nm was chosen to excite S1 → S0
fluorescence transition, and the same observations are made as
with λexc = 260 nm: there is an increase of the fluorescence in
the range ca. 400−480 nm in (AlOH)2−[BDC]2−[NAP]1 vs
(AlOH)2−[BDC]2. This indicates that the origin of that “extra”
emission at ca. 400−480 nm is an emission from adsorbed
naphthalene, Figure 4A and 4B. Therefore, there are two kinds
of spectral changes in Figure 4 after adsorption of naphthalene:
(1) quenching of emission from A100 at ca. 350−400 nm as
observed with λexc = 260 nm (Figure 4A) and (2) increase of
emission due to adsorbed naphthalene at ca. 400−480 nm as
observed with both λexc = 260 (Figure 4A) and 310 nm (Figure
4B). On the other hand, a complete quenching of emission
from the BDC linker in A100 occurs in the adsorption complex
with indole (AlOH)2−[BDC]2−[IND]1.
3.5. Fluorescence Spectra of BDCH2 and IND in
Solution at λexc = 310 nm. We have shown that the
fluorescence from A100 MOF originates from the aromatic
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system of the BDC linker, and fluorescence quenching by
indole in the adsorption complex is due to the π−π interaction
between adsorbed indole and the aromatic system of the linker.
We decided to measure the fluorescence spectrum of a solution
of BDCH2 vs an equimolar solution of BDCH2 and IND.
BDCH2 is insoluble in the nonpolar solvents such as hexane;
therefore, polar DMF was used. Figure 5A shows the
Figure 5. (A) Fluorescence spectra of 0.08 M solution of BDCH2 in
DMF (solid line) and equimolar 0.08 M solution of BDCH2 and IND
in DMF (dashed line) at λexc = 310 nm. (B) Absorption spectra of
solution of BDCH2 in DMF (solid line) and equimolar solution of
BDCH2 and IND in DMF (dashed line).
fluorescence spectra of a 0.08 M solution of BDCH2 in DMF
(solid line) and equimolar 0.08 M solution of BDCH2 and IND
in DMF (dashed line). To interpret the intensity of the two
fluorescence spectra in Figure 5A, the number of photons
absorbed at the excitation wavelength λexc = 310 nm needs to
be the same in a solution of BDCH2 and in solution containing
both BDCH2 and IND. We measured the UV−vis absorption
spectra of a solution of BDCH2 in DMF and a binary equimolar
solution of BDCH2 and indole in DMF. Since these 0.08 M
solutions have too strong absorbance at the wavelength of
interest 310 nm, we had to dilute these solutions with DMF to
decrease absorbance to a measurable value. Figure 5B shows
the absorbance spectra of a 0.08 M solution of BDCH2 in DMF
and a 0.08 M equimolar binary solution of BDCH2 and IND in
DMF after dilution with pure DMF by a factor of 750. One can
see that absorbance at 310 nm for the binary solution
containing equimolar amounts of BDCH2 and indole is only
10% higher than that for the solution with BDCH2 only.
Therefore, the number of absorbed photons is about the same
(∼10% difference) for a solution of BDCH2 alone and solution
of BDCH2 in the presence of IND.
The fluorescence spectra in Figure 5A were measured at λexc
= 310 nm to excite the S1 → S0 transition in BDCH2 to observe
fluorescence quenching of the BDC linker by adsorbed indole.
One can see a strong quenching of the fluorescence (by factor
∼6) from BDCH2 in the presence of an equimolar amount of
IND. Fluorescence quenching of BDCH2 by IND in solution
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(Figure 5) is similar to quenching of the fluorescence from the
BDC linker in A100 by IND in the adsorption complex at λexc =
310 nm, Figure 4B. Quenching of the fluorescence in Figure 5A
occurs in the absence of Al(III) cation; hence, the fluorescence
quenching does not depend on whether the Al(III) cation is
present. Therefore, this is the fluorescence from the BDC linker
in A100 MOF, rather than the LMCT fluorescence that is
quenched by the IND adsorbate.
The fluorescence spectra of the host−guest adsorption
complex (AlOH)2−[BDC]2−[NAP]1 in Figure 4A and 4B are
also expected to originate mostly from the excited states of the
BDC linker. However, when excited at λexc = 310 nm (Figure
4B), the complex shows the significant spectral contribution
from adsorbed NAP. To distinguish between the contribution
to the total fluorescence spectrum due to the emission from the
BDC linker in A100 MOF (that may be quenched by the IND
adsorbate) and any possible emission from either NAP or
perhaps IND adsorbate we performed a complementary
experiment with an excitation wavelength of 372 nm.
3.6. Fluorescence Spectra of the Host−Guest Adsorp-
tion Complexes ( AlOH) 2 −[BDC] 2 −[NAP ] 1 an d
(AlOH)2−[BDC]2−[IND]1 at λexc = 372 nm. Figure 6 shows
Figure 6. Fluorescence spectra of (AlOH)2−[BDC]2 (black line),
complex (AlOH)2−[BDC]2−[NAP]1 (green line), and complex
(AlOH)2−[BDC]2−[IND]1 (red line) at λexc = 372 nm.
the fluorescence spectra of actA100 (AlOH)2−[BDC]2, the
host−guest adsorption complex with naphthalene (AlOH)2−
[BDC]2−[NAP]1, and host−guest adsorption complex with
indole (AlOH)2−[BDC]2−[IND]1 at λexc = 372 nm. As was
checked in the reference experiments with IND and NAP in
solutions and the solid phase (data not shown), λexc = 372 nm
would photoexcite only electronic states in A100 MOF.
For the complex (AlOH)2−[BDC]2−[IND]1, there is a
complete quenching of the fluorescence from the BDC linker.
This is consistent with fluorescence quenching by IND
adsorbate at λexc = 310 nm, Figure 4B. In Figure 6, there is
some decrease of the fluorescence from (AlOH)2−[BDC]2−
(NAP)1; therefore, when NAP in (AlOH)2−[BDC]2−(NAP)1
complex is not photoexcited, quenching of the fluorescence
from the BDC linker occurs. Fluorescence quenching by the
NAP adsorbate is much weaker than that by the IND in the
complex (AlOH)2−[BDC]2−(IND)1 as expected given the
above-mentioned much more efficient intersystem crossing to
the nonemitting states in the excited molecule of IND50
compared to NAP. Those data imply that NAP and IND have
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Table 1. Nanosecond Time-Resolved Fluorescence Data from A100 and Its Complexes
(AlOH)2−[BDC]2 (AlOH)2−[BDC]2−[NAP]1
τ 1 (ns) 3.56 ± 0.06 3.22 ± 0.07
B1 (au) 895.97 939.72
τ2 (ns) 19.79 ± 0.37 16.25 ± 0.24
B2 (au) 208.75 264.30
ratio B1/B2 4.29 3.55
the same mechanism of adsorption on actA100 that is due to
the formation of the π−π adsorption complexes with the
aromatic system of the BDC linker. In order to learn more
about the origin of the fluorescence in the adsorption
complexes of A100 with NAP and IND, we decided to use
the complementary nanosecond time-resolved fluorescence
spectroscopy.
3.7. Nanosecond Time-Resolved Fluorescence Spec-
troscopy of Adsorption Complexes. The nanosecond time-
resolved fluorescence decay curves were obtained from actA100
and complexes of actA100 with IND, NAP, and water at λexc =
366 nm that is close to λexc = 372 nm (Figure 6) at which no
excitation of the adsorbate occurs. Therefore, electronic states
of the BDC linker in A100, but not IND or NAP, were
photoexcited at λexc = 366 nm. The intensity of the nanosecond
time-resolved fluorescence was numerically fitted with one-,
two-, and three-exponential decay functions. The smallest value
of chi-square parameter was obtained in fitting with a
biexponential decay: f(x) = A + B1 exp(−x/τ1) + B2 exp(−x/
τ2). Table 1 shows the obtained numeric values for time
constants τ1 and τ2 and their contributions B1 and B2,
respectively.
All samples show two time constants τ1 and τ2 with similar
numeric values, which indicates the emission from the same
electronic states, i.e., from aromatic ring of the BDC linker as
expected for λexc = 366 nm. Scheme 3 shows the proposed
energy diagram of the fluorescence from BDC in A100 MOF in
the presence of IND adsorbate (top) and NAP adsorbate
Scheme 3. Proposed Energy Diagram of Electronic Levels
and Transitions in the Adsorption Complexes of NAP and
IND with Activated A100 MOF
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2hydA100, (AlOH)2−[BDC]2−(H2O)3 (AlOH)2−[BDC]2−[IND]1
2.91 ± 0.04 3.81 ± 0.05
1431.54 705.54
15.51 ± 0.24 25.74 ± 0.31
261.89 116.67
5.47 6.04
(bottom) that are π−π bonded to the aromatic system of the
BDC linker.
The relatively small ratio B1/B2 for the complex with
naphthalene (AlOH)2−[BDC]2−[NAP]1 is close to that of
actA100 (AlOH)2−[BDC]2. On the other hand, the larger ratio
B1/B2 for the adsorption complex with indole
(AlOH)2−[BDC]2−[IND]1 is close to that of hydA100
(AlOH)2−[BDC]2−(H2O)3. Those relationships imply the
similar kinds of bonding of the adsorbates with similar
functional groups, i.e., that adsorbed IND may be bonded to
A100 in a manner similar to water, by hydrogen bonding. In
order to investigate the relative contributions from the π−π
interactions and H bonding between adsorbed IND or NAP
and A100, we use the complementary DFT calculations, section
3.8; complementary experimental mechanistic research is in
progress.
3.8. DFT Computations of Geometry, Binding Energy,
and Electronic Spectra of Adsorption Complexes of
Naphthalene and Indole with Activated A100 MOF. The
M06-2X exchange/correlation density functional has been
thoroughly tested52−57 and found to incorporate some
medium-range dispersion interactions. Calculations on the
model complex NAP-MIL-53(Al) with a naphthalene molecule
required 250 atoms and 1758 basis functions with the
LANL2DZ basis set. Since LANL2DZ is a rather small basis
set, the basis set superposition errors (BSSE) in the binding
energies of both NAP and IND were quite large (>5 kcal/mol).
For that reason, the binding energies of both NAP and IND
were corrected for BSSE by using the counterpoise method.58
In order to match the conditions of the adsorption
experiment and the DFT computations, the “low-coverage
limit” with either IND or NAP was chosen, namely, in the
stoichiometr ic host−guest adsorpt ion com plexes
(AlOH)2−[BDC]2−[NAP]1 and (AlOH)2−[BDC]2−[IND]1
there is, on average, one adsorbate molecule per structural
unit of the MOF. The second adsorbed NAP or IND molecule
would be located inside the next unit; thus, adsorbed NAP or
IND molecules would not interact with each other. Therefore,
in the low-coverage limit as pertinent to the choice of the
relevant cluster for the DFT calculations, only the interactions
between the adsorbate molecule and the adsorption site (BDC
linker in this case) are to be taken into account. The cluster
with more than one adsorbed molecule per cavity would
correspond to the higher adsorption capacities that are to be
found at the adsorption equilibrium in solution. Those
structures would not properly model the stoichiometric
host−guest adsorption complexes of A100 MOF that were
maintained in vacuum (see Experimental and Theoretical
Methods) to remove any weakly bound NAP or IND. Thus, the
clusters with more than one adsorbate molecule per cavity were
not further considered by us in this study, and we used clusters
with one molecule per cavity.
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Figure 7A shows the optimized structure of the cluster with
one adsorbed NAP molecule, and Figure 7B shows that with
one adsorbed IND molecule.
Figure 7. Optimized structure of model cluster of MIL-53(Al) with
(A) naphthalene and (B) indole: black atoms, carbon; white atoms,
aluminum; small white atoms, hydrogen; blue atom, nitrogen.
The Cartesian coordinates of the MIL-53(Al) model cluster
and the model complex with one molecule of NAP or IND
optimized at the M06-2X/LANL2DZ level are available in
Table S1, Supporting Information. In Figure 7A, the NAP
molecule binds parallel with the bottom of the cavity in the gap
between two BDC linkers. In this orientation, the NAP
molecule has a “parallel displaced” orientation59 with the 6-
membered π system of the BDC linker. The parallel orientation
of the NAP molecule suggests the interactions between the
aromatic π system of adsorbed NAP and that of the BDC
linker. The distance between the NAP plane and the BDC
linker plane is 3.08 Å, Figure 7A. The spatial limit to the π−π
interactions between two atoms is the sum of their van der
Waals radii rvdW. For carbon,60 the rvdW = 1.77 Å yields the long-
range limit for the π−π interaction at twice the rvdW or 3.54 Å.
Therefore, the distance between the plane of the NAP molecule
and the plane of the BDC linker in Figure 7A at 3.08 Å is within
the typical range of the π−π interactions. In contrast to the
NAP molecule, the molecular plane of IND is somewhat tilted
with respect to the bottom of the MIL-53(Al) cavity, Figure 7B,
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apparently to accommodate the hydrogen bond. The IND
molecule is situated above one BDC linker to allow the
hydrogen atom in the NH group to interact with an oxygen
atom in the COO group of the adjacent BDC linker. Hydrogen
bonding is detected between the NH hydrogen of the IND
molecule and an oxygen atom of the BDC linker, with the
calculated NH---O distance of 2.59 Å. The recent review of the
typical geometry of the hydrogen-bonded NHO groups60
provides the length distribution with a center at 2.9 Å.
Therefore, the calculated length of the NH---O bond in the
cluster of MIL-53(Al) with indole corresponds to rather short
and strong hydrogen bonding.
A critical geometrical analysis of the π−π stacking in the
complexes of aromatic nitrogen-containing ligands concluded61
that the typical π−π interaction occurs via an offset or slipped
stacking arrangement, i.e., the interacting rings are parallel
displaced. Further, in complexes with typical π−π stacking,61
the ring normal and the vector between the ring centroids
would form an angle of about 20° up to centroid−centroid
distances of 3.8 Å. This is observed in Figure 7B for adsorbed
IND: the benzene aromatic ring of IND is located over the
benzene ring of the BDC linker, with a ring−ring distance of ca.
3.25 Å. Therefore, the DFT computations indicate the strong
π−π stacking interaction between the aromatic system of
adsorbed IND and the aromatic system of the BDC linker. This
π−π stacking interaction takes place simultaneously with the H
bonding of adsorbed IND with BDC linker as discussed above.
Table 2 shows the calculated binding energies (without and
Table 2. Binding Energies of IND and NAP to MIL-53(Al)
Cluster
binding energy binding energy BSSE correcteda
cluster (kcal/mol) (kcal/mol)
MIL- −17.9 −10.9
53(Al)+NAP
MIL- −20.5 −13.8
53(Al)+IND
a
BSSE represents basis set superposition errors.
with counterpoise correction) for adsorption of one NAP and
IND molecule into the cavity of the MIL-53(Al) model cluster
computed at the M06-2X/LANL2DZ level of theory.
For the cluster with one adsorbed IND molecule, IND
molecule binds 2.9 kcal/mol more strongly than one adsorbed
NAP molecule. The enhanced binding can be attributed to
hydrogen bonding between the NH hydrogen of the IND
molecule and an oxygen atom of the BDC linker. In addition,
there are two short CH---O distances between IND (Figure
7B) and different COO groups of the MIL-53(Al) model, as
well as two short CH---O distances between NAP and different
COO groups of the MIL-53(Al) model (Figure 7A). In both
cases, the short distances are between the CH hydrogen atoms
of the adsorbate molecule and the COO group on one linker
forming the end of the cavity of MIL-53(Al) cluster. The
distances are 2.24 and 2.45 Å in the cluster with adsorbed IND
and 2.57 and 2.62 Å in the cluster with adsorbed NAP. In the
case the cluster with IND, the CH---O interactions are short
enough to suggest that they contribute to binding. Overall, our
DFT data on the energy and geometry of binding of IND and
NAP to the model cluster of MIL-53(Al), Figure 7A and 7B
and Table 2, indicate a strong π−π interaction between
adsorbed IND and NAP and BDC linker of MIL-53(Al).
Therefore, our DFT data are consistent with quenching of
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emission from the BDC linker in A100 after the formation of
the host−guest adsorption complexes with IND and NAP,
Figure 6. Yet another important conclusion of our DFT study is
that in the adsorption complex with IND, the NH---O
hydrogen bond with a NH---O distance of 2.59 Å is rather
short and strong. In order to investigate the possibility of
preferential binding of IND vs NAP to A100 MOF, one needs
to change the number and/or strength of hydrogen bonds. The
obvious method is to study the adsorption of IND vs NAP on
A100 MOF with a large amount of preadsorbed water
molecules that can form hydrogen bonds with IND but not
NAP adsorbate.
3.9. Adsorption of IND and NAP on Hydrated A100 in
Suspension. The kinetics of adsorption of IND or NAP on
hydrated A100 or hydrated MIL-53(Al) in solution and the
adsorbed amounts were not reported, to our knowledge. Figure
8A shows the in-situ time-dependent fluorescence measure-
ments at λexc = 310 nm in suspension of 2hydA100 in 0.08 M
solution of IND in n-heptane.
Figure 8. (A) Area of the in-situ fluorescence spectra of 2hydA100 in
0.08 M solution of IND in n-heptane at λexc = 310 nm vs adsorption
time. (B) Adsorption kinetics of IND on 2hydA100 by UV−vis
spectroscopy.
The Y axis shows the integrated area of the fluorescence
spectrum, with the Raleigh excitation peak excluded. It was
determined in the reference experiments that a 0.08 M solution
of IND in n-heptane shows the negligible fluorescence at the
experimental settings used. Therefore, the integrated fluo-
rescence in Figure 8A originates from the electronic states of
the π system of the BDC linker in A100 MOF. In Figure 8A,
one can see the progressive decrease of the fluorescence of
A100 as a result of quenching of the fluorescence of the BDC
linker by adsorbed IND, until the plateau after ca. 60 min.
Therefore, the adsorption of indole proceeds on hydrated
2hydA100 that contains three preadsorbed water molecules per
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structural unit. Figure 8B shows the kinetics of adsorption of
IND on 2hydA100 in the same suspension as measured in
parallel with the in-situ fluorescence spectra by the comple-
mentary ex-situ UV−vis spectroscopy of the liquid phase of the
suspension. In ca. 60 min, adsorption equilibrium is achieved,
which is consistent with the plateau of the in-situ time-
dependent fluorescence in Figure 8A. The equilibrium of
adsorption of indole on the activated MIL-53(Al) in n-octane23
was achieved in less than 1 h. The adsorption kinetics on
hydrated A100 MOF, Figure 8B, proceeds on a similar time
scale, which may indicate the diffusion-limited kinetics.
The amount of IND adsorbed on 2hydA100 in equilibrium
was determined by UV−vis absorption spectroscopy (Figure
8B), and the corresponding adsorption complex has the
formula (AlOH)2−[BDC]2−[IND]0.6−(H2O)x. Experimental
techniques available to us do not allow answering the question
whether the amount of preadsorbed water in 2hydA100
changes as adsorption of indole on 2hydA100 in suspension
proceeds. The similar kinetic experiment on the adsorption of
naphthalene from solution in n-heptane on 2hydA100 was
conducted by us (data not shown), and the adsorption
equilibrium was achieved in about 40 min. The amount of
NAP adsorbed onto 2hydA100 in equilibrium was determined
by a similar procedure using UV−vis absorption spectroscopy.
Scheme 4 shows the stoichiometry of adsorption of NAP and
Scheme 4. Stoichiometry of Adsorption of NAP and IND on
Hydrated A100 in n-Heptane
IND on 2-hydA100 in the suspension in n-heptane, and the
adsorbed amount of NAP is twice smaller on a molar basis than
that of IND.
Therefore, one can conclude that the preferential adsorption
of IND over NAP on hydrated A100 MOF occurs. The
hydrated A100 prepared by us contains higher amounts of
adsorbed water than the reported12 hydrated MIL-53(Al) with
one water molecule per structural unit. The presence of the
large amounts of preadsorbed polar molecules other than water
in the micropores of A100 and MIL-53(Al) MOFs is expected
to lead to the higher selectivity of adsorption of polar aromatic
N-heterocyclic compounds vs nonpolar aromatic hydrocarbons
due to hydrogen bonding. Experiments are in progress to
investigate the selectivity of adsorption of aromatic and
heterocyclic adsorbates on Al-MOFs with preadsorbed polar
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molecules. Another conclusion of this study is that the
molecules of heterocyclic aromatic adsorbate can be used as a
fluorescent “self-marker” to learn about the π−π interactions
between the linker in the MOF and the adsorbate molecule in
the host−guest adsorption complexes. In this approach, the
linker in the MOF does not need to show a strong fluorescence
(e.g., in heteroaromatic linker) if the quenching of the
adsorbate fluorescence occurs; experiments are in progress to
test this hypothesis in the broader context.
4. CONCLUSIONS
The origin of the fluorescence from A100 MOF is the
intralinker fluorescence, i.e., emission from the π system of
benzene ring of the BDC linker. Activated A100 forms the
stoichiometric host−g ue s t adso r p ti o n co mp l ex es
(AlOH)2−[BDC]2−[NAP]1 and (AlOH)2−[BDC]2−[IND]1
with naphthalene and indole, and either adsorbed molecule is
π bonded to the aromatic system of the BDC linker. The origin
of quenching of the intralinker fluorescence in A100 MOF is
due to heteroaromatic indole adsorbate and, to a much lesser
extent, aromatic naphthalene adsorbate. The DFT calculations
reveal the strong interactions due to π−π stacking between
adsorbed NAP or IND and the aromatic system of the BDC
linker as well as a strong H bonding between the NH group of
adsorbed IND and the oxygen atom in the COO group of the
BDC linker. The highest amount of water adsorbed on A100
MOF corresponds to (AlOH)2−[BDC]2−(H2O)8. The in-situ
time-dependent fluorescence spectroscopic study of kinetics
and capacity of adsorption on hydrated A100 in n-heptane
yields the preferential adsorption of indole vs naphthalene.
■
ASSOCIATED CONTENT
*
S Supporting Information
Cartesian coordinates of the MIL-53(Al) model cluster and
model clusters with one molecule of NAP or IND optimized at
the M06-2X/LANL2DZ level. This material is available free of
charge via the Internet at http://pubs.acs.org.
■ AUTHOR INFORMATION
Corresponding Author
*Phone: +1-856-225-6282. E-mail: alexsam@camden.rutgers.
edu.
Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS
A.S. thanks Rutgers University for his Research Council Grant
no. 202221 and Dr. Jim Mattheis from Horiba Scientific for
access to the Fluorolog-3 spectrometer. M.M. acknowledges the
Alabama Supercomputer Center for a generous allocation of
computer time.
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