Exploring physical and chemical properties in new multifunctional indium-, bismuth-, and zinc-based 1D and 2D coordination polymers

Article abstract of DOI:10.1039/c7dt04287f

Main group element coordination polymers (MGE-CPs) are important compounds for the development of multifunctional materials. However, there has been a shortage of studies regarding their structural, optical, catalytic, mechanical, and antibacterial proper

Full text of DOI:10.1039/c7dt04287f

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D'Vries, D. F. Lionello, L. M. Aguirre Diaz, M. Spinosa, C. Costa, M. C. Fuertes, R. A. Pizarro, A. M. M.
Kaczmarek, J. A. Ellena, L. ROZES, M. Iglesias, R. Van Deun, C. Sanchez, A. Monge and G. Soler Illia,
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Exploring Physical and Chemical Properties in new Multifunctional
Indium, Bismuth and Zinc based 1D and 2D Coordination Polymers
G. E. Gomez,a,b* R. D’Vries,c,d* D. F. Lionello,a,e L. M. Aguirre-Díaz,f M. Spinosa,g C. S. Costa,h M. C.
Fuertes,a,e R. A. Pizarro,h A. M. Kaczmarek,i J. Ellena,d L. Rozes,j M. Iglesias,f R. Van Deun,i C.
Sanchez,j* M. A. Mongef and G. J. A. A. Soler Illiab*
Received 00th January 20xx,
Accepted 00th January 20xx
DOI: 10.1039/x0xx00000x
www.rsc.org/
Main group elements coordination polymers (MGE-CPs) are important compounds for the development of multifunctional
materials. However, studies regarding to structural, optical, catalitic, mechanical or antibacterial properties have strikingly
less reported. In this work, an exhaustive study of a set of crystalline MGE-CPs obtained from bismuth and indium metals,
iminodiacetate, 1,2,4,5-benzenetetracarboxylate, and 2,2’-bipyridine as building blocks is presented. An in-deep
topological analysis of the networks was carried out. Besides, nanoindentation studies were performed on two
representative low dimensional compounds in order to find the relationships between their structural features and the
intrinsic mechanical properties (hardness and elasticity). The solid state photoluminescence (SSPL) properties were also
studied in terms of excitation, emission, lifetimes values and CIE chromaticites. Moreover, the heterogeneous catalytic
activities of the compounds were evaluated in the cyanosilylation reaction using a set of carbonylic substrates under
solvent-free conditions. Finally, the inhibitory effect of the Bi-CPs on the growth of microorganisms such as Escherichia
coli, Salmonella enterica serovar Typhimurium and Pseudomonas aeruginosa, which are associated with relevant
infectious
diseases,
is
reported.
focus of research due to its unique properties such as gas
sorption,1 optics2 and heterogeneous catalysis.3 In comparison
with transition metals from d and f block, the main group
elements (MGE) were less explored for designing new
coordination compounds. In the last years most of metal ions
have been incorporated into these materials, but only recently
Bi3+-compounds with optical4 or catalytic5 properties have
been reported. For this reason, the synthesis and studies
related to Bi-CPs is surprisingly scarce.
Introduction
Inorganic–organic hybrid compounds as coordination polymers
(CPs) or Metal Organic Frameworks (MOFs) have becoming the
a.Gerencia de Química, Centro Atómico Constituyentes, Comisión Nacional de
Energía Atómica, Av. Gral. Paz 1499, 1650 San Martin, Buenos Aires, Argentina.
*E-mail: gegomez@unsl.edu.ar
Particularly, our research has been addressed on the synthesis
of new CPs and MOFs with optical,6 mechanical,7 catalytic,8,9,10
thermo8,11, chemical6b and sensing properties12 exploring the
structure-property relationships. Moreover, the catalytic
properties of In-CPs have been widely explored by Monge’s
group finding exceptional correlations between the structures
and its catalytic performances.13
b.Instituto de Nanosistemas. Universidad Nacional de San Martín. Av. 25 de Mayo
1021, San Martín, Buenos Aires, Argentina.
c. Facultad de Ciencias Básicas, Universidad Santiago de Cali, Calle 5 # 62-00, Cali,
Colombia. *E-mail: gsoler-illia@unsam.edu.ar
d.Instituto de Física de São Carlos, Universidade de São Paulo, CP. 369, 13560-970,
São Carlos - SP, Brasil. *E-mail: richard.dvries00@usc.edu.co
e. Instituto Sabato, UNSAM-CNEA, Av. Gral. Paz 1499, B1650KNA San Martín,
Buenos Aires, Argentina.
f. Departamento de Nuevas Arquitecturas en Química de Materiales, Materials
Science Factory, Instituto de Ciencia de Materiales de Madrid–Consejo Superior de
Investigaciones Científicas, Sor Juana Inés de la Cruz 3, Madrid 28049, Spain.
g.Programa Nacional de Gestión de Residuos Radiactivos-PNGRR, Comisión
Nacional de Energía Atómica, Av. Gral. Paz 1499, 1650 San Martin, Buenos Aires,
Argentina.
Because of its geometrically flexible coordination
environments, the trivalent Bi ion can be regarded as a novel
node in the construction of CPs. Moreover, bismuth leads to
unpredictable and diverse of structures since it presents a
h.Departamento de Radiobiología, Gerencia de Química Nuclear y Ciencias de la
Salud, Comisión Nacional de Energía Atómica, Av. Gral. Paz 1499, 1650 San
Martin, Buenos Aires, Argentina.
14
variety of coordination numbers. In this context, Inge et al.
recently reported an 8-coordinated Bi-MOF constructed from a
tricarboxylate linker, revealing an unprecedented topological
complexity.
i.
L3 – Luminescent Lanthanide Lab, Ghent University, Department of Chemistry,
Krijgslaan 281, Building S3, 9000 Gent, Belgium.
UMR 7574 Chimie de la Matière Condensée de Paris, UPMC Univ. Paris 06-CNRS,
j.
Collège de France, 11 place Marcelin Berthelot, 75231, Paris Cedex 05, France. *E-
mail: clement.sanchez@upmc.fr
Electronic Supplementary Information (ESI) available: Electronic supplementary
information (ESI) available: Synthetic procedure details, experimental X-ray
powder patterns, TGA and DSC profiles, FTIR spectra and decay luminescence
profiles. CCDC 1561408–1561411. See DOI: 10.1039/x0xx00000x
From the point of view of the design of new CPs, during last
decade iminodiacetic and 1,2,4,5-benzenetetracarboxylic acids
have been employed as building blocks for the synthesis of CPs
and MOFs as multifunctional platforms15.
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On the other hand, diverse strategies have been proposed to 2.4. Powder X-ray diffraction (PXRD): PXRD patterns were
overcome the increasing antibiotic resistance observed in obtained with a Rigaku D-MAX-IIIC diffractometer using CuKα
several pathogenic microorganisms.16 In this sense, due their radiation (λ1= 1.54056 Å, λ2= 1.54439 Å) (see SI section S4).
novel physicochemical properties, metallic or oxides 2.5. Scanning electron microscopy (SEM): SEM micrographs
nanoparticles (NPs) have been developed to counteract and Energy Dispersive Spectroscopy (EDS) (SI section S5) were
microbial pathogens.16 In the case of Bi, different compounds obtained with FEI Quanta 200 equipment. Samples were
are being used against ulcers and treatments of gastritis, placed on an adhesive carbon tape coated with gold for the
diarrhoea and dyspepsia.17 Moreover, bismuth derivatives (for observations.
example bismuth subsaliciylate and bismuth citrate) have been 2.6. Single-Crystal structure determination (SCXRD). SCXRD
used long before as antimicrobial agents against several data for compounds Bi-1, Bi-2 and Zn-1 were collected at room
bacterial species, particularly Helycobacter pylori, a bacterium temperature (293 K) on a Rigaku XTALAB-MINI diffractometer
responsible for peptic ulcer and gastric cancer17e. Their using MoKα radiation (0.71073 Å) monochromated by
antimicrobial activity were observed at relatively high graphite. In-1 compound was collected at room temperature
concentrations due to their limited water solubility.17 In (296 K) on a Bruker APEX-II CCD diffractometer using MoKα
addition, it has been demonstrated that Bi-NPs reduce biofilm radiation (0.71073 Å) monochromated by graphite.
(growth of microorganisms on solid surfaces) formation in The cell determination and the final cell parameters of Bi-1
, Bi-
bacteria and fungus such as Streptococcus mutans and and Zn-1 were obtained on all reflections using the software
2
Candida albicans.19,20 Biofilms represent a great problem for CrystalClear.23 Data integration and scaled was carried out
industry and human health because they form on a wide using the software CrystalClear23 and CrysAlisPro.24 The
variety of surfaces, possess high resistance to antimicrobial structures were solved and refinement with SHELXS-201325
agents and are very difficult to eradicate.21
software, included in WinGX26 and Olex2.27 Cell determination
Besides, to understand the processability and the mechanical and final cell parameters of In-1 crystals were obtained on all
properties of the new materials, nanoindentation studies have reflections using the software Bruker SAINT included in APEX2
recently been adopted. Thanks to pioneering work of software suite.28 Data integration and scaled was carried out
Cheetham22, nanoindentation tests have been applied to using the software Bruker SAINT.27 In all cases non-hydrogen
demonstrate the intrinsic correlations between the crystal atoms of the molecules were clearly resolved and full-matrix
packing and the anisotropic mechanical properties (such as least-squares refinements of these atoms with anisotropic
density, stability and elasticity) in MOF materials.
thermal parameters were performed. Besides, hydrogen
The present work involves a complete study regarding the atoms were stereochemically positioned and refined by the
characterization, riding model.25 ORTEP diagrams for all structures were
synthesis
strategies,
photophysical
mechanical and catalytic analysis and antimicrobial activity of a prepared with Diamond.29 TOPOS30 and Mercury31 programs
set of CPs based in main-group elements (MGE-CPs), more were used in the preparation of the artwork of the polyhedral
specifically two Bi-CPs and one In-CP.
and topological representations.
2.7. Mechanical characterization: samples were prepared for
mechanical characterizations including single crystals in acrylic
2.0. Experimental section
2.1. Synthesis: [Bi(1,2,4,5-BTC)0.5(2,2’-bipyridine)(NO3)(DMF)] resin (SUBITON®). Nanoindentation (NI) experiments were
Bi-1), [Bi(IDA)(IDAH)] (Bi-2), [In(IDA)(Cl)] (In-1) and [Zn(1,2,4,5- performed using an Agilent G200 Nano Indenter at room
BTC)0.5(2,2’-bipyridine)(H2O)] Zn-1), were obtained as temperature. A Berkovich diamond tip with a final rounding of
(
(
crystalline solids under solvothermal conditions using 43 mL 20 nm was used in this study. The tip was calibrated using a
Teflon-lined Parr reactors. The solid reactants and solvents standard fused silica sample. A group of 5 crystals were tested,
were used as received without purification from Across an array of 5x5 measurements up to a maximum penetration
Organics (1,2,4,5-benzenetetracarboxylic acid) and Sigma- depth of 1200 nm were carried out on each selected crystal.
Aldrich
dimethylformamide, iminodiacetic acid, Zn(NO3)2∙6H2O and measurements applying the Oliver & Pharr model, described in
InCl3) (see SI section S1 for synthesis details).
our previous work.7
2.2. Fourier transform infrared spectroscopy (FTIR): FTIR 2.8. Solid State Luminescence Measurements: The steady
spectra were recorded with Nicolet Protégé 460 state and time resolved luminescence measurements were
(2,2’-bipyridine,
Bi(NO3)3∙5H2O,
N,N’- Elastic modulus (E) and hardness (H) were calculated from the
a
spectrometer in the 4000-400 cm−1 range with 64 scans and a performed on an Edinburgh Instruments FLSP920
spectral resolution of 4 cm−1 by the KBr pellet technique. The spectrometer setup, using a 450 W xenon lamp as the steady
FTIR spectra and band assignments are displayed in SI section state excitation source and an EPLED as the time resolved
S2.
excitation source with a fixed excitation wavelength of 331
2.3. Thermal Analysis: Thermogravimetric Analysis (TGA) and nm. The emission was detected by a Hamamatsu R928P PMT
Differential Scanning Calorimetry (DSC) were performed with photomultiplier tube. Excitation spectra were corrected for the
Shimadzu TGA-51 and DSC-60 apparatus under flowing air at xenon lamp emission profile, whereas emission spectra were
50 mL min-1, at a heating rate of 10 °C min-1. TGA and DSC corrected for the detector response curve. All measurements
curves are displayed in SI section S3.
were carried out at a step size of 1 nm.
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2.9. Catalytic Activity: Considering the nature of the new After the followed procedure detailed in (Scheme 1), the
materials, among all possible organic transformations, only phases were characterized by PXRD and EDS in order to
those which require a Lewis acid as catalyst, were taken into confirm their purity (see SI section S4 and S5). The
account. So, as
cyanosilylation reaction was chosen in order to evaluate the identified in Bi-1
catalytic activity of Bi-1 Bi-2 and In-1 materials. In this order, crystals (Figure 1). Good quality crystals were carefully
a
standard organic transformation the morphologies diversity was studied by SEM; plate habits were
,
Bi-2 and Zn-1 meanwhile In-1 exhibited cubic
,
catalytic amounts of the selected material (0.5mol %, 1mol % selected in order to perform SCXRD. The exhibited table in SI
and 2.5mol %) were placed in a Schlenk tube under nitrogen section S6 summarizes the crystallographic data for all the
atmosphere without solvents, together with the corresponding synthesized compounds.
carbonyl compound (1 equivalent); trimethylsilyl cyanide (1.1
equivalent) was then added dropwise by syringe. The mixture
was stirred until disappearance of the carbonyl compound; the
kinetics of the reaction and its yield were checked by GC-MS.
3.0. Antibacterial assays
.
3.0.1. Stock solutions of bismuth compounds
Saturated aqueous solutions of the relatively insoluble
compounds Bi-1, Bi-2 and Bismuth citrate (Bi-cit) (Merck) were
Scheme 1: Synthesis of the reported CPs.
prepared in distilled and sterilized water by 0.22-µm-pore-size
filters. Bi-cit was employed as control because, which is known
as a bismuth derivative inhibitor of bacterial growth16b. The
concentrations of bismuth compounds were expressed as
elemental bismuth determined by Total Reflection X-ray
Fluorescence Spectrometry (PicoFox S2 TXRF – Bruker). Bi-NPs
and Bi-cit concentrations used for this study depended on their
limited water solubility.
3.0.2. Bacterial strains and growth conditions
. The employed
set of bacteria were Escherichia coli (E. coli, strain K12),
Salmonella enteric serovar Typhimurium (S. Typhimurium,
strain LT2) and Pseudomonas aeruginosa (P. aeruginosa, strain
PAO1). For assays with planktonic (free) cells, E. coli, S.
Typhimurium and P. aeruginosa were cultivated in Nutrient
Broth (Difco) at a temperature of 37 °C. For biofilm assays, P.
aeruginosa was grown in LB broth (10 g tryptone, 5 g yeast
extract and 5 g NaCl in 1000 ml distilled water) at 37 °C.
3.0.3. Effect of Bi-NPs on planktonic cultures and biofilm
formation. For assays with planktonic cultures, sterile Bi-
compounds were serially suspended in tubes containing 1
milliliter of Nutrient Broth. Overnight cultures of the three
bacterial strains were diluted 1/100 in saline solution and 100
Figure 1: Micrographs of Bi-1 (a), Bi-2 (b) and In-1 obtained
with (d) and without (c) growth modulator.
ꢀ
l were added to each prepared tube as described. The tubes
4.2. Crystal Structure Descriptions
were incubated for 24 h at 37 °C. Cell mass was evaluated by
optical density at 650 nm wavelength (OD650). Quantification
of viable microorganisms was determined by plate count in
Nutrient Agar (Difco) at 37 °C and expressed by colony forming
units per ml (CFU/ml). Tubes without Bi-compounds were used
as control. For studies of biofilm formation, overnight cultures
of P. aeruginosa were diluted 1/100 in LB in a final volume of
Bi-1 compound crystallizes in the triclinic Pī space group. The
primary building unit (PBU) consists in a nine-coordinated
arrangement (BiO7N2), where seven oxygen atoms belonging
to 1,2,4,5-BTC, DMF and nitrate, and two nitrogen atoms from
the 2,2’-bipyridine form a trigonal prism square-face tricapped
polyhedron (TPRS-9)33 (Figure 2 left). As can been seen in
Figure 2 (right), the asymmetric unit of Bi-1 is composed by
one trivalent Bi cation, one nitrate anion, one DMF and one
2,2’-bipyridine; in addition to a half of a crystallographically
independent 1,2,4,5-BTC ligand.
100 ꢀl in absence or presence of different concentrations of Bi-
compounds in 96-well microplates. After 24 h incubation at 37
°C in a moist chamber, planktonic cells were discarded and
biofilm attached to the surface of microplate wells was
quantified by the “method of crystal violet stain”.32
In this compound each 1,2,4,5-BTC ligand is coordinated to
four Bi centers in chelate η2 mode, giving rise to chains along
[1 0 0] direction (Figure 3 left) with a intermetallic distances of
6.3594(6) and 9.3852(7) Å. The Bi-O bond lengths are in the
4.0. Results
4.1. Synthesis
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range 2.326(5)-2.77(1) Å as it was seen in analogous Bi-
MOFs.14
The crystal structure of Bi-1 was analyzed with TOPOS program
in order to determine the underlying topology34 of the
associated simplified net. Through this simplification it is
possible to observe that the carboxylate ligand acts as 4-
connected node and the metal center acts as bridge forming
“ribbon-like” chains (Figure 3 left). In addition, the compound
can be classified as I0O1 according to the proposed
classification suggested by Cheetham et al.35 describing
“coordination polymeric chains”.
Figure 4: a) Polymeric chain and decorated simplified chain
along [1 0 0] direction and b) crystal packing view into bc plane
of Zn-1 compound.
Bi-2 was obtained as a crystalline solid belonging to monoclinic
C2/c space group. The asymmetric unit is formed by one
crystallographically independent trivalent Bi cation and two
structurally different types of iminodiacetate ligand (IDA and
protonated IDAH). The PBU can be described as 8-coordinated
Figure 2: Polyhedron representation of the PBU (left) and 50% metal center (BiO7N) formed by seven oxygens and one
of probability thermal ellipsoids diagram showing for Bi-1 nitrogen atom from the ligands, forming a square antiprism
(right). Hydrogen and disordered atoms were omitted for polyhedron (SAPR-8) arrangement. In this case, the metal
clarity.
centers are joined by the ligand forming dimmeric sharing
edge SBUs (Bi2N2O12) with a intermetallic distance of 3.9612(9)
The 3D supramolecular structure (Figure 3) is based on weak Å. The formation of the dimmeric SBUs is due to µη2 and µ2η2
hydrogen bonds that join the chains along [0 1 0] and [0 0 1] coordination modes of the carboxylate groups respectively
directions, with distances C9-H9∙∙∙O6 = 3.248(1) and C18- (see SI section S8).
H18A∙∙∙Cg = 3.460(2) Å, respectively (Cg ring = C2, C3, C4, C2*,
C3*, C4*).
Figure 5: PBU representation of the Bi3+ cation (left) and 50%
of probability thermal ellipsoids diagram showing for Bi-2
(right). Hydrogen and disordered atoms were omitted for
clarity.
Figure 3: a) Polymeric chain and decorated simplified chain
along [1 0 0] direction and b) crystal packing view into bc plane
of Bi-1 compound.
In the extended structure the IDA acts as tridentated ligand
blocking the coordination sphere of the Bi3+, while the IDAH
ligand join the SBUs along [0 0 1] direction giving rise to
“ribbon-like” chains (Figures 5 left and SI section S8). Besides
the IDAH ligands join two metallic centers forming dimmeric
SBUs, acting as 4-connected nodes. The 3D supramolecular
crystal packing (Figure 5 right) is given by hydrogen bonds
along [1 0 0] direction with distances N1-H1∙∙∙O4 = 2.932(6)
and C2-H2C∙∙∙O2 = 3.175(8) Å. Similar interactions are involved
along [0 1 0] direction with distances N2-H2B∙∙∙O2 = 2.908(7)
and N2-H2A∙∙∙O4 = 3.091(6) Å.
For comparative purposes Zn-1 compound36,37 was obtained. A
deeper crystallographic description can been found in SI
section S7. Similarly to Bi-1, here the 1,2,4,5-BTC ligand is
coordinated to four metallic centers giving rise to “ribbon-like”
chains along [1 0 0] direction with intermetallic distances of
7.6958(7) and 8.0797(8) Å (Figure 4 a). Despite presenting
different coordination number, both compounds exhibit
similar arrangement of the ligand giving rise to 1D
coordination polymers.
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(a)
(b)
(c)
Figure 6: Polyhedron and simplified representation of the
chains (left) and crystal packing view along [0 0 1] direction of
Bi-2 (right).
(d)
The 3D supramolecular structure is formed by strong hydrogen
bonds and π-π stacking interactions with distances O5-
H5A∙∙∙O1 = 2.657(3) and Cg…Cg = 3.758(2) Å, along [0 0 1] and
[0 1 0] directions respectively.
In-1 crystallizes in the Pnma orthorhombic space group. The
metal environment is formed by one Cl atom, one nitrogen
and four oxygen atoms, giving rise to a distorted octahedral
geometry (Figure 6 left). The asymmetric unit is formed by a
half of In3+ cation, chloride anion and IDA ligand. The ORTEP
diagram of In-1 is displayed in the Figure 7 right. Each ligand is
coordinated in µ3 chelate fashion through the protonated
nitrogen atom and two oxygen atoms of the carboxylate
group. Beside the carboxylate groups exhibits µη2 coordination
mode linking a pair of metallic centers (intermetallic distance =
5.645(2) Å) along [0 1 1] and [0 -1 -1] directions (Figure 8).
Figure 8: Representation of the 2D covalent network (a),
topological simplification (b), 3D crystal packing (c) and the
coordination modes of the IDA ligand in In-1 (d).
4.3. Nanomechanical properties
Dense CPs incorporate infinite inorganic connectivity,
especially those based on metal-oxygen-metal motifs. During
last years, there has been an intense interest focused on CPs
showing unique physical properties associated with their
structures, which includes magnetic, electrical, optical and
multiferroic properties. In spite of that, studies inherent with
mechanical features of CPs are scarce. Besides, for developing
MOFs/CPs sensing devices, it is required good film stiffness
and film-to-substrate adhesion strength. Moreover, elastic
properties of the underlying framework are dominant in the
performance of piezoelectric devices (such as actuators and
sensors) and MOFs coatings or membranes.38
Figure 7: Polyhedron representation of the In3+ (left) and 50%
of probability thermal ellipsoids diagram showing for In-1
compound (right).
The junction of the metallic centers gives rise to layers in the
(011) plane. As far as we know, this structure was topologically
analyzed by first time. In this case each metal acts as 4-
connected node joined by the ligand forming a sql/Shubnikov
topology net with point symbol (44.62) (Figure 8b). The 3D
supramolecular structure is formed by the Cl∙∙∙H-N interaction
with a distance of 2.719(6) Å which enables the stacking of the
covalent layers along [1 0 0] direction (Figure 8c).
Figure 9: P–h profiles (a) of In-1 crystals. Studied planes, in
normal direction to the nanoindenter (b). Indented cube
crystals (c and d).
In this context, it was highlighted the special interest for the
mechanical characterization of low dimensional 1D or 2D
frameworks due to the possibility of delamination (“top-down”
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fabrication) and further deposition onto different substrates to 4.4. Solid-state photoluminescent properties (SSPL)
build membranes and thin-films composites.39,40 To elucidate According to a significant number of specialized articles2 about
structural-mechanical properties, NI experiments were photoluminescent (PL) properties, optical materials can be
performed on selected single crystals of In-1 and Bi-2 as characterized by specific studies: (1) emission spectra
representative models (Figures 9a and 10a). In both cases, a (recorded as intensity vs wavelength), (2) quantum yields
5x5 field of NI was applied on the single crystals. With the (QYs), and (3) the observed lifetime (τobs) which refer to the
purpose of avoid ambiguities, NI experiments on the acrylic efficiency of the luminescence process and the average time
substrate were made (see displacement (
P-h) curves in SI the molecule stays in its excited state before emitting a
section S9) as a control experiment, obtaining H and E values photon, respectively.
of 0.11±0.01 and 2.8±0.1 GPa respectively.
In contrast to the narrow and well predictable emissions of 4f-
The crystallographic planes which probabilistically are exposed 4f transitions in rare earths elements43, the PL in transition
in In-1 compound, also coincident to those which divides the metals and MGE commonly exhibits broad bands. The excited
nanolayers, are the family of h00 ones. In SI section S1, it is states in TM and MGE-based compounds are different from
clear to identify a preferential orientation into the [2 0 0] the ground state and, often, considerably anti-bonding
planes. These planes are exposed by deposition of the layers, producing broad emissions and large stokes shifts. Besides,
which are located the direction in which non-covalent many types of PL might occur in the same compound, being a
interactions ensure the packing of the layers (see Figure 9b). challenge the identification of the electronic transitions.
The same family of 200 planes in Bi-2 (Figure 10b) exposes a LMCT (ligand to metal charge transition) might occur in TM
higher concentration of metallic polyhedral, conferring and MGE-CPs with metals in high oxidation states,
structural stiffness. As can be seen in Figure 9 and 10 c and d, nevertheless the assignment of LMCT in these compounds is
the “Berkovich marks” were identified after NI measurements. often difficult, especially in mixed ligand systems. On the other
The averages values of H and E measured for In-1 were 1.8±0.1 hand, the most likely candidates for metal-centered emission
GPa and 24.3±0.8 GPa, respectively, and for Bi-2 were and are CPs containing s2-ions such Pb2+ and Bi3+, where it is
1.1±0.1 GPa and 12.4±0.5 GPa. The obtained values from Bi-2 possible to observe s-p transitions44.
are considerably lower compared to In-1, possibly due to a The SSPL properties of Bi-1, Bi-2 were studied by recording
decrease in stiffness for being a one-dimensional. excitation-emission spectra, calculating lifetime values and
It is important to note the presence of “pop-in”, or quantificating the color emission (QC) in comparison with the
displacement events, in the NI performed experiments, which respective starting reactants (Bi(NO3)3, H2IDA and H4BTC).
appears due to the breakages of intermolecular weak bonds. Usually, the spectroscopy of Bi3+ with s2 configuration in the
Similar displacements have been reported in low-dimensional ground state and sp configuration in the first excited state is
CPs
such
as
[Yb2(3-OHNDS)2(1,10-phen)2(H2O)]∙3H2O7, discussed in Russell–Saunders-type electronic energy terms.
[Cu(H2O)2(O3PCH2CO2)2]41 and [Mn(2,2-dms)]40.
Intense fluorescent emissions could be assigned to LMCT or
According to the classification reported by Cheetham and the 1P1
colleagues42, In-1 was located into the “dense hybrids” type trivalent Bi3+ ions.45 In Bi-compounds, the dominant excitation
← ←
1S0 and 3P1 1S0 transitions of the s2 electron of
materials and close to MOFs with similar mechanical transition is commonly ascribed to the population of the
3
performance (SI section 10).
excited state P1 from ground state 1S0 (allowed by spin-orbit
coupling), being the 3P0 level strongly forbidden and
a
1S0
1S0
1
metastable state. At high temperatures, the emission P1
transition is the most frequent in relation with 3P1
→
→
transition, evidenced as broad bands accompanied with
splitting components.46
Therein, the emission peaks of Bi-1 are located in longer
wavelength (446, 486 and 511 nm) compared to Bi-2 (421, 435
and 464 nm) (Figure 11). The signal located at 511 nm in Bi-1
could be attributed to
and 2,2’-bipyridine ligands. For Bi-2, the contribution of the
* transition from IDA carboxylate linker cannot be
π←π* and/or n←π* from 1,2,4,5-BTC
n
←π
discarded. Moreover, it is remarkable that the band splitting
between both spectra is different, meanwhile the intensities
are similar. For an in-depth analysis, Zn-1 was obtained and
compared to Bi-1. Due to the fact that Zn-1 and Bi-1 have the
same set of coordinated ligands, both compounds exhibit
broad bands. The phosphorescence emitting bands were
Figure 10: P–h profiles (a) of Bi-2 crystals. Studied planes, in further analyzed by recording intensity decay curves (see SI
normal direction to the nanoindenter (b). Indented single section S11), and luminescence lifetimes were calculated by
crystals (c and d).
fitting mono-exponential functions, I=A∙exp(-t/
τobs). The
corresponding yielded τobs were 16.7 s and 0.52
ꢀ
ꢀs for Bi-1
6 | J. Name., 2012, 00, 1-3
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and Bi-2, respectively. The τobs values of the Bi-CPs are higher green luminescence.47 Basing on this analysis, Bi-1 and Bi-2 can
compared to Bi(NO3)3, H2IDA and H4BTC (1.03, 1.32 and 1.02 ns be used as precursor materials for blue-light OLED/LEDs
respectively).
devices
These differences might be related to their different
coordination environment around Bi3+ ions47, as Bi is nine- 4.5. Catalytic Activity
coordinated in Bi-1, while eight-coordinated in Bi-2. The SSPL Cyanosilylation reactions (CSRs) are important carbon–carbon
and excitation spectra of both Bi-CPs suggest that two bond-forming processes that are catalyzed by Lewis
different emission metal center are responsible for the acids/bases that can be used in homogeneous49, or
resultant luminescence components. It is noticeable that the heterogeneous50. Among all the alternatives, MOFs and CPs
two maximum in the excitation spectra are shifted by 30 nm, are good choices in the heterogeneous catalysts for Lewis acid
which is ascribed to the absorption of bismuth emitting center. reactions owing to their unique reactivity and selectivity under
mild reaction conditions.8,10,13 So, taking into account the
excellent Lewis acid activity displayed by several In-MOFs
reported in the literature,10,11,13 we decided to test the
catalytic activity of Bi-1, Bi-2 and In-1 in the cyanosilylation of
acetophenone (Table 1).
It was found that the reactivity changes as a function of the
metal nature and the number of catalytic active sites
presented in each structure. A study of the kinetic profile
(Figure 12) was made, to understand the catalytic performance
of each material and to determine their Turn Over Frequencies
(TOFs) values.
The PXRD patterns of the recovered Bi-2 and In-1 after the
catalytic reactions indicate that these materials do not suffer
any structural change. However, Bi-1 do not maintain its
structural integrity after the catalytic reaction (see SI, section
S13), and will be not considered as heterogeneous catalyst for
further experiments.
Table 1. Screening of materials as catalysts for cyanosilylation
reaction using acetophenone as carbonyl source.
Metal CN
Dimensionality
9, 1D
Yield (%) b
time (h)
86 (4)
70 (4)
96(4)
98 (4)
90(6)
90(3)
TOF
TON
Material
Topology
c
d
Bi-1a
Bi-2a
In-1a
In-1 e
In-1 f
Chain
Chain
sql
sql
sql
184
33
76
-
-
-
86
70
96
40
180
90
8, 1D
6, 2D
6, 2D
6, 2D
Figure 11: Top: Excitation (left) and emission (right) spectra of
Bi-CPs in comparison with Bi(NO3)3, H2IDA, H4BTC and Zn-1
Down: Chromaticities (CIE 1931) exhibited by Bi-1 Bi-2 and Zn-
.
,
g [51]
1.
InBr3
Salt
-
Blank
N.A
N.A
28(24)
N.A
N.A
b
a Solvent free reaction at 25ºC and 1 mol% of catalyst under N2 atmosphere,
The QC for optical materials enables to an accurate
comparison between different materials related with its light-
emitting performance. In this sense, the color coordinates are
usually calculated employing the CIE (Commission
International de L’Éclairage) system (SI section S12), proposed
in 1931.48 According to this approach, Bi-1 and Bi-2 were
identified with bluish green and bluish purple emissions
respectively (Figure 11 bottom). In comparison, similar
colorimetric and spectroscopic features were observed in
analogous Bi-HPyr (H4Pyr=1,2,4,5-BTC) which exhibited pale
c
d
Yields (GC-MS), TOF: ꢁχ x [mol of reactant / mol catalyst]/ ꢁt), TON: (χ/ mol
catalyst), e Reaction employing 2.5 mol% of catalyst loading, f Reaction employing
g
0.5 mol% of catalyst loading, homogeneous catalyst [1 mol%] using CH2Cl2 as
solvent.
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Table 2. Scope of the In-1 cyanosilylation of ketones.a
time
(h)
4
Yield
(%)b
96
Entry
Ketone
TON c
1
acetophenone
96
89
80
98
96
97
99
85
2
3
4
5
6
7
8
4-methylacetophenone
2-methylacetophenone
Cyclopentanone
8
89
8
80
3.5
4
98
cyclohexanone
96
4-methylcyclohexanone
2-hexanone
4
97
3
˃99
85
3-hexanone
3
a
Solvent free reaction at 25 ºC and
1 mol% of catalyst under N2
atmosphere, b product Yields (GC-MS) and c TON: (χ/ mol catalyst).
The results of the reactions carried out with acetophenone
derivatives with electron-donating substituents such as 2-
methylacetophenone and 4-methylacetophenone, showed
yiels of 80% and 89% respectively.
Figure 12: Kinetic profiles of Bi-1, Bi-2 and In-1 catalysts in the
cyanosilylation of acetophenone.
The recyclability tests shows that In-1 material maintains its
crystallinity even after ten catalytic cycles, with only a small
decrease of its catalytic activity, probably due to the losses
during the recovery of the catalyst (see SI, section S14). Hot
filtration experiments reveal that In-1 is a truly heterogeneous
catalyst.
From the data presented in Table 1 it is evident that a
structure/catalytic ability relationship exits. The comparison
between Bi-2 and In-1, which have the same organic linker in
their structure, allows the study based on the nature of the
metal cation. It would be expected that Lewis acid behavior
follows In-1
acid strength. Besides indium catalyst with octahedral metal
centers forms covalent framework with higher
> Bi-2 order, based on the cation size impact in the
4.6. Antibacterial assays
a
Firstly, effects of Bi-NPs and Bi-cit on the cell growth of
dimensionality (2D layers) than Bi-2 (1D chains) material. This
higher covalent disposition of In-1 clearly seems to favor the
interaction between the available active sites of the catalyst
with the substrates, even for the most sterically hindered
ones, as can be appreciated in Table 2.
planktonic cultures of E. coli
, S. Typhimurium and P.
aeruginosa, were analyzed. Figure 13 shows that Bi-1 required
1.2 µg∙ml-1 to decrease 6 logs in E. coli and P. aeruginosa and 7
logs in S. Typhimurium (viable counts compared to controls). In
contrast, 295 µg∙ml-1 of Bi-2 were required to reduce 2 logs the
cell viability of E. coli and S. Typhimurium, and 4 logs in P.
The scope of the reaction was studied for the cyanosilylation
of ketones using In-1 as catalyst (Table 2). In case of non-
aromatic ketones (Table 2, entries 4-8), higher yields were
obtained compared to the aromatic ones (Table 2, entries 1-3).
Reactions with linear aliphatic ketones (Table 2, entries 7-8)
proceeded efficiently giving the corresponding product at
shorter times with yields over 85%. The cyclic ketones (Table 2,
entries 4-6) higher yields were obtained (˃97%). Finally, the
less reactive aromatic ketones also reached good yields (80-
96%).
aeruginosa (Figure 13b). Bi-cit decreased cell viability 1.5-2
logs at 6.8 µg∙ml-1 in all the studied microorganisms (Figure
13). Reduction of cell mass measured by OD650 followed the
same observed tendency for the cell viability (Figure 13).
According to these results, the greatest effect was produced
by Bi-1, not only for the several orders of log reduction, but
also by the lower concentration required for reduction of
bacterial growth (Table 3).
Table 3: Log10 reductions of bacterial viability produced by Bi-
compounds compared to controls, according to the maximum
concentration of compound used.
Organism
Bi-1
Bi-2
Bi-cit
(1.2 µg/ml) (295 µg/ml) (6.8 µg/ml)
E. coli
6
7
6
2
2
4
2
2
S. Typhimurium
P. aeruginosa
1.5
8 | J. Name., 2012, 00, 1-3
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Then the effect of Bi-NPs on biofilm formation of P. aeruginosa
was studied. P. aeruginosa is relevant opportunistic
a
pathogen of humans; given its great capacity to form biofilms
on diverse surfaces causing severe damages to industry and
human health, it is largely employed as model in biofilm
studies. Quantification of biofilms in control and test assays
demonstrated that both Bi-NPs efficiently inhibited biofilm
formation, although Bi-1 produced its antibiofilm effect at
lower concentrations than Bi-2 (Figure 14a). In contrast to Bi-
NPs, Bi-cit did not inhibit biofilm formation at concentrations ≤
g/ml; moreover, it promoted its development. However, at
Figure 14: Effect of Bismuth compounds on biofilm formation
in P. aeruginosa (a). P. aeruginosa was grown in 96 well
microplates in absence or in presence of different
concentrations of Bi-NPs and Bismuth citrate. Biofilms adhered
to the wells were subsequently stained with crystal violet and
the absorbance of the solubilized stain was measured at 575
nm. Error bars represent the standard deviation of at least
three independent experiments (b). Visualization of biofilm
formation in absence or in presence of different
concentrations of Bi-NPs by crystal violet staining.
Representative images are shown.
3
ꢀ
higher concentrations, this effect was reversed and inhibition
of biofilm formation was observed. Representative images of
stained 24 h biofilms illustrate the inhibitory effect of Bi-NPs
on biofilm formation (Figure 14b). It is concluded that both Bi-
NPs are effective antibiofilm agents in P. aeruginosa, being Bi-
1
more powerful than Bi-2.
Conclusions
A set of CPs based on bismuth, indium and zinc were
successfully obtained. Due to the lack of studies regarding to
structural, optical, mechanical and antibacterial properties of
CPs an exhaustive analysis covering these topics was carried
out. These compounds were synthesized from bismuth and
indium salts, IDA, 1,2,4,5-BTC, and 2,2’-bipyridine as building
blocks. The one-dimensional Bi-CPs, [Bi(1,2,4,5-BTC)0.5(2,2’-
bipyridine)(NO3)(DMF)] and [Bi(IDA)(IDAH)], belonged to Pī and
C2/c space groups, meanwhile the layered In-CP, [In(IDA)Cl],
belonged to the Pnma space group. Moreover, an in-deep
analysis of the topology was carried out, where the Bi-CPs
were simplified as “ribbon-like” chains, and sql/Shubnikov
tetragonal plane net with point symbol (44.62).
In order to find relationships between the structural features
and the intrinsic mechanical properties, nanoindentation
studies were performed onto a 1D and a layered compound
(
Bi-2 and In-1). The differences in the mechanical
performances in both compounds were related to their crystal
packing. According to H and E values, the CPs were located
into the “dense hybrids” type materials. These studies are
important to evaluate the mechanical qualities in low
dimensional materials for device development.
Figure 13: Viable organisms/mL and OD650 profiles of Bi-1, Bi-2
The SSPL properties of the Bi-CPs were studied, which involved
excitation–emission, lifetime experiments and quantification
of colour emission. Regarding to these results, the Bi-CPs were
classified as blue-emitters in the visible region, with
performances compared with analogous Bi-compounds and
TM-MOFs. These optical features made Bi-CPs important for
the design of photonic devices with blue light emissions.
From our catalytic studies under solvent-free conditions on
these new CPs we can conclude that the factor which drives
the reaction yield relies on the metal nature and framework
and Bi-cit.
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Journal Name
Vaughn, M. D. Smith, H.-C. zur Loye, Inorg. Chem., 2010, 49
,
dimensionality. Therefore, the catalytic activity decreases in
the following order In-1 Bi-2 In-1 material is capable of work
11001; (d) A. C. Wibowo, M. D. Smith, H.-C. zur Loye,
CrystEngComm, 2011, 13, 426; (e) A. Thirumurugan, W. Li, A.
K. Cheetham, Dalton Trans., 2012, 41, 4126, (f) Liang Kan,
Jiantang Li, Xiaolong Luo, Guanghua Li, Yunling Liu, Inorg.
Chem. Comm., doi.org/10.1016/j.inoche.2017.06.018.
>
.
as a real heterogeneous catalyst, using several hindered
carbonyl derivates at mild reaction conditions reaching high
yields with a good recyclability rate.
5
6
M. Feyand, E. Mugnaioli, F. Vermoortele, B. Bueken, J. M.
Dieterich, T. Reimer, U. Kolb, D. de Vos and N. Stock, Angew.
Chem., 2012, 124, 10519; (b) M. Feyand, E. Mugnaioli, F.
Vermoortele, B. Bueken, J. M. Dieterich, T. Reimer, U. Kolb
Finally, the strong antibacterial effect of the Bi-CPs on E. coli
,
Typhimurium, S. Typhimurium and P. aeruginosa, was
observed and compared to the well known bismuth salt Bi-cit,
especially in the case of Bi-1. The emergence and spread of
antibiotic resistant derivatives constitute an actual problem
that threatens the efficacy of treatment of many bacterial
infections with antibiotics, then it is necessary the
development of novel pathogen eradication methodologies.
and D. de Vos, N. Stock, Angew. Chem. Int. Ed., 2012, 52
10373.
,
(a) G. E. Gomez, M. C. Bernini, E. V. Brusau, G. E. Narda, W.r
A. Massad and A. Labrador, Cryst. Growth Des., 2013, 13
,
5249; (b) R. F. D'Vries, G. E. Gomez, J. H. Hodak and G. J. A. A.
Soler-Illia, J. Ellena, Dalton Trans., 2016, 45, 646; (c) G. E.
Gomez, M. C. Bernini, E. V. Brusau, G. E. Narda, D. Vega, A.
M. Kaczmarek, R. Van Deun and M. Nazzarro, Dalton Trans.,
2015, 44, 3417.
Conflicts of interest
7
8
R. F. D'Vries, G. E. Gomez, D. F. Lionello, M. C. Fuertes, G. J.
A. A. Soler-Illia and J. Ellena, RSC Adv., 2016, 6 (111), 110171.
There are no conflicts to declare.
G. E. Gomez, A. M. Kaczmarek, R. Van Deun, E. V. Brusau, G.
E. Narda, D. Vega, M. Iglesias, E. Gutierrez-Puebla and M.
Ángeles Monge, Eur. J. Inorg. Chem., 2016, 2016 (10), 1577.
R. F. D’Vries, V. A. de la Peña-O’Shea, N. Snejko, M. Iglesias,
E. Gutiérrez-Puebla and M. A. Monge, J. Am. Chem. Soc.,
2013, 135, 5782.
Acknowledgements
9
This work was supported by the Consejo Nacional de
Investigaciones Científicas y Técnicas, ANPCyT PICT 2012-2087
and CNEA. G. E. G. acknowledges the postdoctoral CONICET
fellowship and HYMADE project. R. D. acknowledges
Coordenação de Aperfeiçoamento de Pessoal de Nível
Superior for the CAPES/PNPD scholarship from the Brazilian
Ministry of Education and Universidad Santiago de Cali. D. F. L.
acknowledges doctoral CONICET fellowship. Ramón Castillo
Guerra, Ricardo Montero, Guillermo Arnaldo, Rodrigo Taboada
and Gonzalo Zbihlei, from Departamento de Materiales –
(CNEA), are gratefully thanked for helping with sample
preparation for NI testing. L. M. A.-D., M. I. and M. A. M.
acknowledge the Spanish Ministry of Economy, Industry and
Competitiveness (MINECO-Spain) projects MAT2013-45460-R,
MAT2014-52085-C2-2-P, MAT2016-78465-R and CTQ2014-
61748-EXP, Fondo Social Europeo from the European Union.
Comunidad Autónoma de Madrid S2013/MIT-2740 (PHAMA
2.0). R. V. D. and A. M. K. acknowledge Ghent University’s
Special Research Fund (BOF) for a Posdoctoral Mandate
(project BOF15/PDO/091). J. E. is grateful to CNPq for the
research fellowships. G. J. A. A. S. I. and M. C. F. are members
of CIC-CONICET. Besides, this project has received funding
from the European Union’s Horizon 2020 research and
innovation program H2020-MSCA-RISE-2014, GA Nº 645686.
10 (a) L. M. Aguirre-Díaz, D. Reinares-Fisac, M. Iglesias, E.
Gutiérrez-Puebla, F. Gándara, N. Snejko, M. A. Monge,
Coord. Chem. Rev., 2017, 335, 1. (b) L. M. Aguirre-Díaz, M.
Iglesias, N. Snejko, E. Gutiérrez-Puebla and M. A. Monge, RSC
Adv., 2015, 5, 7058.
11 (a) R. F. D’Vries, Susana Álvarez-García, Natalia Snejko, Luisa
E. Bausá, Enrique Gutiérrez-Puebla, Alicia de Andrés and M.
A. Monge, J. Mat. Chem. C, 2013, 1(39), 6316. (b) R. F.
D’vries, M. Iglesias, N. Snejko, E. Gutiérrez-Puebla, M. A.
Monge, Inorg. Chem., 2012, 51, 11349-11355.
12 (a) G. E. Gomez, E. V. Brusau, A. M. Kaczmarek, C. Mellot-
Draznieks, J. Sacanell, G. Rousse, R. Van Deun, C. Sanchez, G.
E. Narda and G. J. A. A. Soler Illia, Eur. J. Inorg. Chem., 2017,
2017 (17), 2321. (b) A. A. Godoy, G. E. Gomez, A. M.
Kaczmarek, R. Van Deun, O. J. Furlong, F. Gándara, M. A.
Monge, M. C. Bernini, G. Narda, J. Mater. Chem. C, 2017, 5,
12409-12421.
13 (a) L. M. Aguirre-Díaz, F. Gándara, M. Iglesias, N. Snejko, E.
Gutiérrez-Puebla and M. A. Monge, J. Am. Chem. Soc., 2015,
137, 6132. (b) L. M. Aguirre-Díaz, M. Iglesias, N. Snejko, E.
Gutiérrez-Puebla and M. A. Monge, Chem. Eur. J. 2016, 22
,
6654. (c) D. Reinares-Fisac, L. M. Aguirre-Díaz, M. Iglesias, N.
Snejko, E. Gutiérrez-Puebla, M. A. Monge and F. Gándara, J.
Am. Chem. Soc., 2016, 138 (29), 9089.
14 A. K. Inge, M. Köppen, J. Su, M. Feyand, H. Xu, X. Zou, M.
O'Keeffe and N. Stock, J. Am. Chem. Soc., 2016, 138, 1970.
15 (a) X. X. Wang, B. Yu and K. Van Hecke, RSC Adv., 2014,
4(106), 61281-61289. (b) J.-M. Hao, L. N. Wang, K. Van
Hecke, G.-H. Cui, Inorg. Chem. Comm., 2014, 41, 43-46. (c) J.-
M. Hao, B.-Y. Yi, K. Van Hecke, G.-H. Cui, CrystEngComm,
2015, 17, 2279-2293. (d) L.-M. Zhang, D.-Y. Deng, G. Peng, L.
Liang, G.-Q. Lan, H. Deng, CrystEngComm., 2012, 14, 8083-
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