30 research outputs found
Modular Assembly of Metal–Organic Supercontainers Incorporating Sulfonylcalixarenes
A new strategy for the design of container molecules
is presented.
Sulfonylcalix[4]Âarenes, which are synthetic macrocyclic containers,
are used as building blocks that are combined with various metal ions
and tricarboxylate ligands to construct metal–organic “supercontainers”
(MOSCs). These MOSCs possess both endo and exo cavities and thus mimic
the structure of viruses. The synthesis of MOSCs is highly modular,
robust, and predictable. The unique features of MOSCs are expected
to provide exciting new opportunities for the exploration of their
functional applications
Modular Assembly of Metal–Organic Supercontainers Incorporating Sulfonylcalixarenes
A new strategy for the design of container molecules
is presented.
Sulfonylcalix[4]Âarenes, which are synthetic macrocyclic containers,
are used as building blocks that are combined with various metal ions
and tricarboxylate ligands to construct metal–organic “supercontainers”
(MOSCs). These MOSCs possess both endo and exo cavities and thus mimic
the structure of viruses. The synthesis of MOSCs is highly modular,
robust, and predictable. The unique features of MOSCs are expected
to provide exciting new opportunities for the exploration of their
functional applications
Modular Assembly of Metal–Organic Supercontainers Incorporating Sulfonylcalixarenes
A new strategy for the design of container molecules
is presented.
Sulfonylcalix[4]Âarenes, which are synthetic macrocyclic containers,
are used as building blocks that are combined with various metal ions
and tricarboxylate ligands to construct metal–organic “supercontainers”
(MOSCs). These MOSCs possess both endo and exo cavities and thus mimic
the structure of viruses. The synthesis of MOSCs is highly modular,
robust, and predictable. The unique features of MOSCs are expected
to provide exciting new opportunities for the exploration of their
functional applications
Synthetic Supercontainers Exhibit Distinct Solution versus Solid State Guest-Binding Behavior
The
phase-dependent host–guest binding behavior of a new
family of synthetic supercontainers has been probed in homogeneous
solution and at liquid–liquid, solid–liquid, and solid–gas
interfaces. The synthetic hosts, namely, type II metal–organic
supercontainers (MOSCs), are constructed from the assembly of divalent
metal ions, 1,4-benzenedicarboxylate (BDC) linker, and sulfonylcalix[4]Âarene-based
container precursors. One member of the MOSCs, MOSC-II-tBu-Ni, which
is derived from NiÂ(II), BDC, and <i>p</i>-<i>tert</i>-butylsulfonylcalixÂ[4]Âarene (TBSC), crystallizes in the space group <i>R</i>3Ě… and adopts pseudo face-centered cubic (fcc) packing,
whereas other MOSCs, including TBSC analogue MOSC-II-tBu-Co, <i>p</i>-<i>tert</i>-pentylsulfonylcalixÂ[4]Âarene (TPSC)
analogues MOSC-II-tPen-Ni/Co, and <i>p</i>-<i>tert</i>-octylsulfonylcalixÂ[4]Âarene (TOSC) analogues MOSC-II-tOc-Ni/Mg/Co,
all crystallize in the space group <i>I</i>4/<i>m</i> and assume a pseudo body-centered cubic (bcc) packing mode. This
solid-state structural diversity is nevertheless not reflected in
their solution host–guest chemistry, as evidenced by the similar
binding properties of MOSC-II-tBu-Ni and MOSC-II-tBu-Co in solution.
Both MOSCs show comparable binding constants and adsorb ca. 7 equiv
of methylene blue (MB) and ca. 30 equiv of aspirin in chloroform.
In contrast, the guest-binding behavior of the MOSCs in solid state
reveals much more variations. At the solid–liquid interface,
MOSC-II-tBu-Co adsorb ca. 5 equiv of MB from an aqueous solution at
a substantially faster rate than MOSC-II-tBu-Ni does. However, at
the solid–gas interface, MOSC-II-tBu-Ni has higher gas uptake
than MOSC-II-tBu-Co, contradicting their overall porosity inferred
from the crystal structures. This discrepancy is attributed to the
partial collapse of the solid-state packing of the MOSCs upon solvent
evacuation. It is postulated that the degree of porosity collapse
correlates with the molecular size of the MOSCs, i.e., the larger
the MOSCs, the more severe they suffer from the loss of porosity.
The same principle can rationalize the negligible N<sub>2</sub> and
O<sub>2</sub> adsorption seen in the larger MOSC-II-tPen-Co and MOSC-II-tOC-Ni/Mg/Co
molecules. MOSC-II-tPen-Ni features an intermediate molecular size
and endures a partial structural collapse in such a way that the resulting
pore dimension permits the inclusion of kinetically smaller O<sub>2</sub> (3.46 Ă…) but excludes larger N<sub>2</sub> (3.64 Ă…),
explaining the observed remarkable O<sub>2</sub>/N<sub>2</sub> adsorption
selectivity
Europium Pyrimidine-4,6-dicarboxylate Framework with a Single-Crystal-to-Single-Crystal Transition and a Reversible Dehydration/Rehydration Process
In
this paper, a novel three-dimensional (3D) porous lanthanide–organic
framework, Eu<sub>2</sub>(μ<sub>4</sub>-pmdc)<sub>2</sub>(OH)<sub>2</sub>·3H<sub>2</sub>O (<b>1</b>), which is stable up
to 400 °C, has been hydrothermally synthesized and characterized.
It shows intriguing single-crystal-to-single-crystal transformation
and reversible dehydration/rehydration phenomenon upon removal and
rebinding of the lattice water molecules, which is supported by single-crystal
X-ray diffraction, powder X-ray diffraction, and photoluminescence
data
Europium Pyrimidine-4,6-dicarboxylate Framework with a Single-Crystal-to-Single-Crystal Transition and a Reversible Dehydration/Rehydration Process
In
this paper, a novel three-dimensional (3D) porous lanthanide–organic
framework, Eu<sub>2</sub>(μ<sub>4</sub>-pmdc)<sub>2</sub>(OH)<sub>2</sub>·3H<sub>2</sub>O (<b>1</b>), which is stable up
to 400 °C, has been hydrothermally synthesized and characterized.
It shows intriguing single-crystal-to-single-crystal transformation
and reversible dehydration/rehydration phenomenon upon removal and
rebinding of the lattice water molecules, which is supported by single-crystal
X-ray diffraction, powder X-ray diffraction, and photoluminescence
data
Europium Pyrimidine-4,6-dicarboxylate Framework with a Single-Crystal-to-Single-Crystal Transition and a Reversible Dehydration/Rehydration Process
In
this paper, a novel three-dimensional (3D) porous lanthanide–organic
framework, Eu<sub>2</sub>(μ<sub>4</sub>-pmdc)<sub>2</sub>(OH)<sub>2</sub>·3H<sub>2</sub>O (<b>1</b>), which is stable up
to 400 °C, has been hydrothermally synthesized and characterized.
It shows intriguing single-crystal-to-single-crystal transformation
and reversible dehydration/rehydration phenomenon upon removal and
rebinding of the lattice water molecules, which is supported by single-crystal
X-ray diffraction, powder X-ray diffraction, and photoluminescence
data
Europium Pyrimidine-4,6-dicarboxylate Framework with a Single-Crystal-to-Single-Crystal Transition and a Reversible Dehydration/Rehydration Process
In
this paper, a novel three-dimensional (3D) porous lanthanide–organic
framework, Eu<sub>2</sub>(μ<sub>4</sub>-pmdc)<sub>2</sub>(OH)<sub>2</sub>·3H<sub>2</sub>O (<b>1</b>), which is stable up
to 400 °C, has been hydrothermally synthesized and characterized.
It shows intriguing single-crystal-to-single-crystal transformation
and reversible dehydration/rehydration phenomenon upon removal and
rebinding of the lattice water molecules, which is supported by single-crystal
X-ray diffraction, powder X-ray diffraction, and photoluminescence
data
Europium Pyrimidine-4,6-dicarboxylate Framework with a Single-Crystal-to-Single-Crystal Transition and a Reversible Dehydration/Rehydration Process
In
this paper, a novel three-dimensional (3D) porous lanthanide–organic
framework, Eu<sub>2</sub>(μ<sub>4</sub>-pmdc)<sub>2</sub>(OH)<sub>2</sub>·3H<sub>2</sub>O (<b>1</b>), which is stable up
to 400 °C, has been hydrothermally synthesized and characterized.
It shows intriguing single-crystal-to-single-crystal transformation
and reversible dehydration/rehydration phenomenon upon removal and
rebinding of the lattice water molecules, which is supported by single-crystal
X-ray diffraction, powder X-ray diffraction, and photoluminescence
data
Europium Pyrimidine-4,6-dicarboxylate Framework with a Single-Crystal-to-Single-Crystal Transition and a Reversible Dehydration/Rehydration Process
In
this paper, a novel three-dimensional (3D) porous lanthanide–organic
framework, Eu<sub>2</sub>(μ<sub>4</sub>-pmdc)<sub>2</sub>(OH)<sub>2</sub>·3H<sub>2</sub>O (<b>1</b>), which is stable up
to 400 °C, has been hydrothermally synthesized and characterized.
It shows intriguing single-crystal-to-single-crystal transformation
and reversible dehydration/rehydration phenomenon upon removal and
rebinding of the lattice water molecules, which is supported by single-crystal
X-ray diffraction, powder X-ray diffraction, and photoluminescence
data