16 research outputs found
Red-to-Black Piezochromism in a Compressible PbāIāSCN Layered Perovskite
Red-to-Black Piezochromism in a Compressible PbāIāSCN
Layered Perovskit
Red-to-Black Piezochromism in a Compressible PbāIāSCN Layered Perovskite
Red-to-Black Piezochromism in a Compressible PbāIāSCN
Layered Perovskit
Integration of Intrinsic Proton Conduction and Guest-Accessible Nanospace into a Coordination Polymer
We
report the synthesis and characterization of a coordination
polymer that exhibits both intrinsic proton conductivity and gas adsorption.
The coordination polymer, consisting of zinc ions, benzimidazole,
and orthophosphate, exhibits a degree of flexibility in that it adopts
different structures before and after dehydration. The dehydrated
form shows higher intrinsic proton conductivity than the original
form, reaching as high as 1.3 Ć 10<sup>ā3</sup> S cm<sup>ā1</sup> at 120 Ā°C. We found that the rearranged conduction
path and liquid-like behavior of benzimidazole molecules in the channel
of the framework afforded the high proton conductivity. Of the two
forms of the framework, only the dehydrated form is porous to methanol
and demonstrates guest-accessible space in the structure. The proton
conductivity of the dehydrated form increases by 24 times as a result
of the in situ adsorption of methanol molecules, demonstrating the
dual functionality of the framework. NMR studies revealed a hydrogen-bond
interaction between the framework and methanol, which enables the
modulation of proton conductivity within the framework
Coordination-Network-Based Ionic Plastic Crystal for Anhydrous Proton Conductivity
An ionic coordination network consisting of protonated
imidazole
and anionic one-dimensional chains of Zn<sup>2+</sup> phosphate was
synthesized. The compound possesses highly mobile ions in the crystal
lattice and behaves as an ionic plastic crystal. The dynamic behavior
provides a proton conductivity of 2.6 Ć 10<sup>ā4</sup> S cm<sup>ā1</sup> at 130 Ā°C without humidity
Reversible Solid-to-Liquid Phase Transition of Coordination Polymer Crystals
The solid-to-liquid
phase transition, a fundamental process commonly
observed for various types of substances with significant potential
for application, has been given little attention in the field of coordination
polymers (CPs) despite the rich functionality of these compounds.
In this article, we report the reversible solid-to-liquid phase transition
of crystalline CPs. These CPs are composed of zinc ions, phosphate,
and azoles, and a well-balanced composition, ionicity, and bond strength
afford āmeltingā CPs. We examined the structure of one
such melting framework in the liquid and glass states and found that
the coordination bonds are not fully preserved in the liquid state
but are re-formed in the glass state. As a demonstration, we fabricated,
via phase transition, a thin film with an aligned crystal orientation
and a monolith crystal of the CP
Inherent Proton Conduction in a 2D Coordination Framework
We synthesized a coordination polymer consisting of Zn<sup>2+</sup>, 1,2,4-triazole, and orthophosphates, and demonstrated for
the first
time intrinsic proton conduction by a coordination network. The compound
has a two-dimensional layered structure with extended hydrogen bonds
between the layers. It shows intrinsic proton conductivity along the
direction parallel to the layers, as elucidated by impedance studies
of powder and single crystals. From the low activation energy for
proton hopping, the conduction mechanism was found to be of the Grotthuss
fashion. The hopping is promoted by rotation of phosphate ligands,
which are aligned on the layers at appropriate intervals
Postsynthesis Modification of a Porous Coordination Polymer by LiCl To Enhance H<sup>+</sup> Transport
A Ca<sup>2+</sup> porous coordination polymer with 1D channels
was functionalized by the postsynthesis addition of LiCl to enhance
the H<sup>+</sup> conductivity. The compound showed over 10<sup>ā2</sup> S cm<sup>ā1</sup> at 25 Ā°C and 20% relative humidity.
Pulse-field gradient NMR elucidated that the fast H<sup>+</sup> conductivity
was achieved by the support of Li<sup>+</sup> ion movements in the
channel
Synthesis and Porous Properties of Chromium Azolate Porous Coordination Polymers
We developed a new
route for synthesis of Cr-based porous coordination polymers (PCPs)
with azole ligands and characterized the unique open structures by
single-crystal X-ray studies and other spectroscopy techniques. Chromium-based
PCPs have been prepared from azolate ligands 3,5-dimethyl-1<i>H</i>-pyrazole-4-carboxylic acid (H<sub>2</sub>dmcpz) and 1,4-diĀ(1<i>H</i>-tetrazole-5yl)Ābenzene (H<sub>2</sub>BDT) by solvothermal
reactions under an Ar atmosphere. [Cr<sub>3</sub>OĀ(Hdmcpz)<sub>6</sub>(DMF)<sub>3</sub>]āDMF (<b>1</b>āDMF) is a coordination
compound that forms a hydrogen-bonded porous network. [Cr<sub>3</sub>OĀ(HBDT)<sub>2</sub>(BDT)ĀCl<sub>3</sub>)]āDMF (<b>2</b>āDMF) possesses a new type of trinuclear chromium Ī¼<sub>3</sub>-O unit cluster and the novel topology of a Cr-based PCP with
700 m<sup>2</sup> g<sup>ā1</sup> of BrunauerāEmmettāTeller
surface area. [CrĀ(BDT)Ā(DEF)]āDEF (<b>3</b>āDEF)
is structurally flexible and reactive to O<sub>2</sub> molecules because
of the unsaturated Cr<sup>2+</sup> centers. This is the first report
of a Cr-based PCP/metalāorganic framework with noncarboxylate
ligands and characterization by single-crystal X-ray diffraction
Synthesis and Porous Properties of Chromium Azolate Porous Coordination Polymers
We developed a new
route for synthesis of Cr-based porous coordination polymers (PCPs)
with azole ligands and characterized the unique open structures by
single-crystal X-ray studies and other spectroscopy techniques. Chromium-based
PCPs have been prepared from azolate ligands 3,5-dimethyl-1<i>H</i>-pyrazole-4-carboxylic acid (H<sub>2</sub>dmcpz) and 1,4-diĀ(1<i>H</i>-tetrazole-5yl)Ābenzene (H<sub>2</sub>BDT) by solvothermal
reactions under an Ar atmosphere. [Cr<sub>3</sub>OĀ(Hdmcpz)<sub>6</sub>(DMF)<sub>3</sub>]āDMF (<b>1</b>āDMF) is a coordination
compound that forms a hydrogen-bonded porous network. [Cr<sub>3</sub>OĀ(HBDT)<sub>2</sub>(BDT)ĀCl<sub>3</sub>)]āDMF (<b>2</b>āDMF) possesses a new type of trinuclear chromium Ī¼<sub>3</sub>-O unit cluster and the novel topology of a Cr-based PCP with
700 m<sup>2</sup> g<sup>ā1</sup> of BrunauerāEmmettāTeller
surface area. [CrĀ(BDT)Ā(DEF)]āDEF (<b>3</b>āDEF)
is structurally flexible and reactive to O<sub>2</sub> molecules because
of the unsaturated Cr<sup>2+</sup> centers. This is the first report
of a Cr-based PCP/metalāorganic framework with noncarboxylate
ligands and characterization by single-crystal X-ray diffraction
Postsynthesis Modification of a Porous Coordination Polymer by LiCl To Enhance H<sup>+</sup> Transport
A Ca<sup>2+</sup> porous coordination polymer with 1D channels
was functionalized by the postsynthesis addition of LiCl to enhance
the H<sup>+</sup> conductivity. The compound showed over 10<sup>ā2</sup> S cm<sup>ā1</sup> at 25 Ā°C and 20% relative humidity.
Pulse-field gradient NMR elucidated that the fast H<sup>+</sup> conductivity
was achieved by the support of Li<sup>+</sup> ion movements in the
channel