Coinage Metal Halide Clusters: From Two-Dimensional Ring to Three-Dimensional Solid-State-Like Structures

ChemPhysChem ◽  
2006 ◽  
Vol 7 (11) ◽  
pp. 2286-2289 ◽  
Author(s):  
Robert P. Krawczyk ◽  
Anton Hammerl ◽  
Peter Schwerdtfeger
Keyword(s):  
Solid State ◽  
Three Dimensional ◽  
Metal Halide ◽  
Two Dimensional ◽  
Coinage Metal

Colossal Barocaloric Effects with Ultralow Hysteresis in Two-Dimensional Metal–Halide Perovskites

2021 ◽  
Author(s):  
Jarad Mason ◽  
Jinyoung Seo ◽  
Ryan McGillicuddy ◽  
Adam Slavney ◽  
Selena Zhang ◽  
...  
Keyword(s):  
Carbon Dioxide ◽  
Phase Transitions ◽  
Solid State ◽  
Hydrostatic Pressure ◽  
Metal Halide ◽  
Two Dimensional ◽  
Vapor Compression ◽  
Entropy Changes ◽  
Halide Perovskites ◽  
Solid State Cooling

Abstract Nearly 4,400 TWh of electricity—20% of the total consumed in the world—is used each year by refrigerators, air conditioners, and heat pumps for cooling. In addition to the 2.3 Gt of carbon dioxide emitted during the generation of this electricity, the vapor-compression-based devices that provided the bulk of this cooling emitted fluorocarbon refrigerants with a global warming potential equivalent to 1.5 Gt of carbon dioxide into the atmosphere. With population and economic growth expected to dramatically increase over the next several decades, the development of alternative cooling technologies with improved efficiency and reduced emissions will be critical to meeting global cooling needs in a more sustainable fashion. Barocaloric materials, which undergo thermal changes in response to applied hydrostatic pressure, offer the potential for solid-state cooling with high energy efficiency and zero direct emissions, as well as faster start-up times, quieter operation, greater amenability to miniaturization, and better recyclability than conventional vapor-compression systems. Efficient barocaloric cooling requires materials that undergo reversible phase transitions with large entropy changes, high sensitivity to hydrostatic pressure, and minimal hysteresis, the combination of which has been challenging to achieve in existing barocaloric materials. Here, we report a new mechanism for achieving colossal barocaloric effects near ambient temperature that exploits the large volume and conformational entropy changes of hydrocarbon chain-melting transitions within two-dimensional metal–halide perovskites. Significantly, we show how the confined nature of these order–disorder phase transitions and the synthetic tunability of layered perovskites can be leveraged to reduce phase transition hysteresis through careful control over the inorganic–organic interface. The combination of ultralow hysteresis (< 1.5 K) and high barocaloric coefficients (> 20 K/kbar) leads to large reversible isothermal entropy changes (> 200 J/kg•K) at record-low pressures (< 300 bar). We anticipate that these results will help facilitate the development of barocaloric cooling technologies and further inspire new materials and mechanisms for efficient solid-state cooling.

scholarly journals Different Benzendicarboxylate-Directed Structural Variations and Properties of Four New Porous Cd(II)-Pyridyl-Triazole Coordination Polymers

2020 ◽  
Vol 8 ◽  
Author(s):  
Ying Zhao ◽  
Jin Jing ◽  
Ning Yan ◽  
Min-Le Han ◽  
Guo-Ping Yang ◽  
...  
Keyword(s):  
Solid State ◽  
Coordination Polymers ◽  
Three Dimensional ◽  
Two Dimensional ◽  
Gas Sorption ◽  
Structural Variations ◽  
Benzenedicarboxylic Acid ◽  
Topological Framework ◽  
The Stability

Four new different porous crystalline Cd(II)-based coordination polymers (CPs), i. e., [Cd(mdpt)2]·2H2O (1), [Cd2(mdpt)2(m-bdc)(H2O)2] (2), [Cd(Hmdpt)(p-bdc)]·2H2O (3), and [Cd3(mdpt)2(bpdc)2]·2.5NMP (4), were obtained successfully by the assembly of Cd(II) ions and bitopic 3-(3-methyl-2-pyridyl)-5-(4-pyridyl)-1,2,4-triazole (Hmdpt) in the presence of various benzendicarboxylate ligands, i.e., 1,3/1,4-benzenedicarboxylic acid (m-H2bdc, p-H2bdc) and biphenyl-4,4′-bicarboxylate (H2bpdc). Herein, complex 1 is a porous 2-fold interpenetrated four-connected 3D NbO topological framework based on the mdpt− ligand; 2 reveals a two-dimensional (2D) hcb network. Interestingly, 3 presents a three-dimensional (3D) rare interpenetrated double-insertion supramolecular net via 2D ···ABAB··· layers and can be viewed as an fsh topological net, while complex 4 displays a 3D sqc117 framework. Then, the different gas sorption performances were carried out carefully for complexes 1 and 4, the results of which showed 4 has preferable sorption than that of 1 and can be the potential CO2 storage and separation material. Furthermore, the stability and luminescence of four complexes were performed carefully in the solid state.

A new two-dimensional managnese(II) coordination polymer constructed by 2,2′-(1,2-phenylene)bis(1H-imidazole-4,5-dicarboxylate)

2018 ◽  
Vol 74 (5) ◽  
pp. 599-603 ◽  
Author(s):  
Yan-Ju Liu ◽  
Di Cheng ◽  
Ya-Xue Li ◽  
Xiang-Ru Meng ◽  
Huai-Xia Yang
Keyword(s):  
Solid State ◽  
Coordination Polymer ◽  
Three Dimensional ◽  
Dimensional Structure ◽  
Coordination Geometry ◽  
Two Dimensional ◽  
Carboxylate Ligands ◽  
Rich Variety ◽  
Distorted Octahedral ◽  
Solvothermal Conditions

In recent years, N-heterocyclic carboxylate ligands have attracted much interest in the preparation of new coordination polymers since they contain N-atom donors, as well as O-atom donors, and have a rich variety of coordination modes which can lead to polymers with intriguing structures and interesting properties. A new two-dimensional coordination polymer, namely poly[[μ3-2,2′-(1,2-phenylene)bis(4-carboxy-1H-imidazole-5-carboxylato)-κ6 O 4,N 3,N 3′,O 4′:O 5:O 5′]manganese(II)], [Mn(C16H8N4O8)] n or [Mn(H4Phbidc)] n , has been synthesized by the reaction of Mn(OAc)2·4H2O (OAc is acetate) with 2,2′-(1,2-phenylene)bis(1H-imidazole-4,5-dicarboxylic acid) (H6Phbidc) under solvothermal conditions. In the polymer, each MnII ion is six-coordinated by two N atoms from one H4Phbidc2− ligand and by four O atoms from three H4Phbidc2− ligands, forming a significantly distorted octahedral MnN2O4 coordination geometry. The MnII ions are linked by hexadentate H4Phbidc2− ligands, leading to a two-dimensional structure parallel to the ac plane. In the crystal, adjacent layers are further connected by N—H...O hydrogen bonds, forming a three-dimensional structure in the solid state.

Two new CdII MOFs of 1,4-bis(1H-benzimidazol-1-yl)butane and flexible dicarboxylate ligands: luminescence sensing towards Fe3+

2020 ◽  
Vol 76 (11) ◽  
pp. 1024-1033
Author(s):  
Fang-Hua Zhao ◽  
Shi-Yao Li ◽  
Wen-Yu Guo ◽  
Zi-Hao Zhao ◽  
Xiao-Wen Guo ◽  
...  
Keyword(s):  
Aqueous Solution ◽  
Solid State ◽  
Hydrogen Bonds ◽  
Layer Structure ◽  
Three Dimensional ◽  
Supramolecular Network ◽  
Two Dimensional ◽  
X Ray Diffraction ◽  
X Ray ◽  
Vis Spectroscopy

Two new CdII MOFs, namely, two-dimensional (2D) poly[[[μ2-1,4-bis(1H-benzimidazol-1-yl)butane](μ2-heptanedioato)cadmium(II)] tetrahydrate], {[Cd(C7H10O4)(C18H18N4)]·4H2O} n or {[Cd(Pim)(bbimb)]·4H2O} n (1), and 2D poly[diaqua[μ2-1,4-bis(1H-benzimidazol-1-yl)butane](μ4-decanedioato)(μ2-decanedioato)dicadmium(II)], [Cd2(C10H16O4)2(C18H18N4)(H2O)2] n or [Cd(Seb)(bbimb)0.5(H2O)] n (2), have been synthesized hydrothermally based on the 1,4-bis(1H-benzimidazol-1-yl)butane (bbimb) and pimelate (Pim2−, heptanedioate) or sebacate (Seb2−, decanedioate) ligands. Both MOFs were structurally characterized by single-crystal X-ray diffraction. In 1, the CdII centres are connected by bbimb and Pim2− ligands to generate a 2D sql layer structure with an octameric (H2O)8 water cluster. The 2D layers are further connected by O—H...O hydrogen bonds, resulting in a three-dimensional (3D) supramolecular structure. In 2, the CdII centres are coordinated by Seb2− ligands to form binuclear Cd2 units which are linked by bbimb and Seb2− ligands into a 2D hxl layer. The 2D layers are further connected by O—H...O hydrogen bonds, leading to an 8-connected 3D hex supramolecular network. IR and UV–Vis spectroscopy, thermogravimetric analysis and solid-state photoluminescence analysis were carried out on both MOFs. Luminescence sensing experiments reveal that both MOFs have good selective sensing towards Fe3+ in aqueous solution.

Exploring the Ruddlesden−Popper Layered Organic-Inorganic Hybrid Semiconducting Perovskite for Visible-Blind Ultraviolet Photodetection

CrystEngComm ◽  
2021 ◽  
Author(s):  
Yuyin Wang ◽  
Bin Su ◽  
Guoming Lin ◽  
Huiru Lou ◽  
Shouxin Wang ◽  
...  
Keyword(s):  
Physical Properties ◽  
Three Dimensional ◽  
Metal Halide ◽  
Two Dimensional ◽  
Inorganic Hybrid ◽  
Perovskite Materials ◽  
Halide Perovskites ◽  
P Type ◽  
Visible Blind

Compared to the three-dimensional (3D) perovskite materials, the Ruddlesden−Popper (R-P) type two-dimensional (2D) organic-inorganic metal halide perovskites have indicated specific unique physical properties that include moisture-stable behaviours, exciton effects, and...

[1-(Pyrazin-2-yl)ethylidene]hydrazine: a new multitopic ligand for the design of hybrid molecular frameworks

2018 ◽  
Vol 74 (4) ◽  
pp. 424-427
Author(s):  
Muhammad Arif Kassim ◽  
Ubaidullah H. M. Yassin ◽  
Ai Ling Tan ◽  
Anwar Usman ◽  
Malai Haniti S. A. Hamid
Keyword(s):  
Double Bond ◽  
Solid State ◽  
Supramolecular Chemistry ◽  
Title Compound ◽  
Antimicrobial Agents ◽  
Crystal Packing ◽  
Three Dimensional ◽  
Two Dimensional ◽  
Compound C ◽  
Dimensional Network

Hydrazones and their derivatives are closely related to imine compounds and are potential antimicrobial agents. They have also found application in supramolecular chemistry as multitopic ligands to link multiple metal centres for the design of hybrid molecular frameworks. The molecule of the title compound, C6H8N4, consists of an imine linkage with an N—N bond length of 1.3540 (14) Å. This asymmetric compound is nearly planar and adopts an E configuration about the azomethine C=N double bond. In the solid state, there are two intermolecular N—H...N interactions that interconnect the molecules into a two-dimensional network. The three-dimensional arrangement of the crystal packing is further stabilized by intermolecular π–π interactions interconnecting the centroids of the heterocyclic rings.

Synthesis and characterization of a cadmium(II)–organic supramolecular coordination compound based on the multifunctional 2-amino-5-sulfobenzoic acid ligand

2016 ◽  
Vol 72 (12) ◽  
pp. 939-946 ◽  
Author(s):  
Gan-Yin Yuan ◽  
Lei Zhang ◽  
Meng-Jie Wang ◽  
Kou-Lin Zhang
Keyword(s):  
Hydrogen Bonding ◽  
Solid State ◽  
Coordination Compound ◽  
Coordination Compounds ◽  
Structural Characteristics ◽  
Three Dimensional ◽  
Distorted Octahedral Geometry ◽  
Two Dimensional ◽  
Ambient Conditions ◽  
Supramolecular Coordination

Much attention has been paid by chemists to the construction of supramolecular coordination compounds based on the multifunctional ligand 5-sulfosalicylic acid (H3SSA) due to the structural and biological interest of these compounds. However, no coordination compounds have been reported for the multifunctional amino-substituted sulfobenzoate ligand 2-amino-5-sulfobenzoic acid (H2asba). We expected that H2asba could be a suitable building block for the assembly of supramolecular networks due to its interesting structural characteristics. The reaction of cadmium(II) nitrate with H2asba in the presence of the auxiliary flexible dipyridylamide ligandN,N′-bis[(pyridin-4-yl)methyl]oxamide (4bpme) under ambient conditions formed a new mixed-ligand coordination compound, namely bis(3-amino-4-carboxybenzenesulfonato-κO1)diaquabis{N,N′-bis[(pyridin-4-yl)methyl]oxamide-κN}cadmium(II)–N,N′-bis[(pyridin-4-yl)methyl]oxamide–water (1/1/4), [Cd(C7H6NO5S)2(C14H14N4O2)2(H2O)2]·C14H14N4O2·4H2O, (1), which was characterized by single-crystal and powder X-ray diffraction analysis (PXRD), FT–IR spectroscopy, thermogravimetric analysis (TG), and UV–Vis and photoluminescence spectroscopic analyses in the solid state. The central CdIIatom in (1) occupies a special position on a centre of inversion and exhibits a slightly distorted octahedral geometry, being coordinated by two N atoms from two monodentate 4bpme ligands, four O atoms from two monodentate 4-amino-3-carboxybenzenesulfonate (Hasba−) ligands and two coordinated water molecules. Interestingly, complex (1) further extends into a threefold polycatenated 0D→2D (0D is zero-dimensional and 2D is two-dimensional) interpenetrated supramolecular two-dimensional (4,4) layer through intermolecular hydrogen bonding. The interlayer hydrogen bonding further links adjacent threefold polycatenated two-dimensional layers into a three-dimensional network. The optical properties of complex (1) indicate that it may be used as a potential indirect band gap semiconductor material. Complex (1) exhibits an irreversible dehydration–rehydration behaviour. The fluorescence properties have also been investigated in the solid state at room temperature.

Three isomorphous two-dimensional coordination polymers generated from a benzimidazole bridging ligand and ZnX2(X= Cl, Br and I)

2013 ◽  
Vol 69 (4) ◽  
pp. 367-371
Author(s):  
Yue-Feng Zhang ◽  
Jian-Ping Ma ◽  
Qi-Kui Liu ◽  
Yu-Bin Dong
Keyword(s):  
Solid State ◽  
Benzoic Acid ◽  
Coordination Polymers ◽  
Room Temperature ◽  
Three Dimensional ◽  
Luminescent Properties ◽  
Red Shift ◽  
Two Dimensional ◽  
Π Interactions ◽  
Bridging Ligand

A novel bridging asymmetric benzimidazole ligand, 4-{2-[3-(pyridin-4-yl)phenyl]-1H-benzimidazol-1-ylmethyl}benzoic acid, was used to construct three isomorphous two-dimensional coordination polymers, namelycatena-poly[chlorido(μ3-4-{2-[3-(pyridin-4-yl)phenyl]-1H-benzimidazol-1-ylmethyl}benzoato)zinc(II)], [Zn(C26H18N3O2)Cl]n, (I), and the bromide, (II), and iodide, (III), analogues. Neighbouring two-dimensional networks are stacked into three-dimensional frameworksviainterlayer π–π interactions. The luminescent properties of (I)–(III) were investigated and they display an obvious red-shift in the solid state at room temperature.

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