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This paper investigates the synthesis, crystal structure, thermal properties, and energetic performance of two 1D coordination polymers (CPs). The CPs, namely, [Zn(atrz)(DNBA)2(H2O)2]n (1) and [Cd(atrz)(DNBA)2(H2O)2]n (2), were designed and synthesized based on the nitrogen-rich ligand 4,4′-azobis-1,2,4-triazole (atrz) and 3,5-dinitrobenzoic acid (HDNBA) via a mixed ligand strategy using a simple and environment-friendly method. The CPs were characterized by various spectroscopic and analytical techniques along with single-crystal X-ray diffraction (SCXRD). SCXRD analysis reveals a distorted octahedral geometry around the metal ions (Zn/Cd), leading to the formation of a 1D coordination polymer while constructing a 2D structural framework through intermolecular hydrogen bonding. Both the CPs exhibit similar thermal stability but considerably differ in their heat of formation values (1 = −894.43, 2 = 1635.93 kJ mol−1). CP 2 has higher detonation velocity (7.24 km s−1) and pressure (23.67 GPa) compared to 1 (detonation velocity: 6.28 km s−1, detonation pressure: 17.57 GPa) owing to its higher heat of formation and density. Both the CPs exhibit ideal insensitivity to friction and impact stimuli, ensuring their safety during transportation and processing. The value of average activation energy obtained from isoconversion ASTM E698 for 1 and 2 was reported to be 143.8 and 168.0 kJ mol−1, respectively. This study explores the development of energetic CPs through the mixed ligand strategy based on the atrz ligand and incorporating HDNBA as the co-ligand to reduce the sensitivity while maintaining the comparable energetic performance of previously reported atrz-based complexes. This paper also highlights the potential use of CPs as explosives by demonstrating higher energetic performance. [ABSTRACT FROM AUTHOR]

The document is a contents list for the journal CrystEngComm, which focuses on the design and understanding of solid-state and crystalline materials. The list includes various papers on topics such as molecular packing characteristics, crystal structures, photocatalytic activity, crystal growth, and more. The journal is published by The Royal Society of Chemistry, a leading chemistry community. The document also mentions approved training courses offered by the society. [Extracted from the article]

The document is a contents list for the journal CrystEngComm, which focuses on the design and understanding of solid-state and crystalline materials. It includes a list of papers featured in the issue, covering topics such as photocatalytic hydrogen generation, thermal performance of glass coatings, and Zn ion storage performance. The journal is published by The Royal Society of Chemistry, a leading chemistry community. The document also mentions approved training courses offered by the society. [Extracted from the article]

The document is a contents list for the journal CrystEngComm. It highlights various papers and communications published in the journal, including topics such as hydrogen storage, coordination polymers, luminescent sensors, and chemical solution deposition. The cover image features the Tembleque Aqueduct World Heritage Site in Mexico. The journal is published by the Royal Society of Chemistry, a leading chemistry community that connects the world with the chemical sciences. [Extracted from the article]

The document is a contents list for the journal CrystEngComm, which focuses on the design and understanding of solid-state and crystalline materials. The list includes various papers on topics such as hybrid materials, growth of single-crystalline particles, high-pressure phase transitions, coordination polymers, and optical properties of crystals. The journal is published by The Royal Society of Chemistry, a leading chemistry community. The document also mentions professional recognition and development opportunities for scientists. [Extracted from the article]

The document is a contents list for the journal CrystEngComm, which focuses on the design and understanding of solid-state and crystalline materials. It includes a variety of papers on topics such as cocrystals, crystal structures, stimuli-responsive properties, and piezoelectric properties. The journal is published by The Royal Society of Chemistry, a leading chemistry community. The document also mentions approved training courses offered by the society. [Extracted from the article]

The document is a contents list for the journal CrystEngComm, which focuses on the design and understanding of solid-state and crystalline materials. The contents list includes various papers on topics such as acoustic shockwave-induced morphological transformation, copper-organic frameworks, and the assembly of poly(3-hydroxybutyrate). The journal is published by The Royal Society of Chemistry, a leading chemistry community. The document also mentions other journals in the field of environmental science. [Extracted from the article]

Four novel coordination polymers, {Na2[Co3(H2TTHA)2(H2O)12](H2O)2}·4(H2O) (1), {Na[Cu4(H2TTHA)(HTTHA)(H2O)8](H2O)3}·5(H2O) (2), [Cd3(TTHA)(H2O)4] (3) and [Ca5(HTTHA)2(H2O)8] (4), (H6TTHA = 1,3,5-triazine-2,4,6-triamine hexaacetic acid) have been synthesized by self-assembly of the flexible hexapodal acid H6TTHA and corresponding metal salts. The four complexes exhibit novel frameworks with different topologies due to diverse coordination modes and different conformations of the flexible H6TTHA. Complex 1shows a 3D network with (4,4,6)-connected topology constructed from parallel one-dimensional hybrid ribbons with nearly planar 24-membered rings, in which all Co(ii) atoms are located in one plane. Complex 2features a 3D (3,4,4,4,7)-connected network bridged by sodium ions from 2D layer structures which are formed through the interconnection of the tetranucleate units and the flexible ligands. Complex 3possesses hybrid layers constructed from zigzag Cd–O chains. These layers are further linked by the TTHA6−ligands with two configurations, leading to another 3D (3,3,8)-connected framework. The metal ions in complex 4are connected into wall-like infinite metal chains which are bridged by the carboxylate groups of ligands into a 3D (3,3)-connected hybrid framework. The framework is further furnished with the ligands forming hydrophobic channels with approximate sizes 3.5 Å × 9 Å based on the distances of the opposite atoms. The enantiometric pairs of ligands are formed in spite of no asymmetric carbon atom in complexes 1–3. Variable temperature magnetic studies down to 2 K reveal antiferromagnetic interactions in complexes 1and 2. Complexes 3and 4are both highly emissive at room temperature. And the luminescent intensities are largely enhanced once they are frozen to 10 K. [ABSTRACT FROM AUTHOR]

In this paper, a series of coordination polymers, {[Zn(adb)(L1)2]·solvent}n (L1 = solvent = N,N-dimethylacetamide, Hui-3-DMA; L1 = N,N-dimethylformamide and no solvent, Hui-3-DMF; L1 = N,N-diethylformamide and no solvent, Hui-3-DEF) have been synthesized by hydrothermal reactions of Zn(NO3)3·6H2O and 4,4′-(anthracene-9,10-diyl)dibenzoic acid (H2adb). These compounds show similar one-dimensional (1D) zig-zag chain structures, which are limited by the end-coordination of the solvent molecules. Interestingly, these compounds all show blue-emission properties, which could be easily modulated by using different solvents. Among them, Hui-3-DMA presents an excellent quantum yield performance, as high as to 54.1%, which is very promising for blue-emission materials. Moreover, various-temperature fluorescence studies reveal good linear or exponential decline trends for their emission intensity as temperature increases, demonstrating the potential of these compounds as fluorescent thermometers. [ABSTRACT FROM AUTHOR]

CrystEngCommrsc. li/ crystengcomm ISSN 1466- 8033 Volume 26 Number 18 14 May 2024 Pages 2335– 2442 PAPER Juan Olguín et al. Nitro group and K+- based secondary building units for the self- assembly of 3D coordination polymers built on dinuclear dianionic helicate connectors Environmental Science: Atmospheres Connecting communities and inspiring new ideas rsc. li/ submittoEA Fundamental questions Elemental answers GOLD OPEN ACCESS Registered charity number: 207890 [Extracted from the article]

Optically-active luminescent materials based on lanthanoid ions attract significant attention due to their unique spectroscopic properties and the possibility of application as chemical sensors. Five isostructural lanthanoid metal organic frameworks, namely {[Pr(3,4-PDA)(Glu)0.5(H2O)2]CH3CN}(1) and [Ln(3,4-PDA)(Glu)0.5(H2O)2]: Ln = Nd (2), Sm (3), Eu (4), and Tb (5) (where 3,4-PDA = pyridine-3,4-dicarboxylic acid, Glu = glutaric acid), synthesized via the solvothermal method are reported. These lanthanoid metal–organic frameworks were characterized by FTIR, single-crystal X-ray diffraction, powder X-ray diffraction, BET, Hirshfeld surface analysis, DFT calculations, electronic spectroscopy, and photoluminescence techniques. MOFs 1–5 show porous two-dimensional (2D) structures. The luminescence properties of MOFs 4 and 5 demonstrated the range of sensing capabilities for some toxic heavy metals. However, MOFs 4 and 5 are highly sensitive for the detection of Pb2+, exhibiting the most effective luminescence quenching with the lowest detectable change in the signal occurring at ∼0.014 and ∼0.013 ppm of Pb2+ with MOFs 4 and 5, respectively, at room temperature in minutes. The MOF-based luminescence sensors designed in this paper demonstrate a successful and feasible strategy to use pyridine-3,4-dicarboxylic acid-based ligand as an antenna, which can efficiently sensitize Eu3+ and Tb3+ emission. MOFs 4 and 5 show great potential in the application of environmental detection of Pb2+ in water. [ABSTRACT FROM AUTHOR]

In this paper, we showed an example of acid-directed hydrothermal synthesis of three Cd-based metal–organic frameworks (MOFs) under similar conditions, namely, [Cd(TIDB)(AA)0.5(NO3)]n (1), [Cd3(TIDB)2(AA)2(H2O)2(HCOO)2]n (2), and {[Cd4(TIDB)(AA)4(H2O)5](C2H5OH)2(H2O)2}n (3) (TIDB = 1,3,5-tri(1H-imidazol-1-yl)benzene, H2AA = anthracene-9,10-dicarboxylic acid). Compound 1 was synthesized by the introduction of HNO3 as a structure-directing agent. It has 2D coordination networks with the 3,4-c bey topology. The porous 3D supramolecular framework in compound 1 is stabilized by H-bonds. Compound 2 was formed with the use of a HCOOH agent. It has a 3D coordination network with a new 3,4,5-c underlying net topology, and it is also porous. Compound 3 was obtained using a CH3COOH agent. It has a disordered non-porous 3D coordination network. Because 3 was hard to purify, 1 and 2 were chosen for further property investigation. On the one hand, fluorescence studies showed that 1 and 2 are both blue-emitting MOFs with quantum yields of 2.3% and 0.8%, respectively. On the other hand, CO2 cycloaddition performance was also tested, which revealed that 2 has a superior catalytic conversion of epoxybutane at 60 °C and 1 atm with a high yield of up to 95.6%. [ABSTRACT FROM AUTHOR]

In this paper, three new cobalt-based metal organic frameworks (MOFs) with different topologies, namely, {[Co(HL)(tib)(H2O)]·2H2O}n (1), [Co3(L)2(bibp)4(H2O)2]n (2) and [Co2(L)(bip)(μ3-OH)]n (3) (H3L = 3-(3,5-dicarboxylphenoxy)-6-carboxylpyridine, tib = 1,3,5-tirs(1-imidazolyl)benzene, bibp = 4,4′-bis(imidazolyl)biphenyl, bip = 3,5-bis(imidazoly-1-yl)toluene) synthesized by a hydrothermal method, were investigated. Different auxiliary ligands led to the diversity of the three MOFs in terms of structure and properties. Hereafter, the adsorption properties of the MOFs on different dyes were investigated; of interest is that the adsorption performance of MOF 3 on Congo red dye is particularly outstanding, including excellent performance in terms of removal rates, selectivity and recyclability. Its adsorption kinetics and adsorption isotherms were also investigated. Finally, its possible adsorption mechanism was analyzed by zeta potential measurements, infrared spectroscopy and N2 adsorption–desorption isotherms. It was hypothesized that the exquisite confined microenvironments consisting of electrostatic interactions, a suitable pore volume, and complicated van der Waals forces of hydrogen bonding and π–π stacking played a critical role during the adsorption process. It was shown that MOF 3 can be used as an effective adsorbent for the adsorption of Congo red dye in wastewater. [ABSTRACT FROM AUTHOR]

A systematic investigation of the system manganese(II) salt–H2SBA–auxiliary ligand–solvent successfully led to the isolation of six new multidimensional coordination polymers: [Mn5(2-pic)2(DMA)4(SBA)4]·4DMA (1), [Mn3(pyzc)2(DMF)(H2O)(SBA)2]·DMF·H2O (2), [Mn5(pyzc)2(DMA)4(SBA)4]·4DMA (3), [Mn5(mpyzc)2(DMA)4(SBA)4]·4DMA (4), [Mn2(phen)2(H2O)(SBA)2]·2DMA (5) and [Mn3(phen)2(SBA)3]·5DMF (6), where SBA = 4,4′-sulfonyldibenzoate 2-pic = 2-picolinate, pyzc = 2-pyrazinecarboxylate acid, mpyzc = 5-methyl-2-pyrazinecarboxylate and phen = 1,10-phenanthroline. The selected use of N-containing ligands to block the coordination sites of manganese enabled us to understand their influence in controlling the nuclearity and the dimensionality of the extended manganese carboxylate coordination networks. Single crystal X-ray crystallography established that the structures of all the solids were built of homometallic clusters varying from monomeric to pentameric manganese(II) carboxylate units. While the solids 1, 3 and 4 are isostructural, possessing a 2D coordination network containing pentanuclear SBUs of the composition {Mn5N2O3}, the 2D solids 2 and 5 are respectively built from binuclear {Mn2N4O7} and trinuclear {Mn3N2O14} SBUs. The solid 6 is the lone example of a 3D coordination network in this system. Dielectric measurements showed comparable dielectric behavior for the isostructural solids 1, 3 and 4 with ε′ ∼ 17 at room temperature. Relatively lower values observed for 2 and 5 (ε′ ∼ 14) were due to a combined effect of strong manganese carboxylate interaction and the presence of ordered polar guest molecules. Significantly higher values for 6 (∼21) could be attributed to disordered guest molecules. All the six solids exhibited antiferromagnetic behavior at lower temperatures. This paper also discusses the growth of the solids in terms of supramolecular aggregation of manganese carboxylate complex species with or without an auxiliary ligand, proposing a mechanistic pathway to trace the chemical events from molecules to the final solid. [ABSTRACT FROM AUTHOR]

This paper demonstrates the utility of joint applications of X-ray diffraction, solid state (ss) NMR, density functional theory (DFT) and molecular mechanics (MM) calculations for the determination of the stereochemistry of paramagnetic bis(aminoacidato)copper(II) compounds. Solution-based and mechanochemical syntheses of trans-bis(leucinato)copper(II) [Cu(Leu)2] with L - and DL -leucine using different solvents always resulted in the same two-dimensional coordination polymers of the LL (previously reported in the literature) and DL diastereomers. The X-ray crystal and molecular structure of trans-catena-[(μ- D -leucinato)(μ- L -leucinato)copper(II)] (space group C2) has symmetry unrelated D - and L -leucine side-chain conformations. An asymmetrical copper(II) DL -amino acid complex has not been observed so far in a non-centrosymmetric space group. Both LL and DL trans-[Cu(Leu)2] crystals have similar intermolecular bonding. The X-ray powder diffraction and magic-angle spinning (MAS) ssNMR information available from the polycrystalline bulk phase of the two compounds agree with their single-crystal results. Besides, the 2H MAS ssNMR spectrum of the polycrystalline sample synthesized using DL -leucine showed weak signals which were ascribed to a small amount of the LL (DD) stereoisomers. DFT calculations of the Fermi-contact contributions aided the 13C and 2H NMR spectral assignments. DFT conformational analyses of the LL and DL isomers revealed two Leu side-chain conformations as the energetically favorable ones in the gas phase and aqueous solution. These are exactly the conformations whose combinations occur in the observed crystal structures. Similar MM potential energies of LL and DL trans-[Cu(Leu)2] in the crystal lattices suggest that crystallization of DL over LL (DD) diastereomers should be attributed to kinetic rather than thermodynamic effects. [ABSTRACT FROM AUTHOR]

In this paper, three isostructural 1D lanthanide complexes, [Ln(dppc)(H2O)4]n·2nH2O (Ln = Eu, Tb and Eu0.501Tb0.499, named 1-Eu, 2-Tb and Eu0.501Tb0.499), based on 3-(2,4-dicarboxylate phenyl)-2-pyridinecarboxylic acid (H3dppc) have been synthesized and characterized by elemental analysis, IR, PXRD, TG and X-ray crystallography. The complexes exhibit a 1D chain structure, which is further linked into a 3D supramolecular framework by hydrogen bonds. Tuneable emission colour of Eu0.501Tb0.499 is realized by adjusting the excitation wavelength. The sensing properties of 1-Eu and 2-Tb towards Fe3+ and aniline indicate that the two complexes have almost the same superior sensitivity and low detection limit for Fe3+ in aqueous solution, while they have different detection abilities for aniline in DMF solvent. The different detection abilities were discussed by means of PXRD, UV-vis, luminescence lifetimes and molecular surface calculations (Hirshfeld surface analysis and 2D fingerprint plots). [ABSTRACT FROM AUTHOR]

Improving proton conductivity is of great importance for the further application of metal–organic frameworks (MOFs) or metal–organic coordination polymers (MOCPs) in proton exchange membrane fuel cells. In this paper, we proposed a new approach to increase proton conductivities in MOCPs coming from organic ligands, e.g. coordination inducement and MOCP–cocrystal composite formation strategies, which is based on the potential function of organic ligands. By employing the approach, we have successfully synthesized and characterized three crystalline compounds, PPA (1), [Cu(PPA)I] (2) and [Co(PPA)2(BDC)(H2O)2·(PPA)2(H2BDC)2(H2O)] (3) (PPA = 4-(3-pyridinyl)-2-amino pyrimidine, H2BDC = 1,4-benzenedicarboxylic acid). These compounds show high water stabilities and different proton conducting behaviours, especially compound 3 with a proton conductivity of 2.29 × 10−4 S cm−1 at 325 K and ∼97% RH, which is higher than or comparable to those of some reported compounds. More importantly, a persistent increase in proton conductivity is observed from 1 to 3, which is about one order of magnitude. Furthermore, single crystal analyses show that coordination and hydrogen-bonding interactions play a crucial role in improving proton-conductive properties for these compounds. The study reveals that it is practical to boost the proton conductivity of crystal materials by means of their intrinsic merits and the strategy of molecular design. [ABSTRACT FROM AUTHOR]

The present paper reports the structures and the third order nonlinear optical properties of four coordination polymers prepared by hydrothermal methods using nickel acetate or cobalt acetate, bisimidazolyl ligands and different aromatic carboxylic acids, namely [Co(H2O)2(1,2-BIB)2](Co(DBS)(1,2-BIB)]2·7H2O (1), [Ni(H2O)2(1,2-BIB)](CBA)·H2O (2), [Ni(1,2-BIB)(SDA)]·4H2O (3) and [Ni(H2O)(1,2-BIB)(HBTA)]·2H2O (4) (1,2-BIB = 1,2-bis((1H-imidazol-1-yl)methyl)benzene, H2DBS = sodium 3,5-dicarboxybenzenesulfonate, H2CBA = 2-(carboxymethyl)benzoic acid, H2SDA = 4,4′-sulfonyldibenzoic acid and H3BTA = benzene-1,3,5-tricarboxylic acid). Compound 1 has a one-dimensional structure, containing a polymeric cationic chain and a polymeric anionic chain. In compound 2, the Ni(II) ions are alternately linked by 1,2-BIB ligands and CBA ligands to form a joint-like chain structure. In compound 3, the metal ions are connected by 1,2-BIB to form a ladder-like structure, and SDA ligands are located on both sides of the chain. In compound 4, the Ni(II) ions are alternately connected by 1,2-BIB and BTA ligands to form a two-dimensional structure. We investigated the third-order nonlinearity of the compounds by a single-beam Z-scan technique. Interestingly, the compounds exhibit different third-order nonlinearities. Compound 1 has a saturable absorption (SA) and a self-defocusing effect with the nonlinear absorption coefficient β being -12.4 × 10-7 m W-1 and the nonlinear refractive index γ being -8.51 × 10-14 m² W-1. Compound 2 presents only a selfdefocusing effect with the nonlinear refractive index γ being -128.87 × 10-14 m² W-1, while compounds 3 and 4 show a reverse-saturation absorption (RSA) effect with the nonlinear absorption coefficient β being 4.42 × 10-7 and 2.97 × 10-7 m W-1, respectively. We calculated the band structure and the total (TDOS) and partial density of states (PDOS) of the four compounds. The calculated results are satisfactory for explaining the experimental results. This shows that intramolecular MLCTs or LMCTs have a significant impact on the third-order nonlinearity of the compounds. [ABSTRACT FROM AUTHOR]

We suggest in this paper that the combinative use of bent tritopic carboxylate, linear dipyridyl and adaptable Cu2+ ion leads to a higher probability of self-penetrated polymeric networks. This assertion is supported by four structures isolated herein, among which two are self-penetrated, highlighting the potential for controlled assembly of self-penetrating networks. [ABSTRACT FROM AUTHOR]

A series of one-dimensional (1-D) N-succinopyridine-based complexes: [Cu(L−)(H2O)2]Cl·2H2O (1), [Pr(L−)(H2O)4]Cl2 (2), [Ln(L−)(H2O)5]Cl2·3H2O (Ln = Eu (3), Gd (4)), and [Er(L−)(H2O)4]Cl2·H2O (5) (HL = N-succinopyridine (−OOC–CH(N+C5H5)–CH2–COOH)) have been prepared and characterized by single-crystal X-ray diffraction. The frameworks of complexes 1, 2 and 5 constructed from dinuclear metal building blocks exhibit 1-D double-strand loop-like chains; these chains are further connected to each other by hydrogen bonds forming a 3-D supramolecular architecture. Whereas complexes 3 and 4 feature hydrogen bonding 2-D supramolecular networks assembled from 1-D chains that are constructed from mononuclear metal building blocks. The effects of different metal ions, steric hindrance and coordination diversities of HL on the polymeric architectures have been discussed. In addition, thermogravimetric and magnetic properties of these complexes were also investigated in this paper. [ABSTRACT FROM AUTHOR]

A 1-D chain-like hybrid coordination polymer [(CuBr)2(bpy)]n(bpy = 2,2′-bipyridine) was first synthesized viaa hydrothermal reaction of copper(I) bromide with 2,2′-bipyridine (bpy). The most fascinating feature of [(CuBr)2(bpy)]nis the unusual six-member-(Cu3Br3)-ring motif. The skeleton of copper bromide combined with bpy in [(CuBr)2(bpy)]nhas not been reported. In addition, research on pyrolysis of [(CuBr)2(bpy)]nwas reported in this paper. Oriented growth of single crystalline Cu(111) flake, which is usually prepared through depositing onto the surface of high-quality metal films (substrates), was synthesized by simply pyrolyzing [(CuBr)2(bpy)]nby adjusting the heating procedures. No capping reagent was induced to simplify the system. Since most of the research of pyrolysis of coordination polymers focuses on the relationship between the structure of precursor and sinter, the results of this paper show how the reaction conditions affect the morphology of the product and give a simple method for the synthesis of a Cu(111) flake, which has wide application in industry. [ABSTRACT FROM AUTHOR]

A novel three-dimensional (3D) [Ag3(dmtrz)2(CN)]n(1) with a three-fold interpenetrated CdSO4-type net is in situsolvothermal synthesized, and influential factors in the in situreaction are briefly discussed. The luminescent property studies reveal that 1shows green phosphorescent emission upon excitation while other binary silver(i)-dmtrz compounds discussed in this paper only emit blue phosphorescence. [ABSTRACT FROM AUTHOR]

The inside front cover of the journal is presented along with information on an paper titled "Nickel adipate coordination polymers with isomeric dipyridylamide ligands: topological disorder and divergent magnetic properties" by Charmaine L. White and Robert L. LaDuca, published in this issue.