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Sulfur‐coordinated coordination polymers (S−CPs) have unique optoelectrical properties that originate from infinite M−S bond networks. In this study, we synthesized and characterized two polymorphs of a two–dimensional (2D) Pb(II) S−CP with a formula of [Pb(tzdt)(OAc)] (Htzdt=1,3‐thiazolidine‐2‐thione, OAc=acetate). Our findings revealed that the thermodynamic product (KGF‐26) possesses quasi‐2D (−Pb−S−)n layers with weak nonbonded Pb−S bonds, whereas the kinetic product (KGF‐27) has intrinsic 2D (−Pb−S−)n layers with Pb−S bonds. The results of time‐resolved microwave conductivity measurements and first–principles calculations confirmed that KGF‐27 exhibits higher photoconductivity than KGF‐26, which establishes that the inorganic (−Pb−S−)n networks with Pb−S bonds are crucial for achieving high photoconductivity. This is the first experimental demonstration of the impact of the (−M−S−)n networks in S−CPs on photoconductivity through the comparison of crystal polymorphisms. [ABSTRACT FROM AUTHOR]

This study presents a new dehydrogenative synthesis of alkenyl isothiocyanates, providing compounds with bromo and isothiocyanate groups. These reactive functionalities offer versatility for further transformations. Application in an amine sensor utilizing a coumarin-attached product demonstrates practical utility. This streamlined approach facilitates access to alkenyl isothiocyanates, valuable tools for biological studies. [ABSTRACT FROM AUTHOR]

Polyamines, such as putrescine and spermidine, are pivotal in various biological processes across living organisms. Despite their significance, structurally modified polyamines offer a less‐explored avenue for discovering bioactive compounds. The limitation is attributed to the synthetic difficulty of accessing functionalized polyamines. In this study, we accomplished photoredox‐catalyzed functionalization of polyamines to diversify their structure. The rapid functionalization allows attaching fluorophores to the target polyamine, facilitating the development of molecular probes for advancing chemical biology studies. [ABSTRACT FROM AUTHOR]

Coordination polymers containing a sulfur coordination atom (S-CPs) are an emerging class of materials with unique optoelectronic properties resulting from their inorganic metal–sulfur (–M–S–)n networks. Although the structural dimensionalities of (–M–S–)n networks govern the semiconductive properties of S-CPs, few systematic investigations have examined the impact of these dimensionalities on their semiconductive nature. In this study, we explored the relationship between the (–Pb–S–)n dimensionality and photoconductivity. We systematically synthesized Pb(II) S-CPs with the formula [Pb(x-SPhOMe)2] (x = ortho (KGF-32), meta (KGF-33), and para (KGF-34); HSPhOMe = methoxybenzenthiol). Single-crystal X-ray diffraction showed that KGF-32 and KGF-34 featured holodirected coordination spheres, but 1D (–Pb–S–)n chains with [PbO2S4] octahedra and 2D (–Pb–S–)n layers with [PbS6] octahedra, respectively. In contrast, KGF-33 features a 1D (–Pb–S–)n chain comprising a hemidirected [PbS5] coordination sphere. Notably, time-resolved microwave conductivity measurements and first-principles calculations revealed that the 2D-extended (–Pb–S–)n layer with the holodirected [PbS6] octahedron observed in KGF-34 served as a pathway for electron mobility. The findings of this study provide further design strategies for fabricating highly photoconductive Pb(II) S-CPs. [ABSTRACT FROM AUTHOR]

One-dimensional (1D) Cd(II) coordination polymers [Cd(x-SPhOMe)2]n (x = ortho, meta, and para; HSPhOMe = methoxybenzenethiol) containing inorganic 1D (–Cd–S–)n chains were synthesized. Among these, the KGF-31 polymer bearing para-SPhOMe featured a three-strand chain structure assembled via interchain S⋯S interactions and exhibited high photoconductivity and longevity. [ABSTRACT FROM AUTHOR]

The Pb–S‐based coordination polymer (CP), named KGF‐9, [Pb(tadt)]n (tadt = 1,3,4‐thiadiazole‐2,5‐dithiolate), can selectively convert CO2 into HCOO− (>99%) under visible light, with an apparent quantum yield (AQY) of 2.6% at 400 nm, without a cocatalyst. However, KGF‐9 is an intrinsically nonporous CP, and its small specific surface area (<1 m2 g−1) might hinder the realization of its full potential as a photocatalyst. Herein, facile synthetic routes at room temperature are reported through a solid‐state reaction and a liquid‐phase reaction (LPR) using lead(II) acetate as a precursor. The use of lead(II) acetate promotes the deprotonation of the H2tadt ligand, resulting in a faster coordination reaction, a reduced feature size, and a drastic increase in specific surface area (≈10 m2 g−1). A higher AQY for formate production (5.9% at 400 nm) is found for KGF‐9 prepared via a 60 min LPR. The improved photocatalytic activity of the LPR sample is attributed to the presence of long‐lived charge carriers, which is revealed by time‐resolved microwave conductivity measurements. The results of this study provide a simple but effective strategy toward increasing the activity of CP‐based photocatalysts. [ABSTRACT FROM AUTHOR]

Significant research has been conducted on molecular ferroelectric materials, including pure organic and inorganic compounds; however, studies on ferroelectric materials based on coordination metal complexes are scarce. Ferroelectric materials based on coordination metal complexes have tunable structures and designs, with coexistence or synergy between the ferroelectric behavior and magnetic properties. Compared to inorganic compounds, few coordination metal complexes exhibit coupling between the magnetic and dielectric properties. Coordination metal complexes with strong coupling between the magnetic and dielectric properties exhibit dielectric permittivity variations under external magnetic fields. Therefore, they have attracted substantial interest for their potential use in magnetoelectric devices. In this review, we discuss recent advances in coordination metal complexes, that exhibit coupled magnetic functionalities and ferroelectricity or dielectric properties, including single‐molecule magnets, electron delocalization systems, and external stimuli responsive compounds. [ABSTRACT FROM AUTHOR]

Two-dimensional Ag(I) coordination polymers containing a sulfur coordination atom, [Ag(tzdt)]n (KGF-24), and [Ag(tzdt)(TFA)]n (KGF-25) (Htzdt = 1,3-thiazolidine-2-thione, TFA = trifluoroacetate), were synthesized and characterized. Time-resolved microwave conductivity measurements and first-principles calculations revealed that KGF-24 and KGF-25 exhibit charge mobility along their (–Ag–S–)n network. [ABSTRACT FROM AUTHOR]

Ferroelectrics that display electrically invertible polarisation are attractive materials because of their potential for wide-ranging applications. To date, considerable effort has thus been devoted towards developing ferroelectric materials, particularly those comprising organic/inorganic compounds. In these systems, structural dynamics such as atomic displacement and reorientation of polar ions/molecules play a key role in the generation of reversible spontaneous polarisation. Although there are many reports concerned with organic/inorganic ferroelectrics, ferroelectrics based on coordination metal complexes have been largely unexplored despite their often unique electronic and spin state properties. In this feature article, we discuss recent progress involving coordination metal complex-based ferroelectrics where the reversible polarisation originates not only from structural dynamics (represented by proton transfer, molecular motion, and liquid crystalline behaviour) but also from electron dynamics (represented by electron transfer and spin crossover phenomena) occurring at the metal centre. Furthermore, unique synergy effects (i.e. magnetoelectric coupling) resulting from the structural and electron dynamics are described. We believe that this review pertaining to ferroelectric coordination metal complexes provides new insights for fabricating further advanced functional materials such as multiferroics and spintronics. [ABSTRACT FROM AUTHOR]

Hexaazatriphenylene (HAT) derivatives have attracted wide attention because of their electron‐deficient nature and unique self‐assembly properties. In this work, a facile synthesis method for obtaining HAT derivatives with alternating electron‐withdrawing nitrile and electron‐donating alkoxy groups (HATCNOCn) is proposed. Crystal structure analysis indicated that HATCNOCn forms a one‐dimensional columnar structure via strong π–π interactions. Density functional theory calculations revealed that the edge of HATCNOCn is divided into positively and negatively charged sites owing to the presence of alternating nitrile and alkoxy groups, which would induce strong π–π interactions. Thermal analysis and polarizing optical microscopy revealed that HATCNOCn exhibits columnar liquid‐crystal phases. Time‐resolved microwave conductivity measurements further demonstrated the photoconductive nature of HATCNOCn. The proposed strategy could provide a new strategy for the design of novel organic semiconductive materials. [ABSTRACT FROM AUTHOR]

Magnetoelectric (ME) materials exhibiting coupled electric and magnetic properties are of significant interest because of their potential use in memory storage devices, new sensors, or low‐consumption devices. Herein, we report a new category of ME material that shows liquid crystal (LC), ferroelectric (FE), and field‐induced single molecule magnet (SMM) behaviors. Co(II) complex incorporating alkyl chains of type [Co(3C16‐bzimpy)2](BF4)2 (1; 3C16‐bzimpy=2,2'‐(4‐hexadecyloxy‐2,6‐diyl)bis(1‐hexadecyl‐1H‐benzo[d]imidazole)) displayed a chiral smectic C mesophase in the temperature range 321 K–458 K, in which distinct FE behavior was observed, with a remnant polarization (88.3 nC cm−2). Complex 1 also exhibited field‐induced slow magnetic relaxation behavior that reflects the large magnetic anisotropy of the Co(II) center. Furthermore, the dielectric property of 1 was able to be tuned by an external magnetic field occurring from both spin‐lattice coupling and molecular orientational variation. Clearly, this multifunctional compound, combining LC, FE, and SMM properties, represents an entry to the development of a range of next‐generation ME materials. [ABSTRACT FROM AUTHOR]

Diet modification is an important intervention in the management of patients with dysphagia. Food entering the airway, same as oral bacterium, causes pulmonary inflammation; therefore, the elucidation of inflammatory responses to different foods is important. This study aimed to investigate the differences in the severity of inflammatory response induced by intratrachial injection of foods with different nutritional components. Two jelly products, the one containing only carbohydrates (KURIN jelly: Isocal Jelly KURIN®) and the other containing carbohydrates, proteins, and lipids (HC jelly: Isocal Jelly HC®), were prepared. These jelly products (dilution with saline, 50% volume/volume) and saline, as control, were intratracheally administered to Sprague–Dawley rats at a dose of 1 ml/kg (KURIN group (n = 15), HC group (n = 15), Saline group (n = 15)). At 1, 2 and 7 days after administration, lungs were harvested and histological analysis was performed. The severity of induced inflammation was evaluated using the Acute Lung Injury (ALI) score with hematoxylin–eosin staining, and the expression of IL-1β, IL-6 and TNF-α, markers of airway inflammation, were observed with immunostaining. The ALI score in the HC jelly group was significantly higher than the KURIN jelly group and the Saline group (P < 0.01) at 1 and 2 days after administration, while the ALI score in the KURIN jelly group was higher than Saline group only at 2 day after administration. Numerous positive cells for IL-1β, IL-6 and TNF-α were observed only in the HC jelly group at 1 and 2 days after administration. There were no significant histological differences between the three groups at 7 days after administration. Our data suggests that the severity of inflammation caused by aspiration differs depending on the ingredients of the foods, and the nutrients contained in foods might be considered in dietary management for the patients with dysphagia. [ABSTRACT FROM AUTHOR]

The article titled "Polymorphism of Two-Dimensional Semiconducting Coordination Polymers: Impact of a Lead-Sulfur Network on Photoconductivity" explores the different structures and properties of a 2D PbII coordination polymer with Pb-S bonds. The cover picture showcases two polymorphs of the polymer, with one being the thermodynamic product and the other being the kinetic product. The thermodynamic product consists of quasi-2D layers with weak, nonbonded Pb-S bonds, while the kinetic product contains intrinsic 2D layers with Pb-S bonds. The kinetic product exhibits higher photoconductivity due to the presence of the intrinsic 2D layers. The research article by D. Tanaka and co-workers provides more detailed information on this topic. [Extracted from the article]

Ferroelectric spin crossover (SCO) behavior is demonstrated to occur in the cobalt(II) complex, [Co(FPh‐terpy)2](BPh4)2⋅3ac (1⋅3 ac; FPh‐terpy=4′‐((3‐fluorophenyl)ethynyl)‐2,2′:6′,2′′‐terpyridine) and is dependent on the degree of 180° flip–flop motion of the ligand's polar fluorophenyl ring. Single crystal X‐ray structures at several temperatures confirmed the flip–flop motion of fluorobenzene ring and also gave evidence for the SCO behavior with the latter behavior also confirmed by magnetic susceptibility measurements. The molecular motion of the fluorobenzene ring was also revealed using solid‐state 19F NMR spectroscopy. Thus the SCO behavior is accompanied by the flip–flop motion of the fluorobenzene ring, leading to destabilization of the low spin cobalt(II) state; with the magnitude of rotation able to be controlled by an electric field. This first example of spin‐state conversion being dependent on the molecular motion of a ligand‐appended fluorobenzene ring in a SCO cobalt(II) compound provides new insight for the design of a new category of molecule‐based magnetoelectric materials. [ABSTRACT FROM AUTHOR]

Ferroelectric spin crossover (SCO) behavior is demonstrated to occur in the cobalt(II) complex, [Co(FPh‐terpy)2](BPh4)2⋅3ac (1⋅3 ac; FPh‐terpy=4′‐((3‐fluorophenyl)ethynyl)‐2,2′:6′,2′′‐terpyridine) and is dependent on the degree of 180° flip–flop motion of the ligand's polar fluorophenyl ring. Single crystal X‐ray structures at several temperatures confirmed the flip–flop motion of fluorobenzene ring and also gave evidence for the SCO behavior with the latter behavior also confirmed by magnetic susceptibility measurements. The molecular motion of the fluorobenzene ring was also revealed using solid‐state 19F NMR spectroscopy. Thus the SCO behavior is accompanied by the flip–flop motion of the fluorobenzene ring, leading to destabilization of the low spin cobalt(II) state; with the magnitude of rotation able to be controlled by an electric field. This first example of spin‐state conversion being dependent on the molecular motion of a ligand‐appended fluorobenzene ring in a SCO cobalt(II) compound provides new insight for the design of a new category of molecule‐based magnetoelectric materials. [ABSTRACT FROM AUTHOR]

Soft materials represented by polymers, liquid crystals, and colloids are a class of materials that exhibit a variety of unique functionalities which derive from their non-rigid structures. In particular, soft metal complexes incorporating flexible long alkyl chains in their structures have been shown to display synergy between the structural dynamics of the long alkyl chain moieties and the electron dynamics occurring at the metal centre. This review presents a discussion of such soft metal complexes with a focus on spin crossover (SCO) behaviours that are associated with a structural phase transition, including a liquid crystal (LC) transition, arising from the flexible natures of the respective complexes. We also discuss how to fabricate soft materials based on SCO complexes. [ABSTRACT FROM AUTHOR]

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The synthesis of [M(dimphen)(NCS)2] (1; M = FeII), (2; M = CoII), (3; M = MnII) and [Fe(dimphen)(NCSe)2] (4), where dimphen = [1,2-bis(9-methyl-1,10-phenanthrolin-2-yl)ethane], are reported. The crystal packing structures of 1–3, show intermolecular π–π stacking and NCS⋯SCN interactions. The complex 1 shows ferromagnetic interaction, and the complex 2 displays single-molecular magnet behaviour. [ABSTRACT FROM AUTHOR]

Vapor-induced crystal to crystal transformation between non-polar [Fe(sap)(acac)(sol)] (H2sap = 2-salicylideneaminophenol, acac = acethylacetate, sol = MeOH, pyridine) and polar [Fe(sap)(acac)(DMSO)] was demonstrated. It provides an example of switchable ferroelectric behaviour attributted to the structural phase transition triggered by solvent vapour. [ABSTRACT FROM AUTHOR]

A hexagonal cobalt(II) metallacycle and its "lipid packaged" derivatives, [Co6(R-bisterpy)6]X12 (R = H, OC16H33, OC27H55; X = BF4, C12-Glu), have been synthesized and characterized. The compounds incorporating BF4− anions formed sphere-like aggregates while the compounds with C12-Glu lipid anions gave double-layered honeycomb architectures composed of hexagonal stacked tubular structures, which exhibit spin crossover behaviour. [ABSTRACT FROM AUTHOR]

The article titled "Functionalized Polyamine Synthesis with Photoredox Catalysis" discusses the challenges in accessing modified polyamines and their potential for discovering bioactive compounds. The cover image illustrates the use of catalysts irradiated by light to facilitate the rapid functionalization of target polyamines, allowing for the attachment of various substituents. This process can lead to the development of novel bioactive molecules and molecular probes for chemical biology studies. The research article by K. Murakami and co-workers provides more detailed information on this topic. [Extracted from the article]

Lipid packaged iron(II) complex of [Fe(C5C10C12-trz)3](C12-Glu)2 (1) [C5C10C12-trz = 4′,5‴-decyl-1‴-(heptadecyloxy)-1,2,4-triazole, C12-Glu = 4-(1,3-bis-dodecyloxycarbonyl-propylcarbamoyl)-benzenesulfonic acid] have been successfully synthesized and characterized using TEM, DSC, PXRD and magnetic susceptibility. It was observed that lipid packaged compound displayed liquid crystalline phase at room temperature. Furthermore, lipid packaged compound exhibited spin crossover phenomena accompanying the phase transition from liquid crystalline to liquid crystalline. [ABSTRACT FROM AUTHOR]

Zinc(ii) and platinum(ii) complexes [M(X-4-C18-salmmen)] (M = Zn (1) and Pt (2), X = R, S (optical isomer) and rac (racemate), salmmen = N,N′-monomethylenebis-salicylideneimine) were synthesized and investigated. The series of compounds represented by 1 (R, S and rac forms) display liquid crystalline state behaviour at 413 K, and exhibit both ferroelectric and fluorescence properties, while the compounds represented by 2 (R and S, and rac forms) do not display liquid crystal behaviour but do exhibit ferroelectric and fluorescence properties. The ferroelectric behaviour was confirmed by second harmonic generation (SHG) experiments. It is considered that the motion and fluctuation of the long alkyl chains in these complexes results in the observed ferroelectric properties. [ABSTRACT FROM AUTHOR]

A dinuclear helical iron(ii) complex of a new ditopic thiazolylimine ligand (L) has been synthesised via supramolecular assembly. The resulting dinuclear helical cylinder [Fe2L3]·4BF4 was investigated by variable temperature X-ray crystallography, ESI high resolution mass spectrometry, CHN analysis, FT-IR and UV-Vis spectroscopy. The nature of the spin transition was investigated by magnetic susceptibility measurements, and confirmed by VT-SCXRD and X-ray photoelectron spectroscopy. [Fe2L3]·4BF4 displays a complete spin transition with a gradual-abrupt character at T1/2 = 348 K and represents a new example of a dinuclear iron(ii) complex exhibiting a spin transition at high temperature. Both VT-SCXRD and XPS measurements show excellent correlation with the magnetic susceptibility experiments, demonstrating the power of XPS not just to confirm, but also to clearly follow the spin-state transition in Fe(ii) SCO complexes. [ABSTRACT FROM AUTHOR]

The coordination metal complexes can exhibit flexibility in their electronic/magnetic state based on the combination of metal ions and the design of organic coordination ligands. Keywords: coordination complexes; dielectric properties; electronic polarization; ferroelectric materials; magnetic properties EN coordination complexes dielectric properties electronic polarization ferroelectric materials magnetic properties 1 1 1 06/28/23 20230601 NES 230601 B The cover feature image illustrates b the conceptual design of synergetic or coexistence of magnetic and dielectric functionalities in the coordination metal complexes. [Extracted from the article]

Self-assembled hybrid supramolecular architectures formed between amphiphilic anions and long alkylated cationic cobalt(ii) complexes of type [Co(Cn-terpy)2](C12-Glu)2 (n = 15–20) have been synthesized and characterized by TEM, PXRD and magnetic susceptibility measurements. The hybrids display wire or rolled sheet supramolecular arrangements with odd and even alkyl chain dependence, with the cobalt(ii) centres exhibiting gradual spin-crossover behaviours. [ABSTRACT FROM AUTHOR]