Diversity in Supramolecular Solid-State Architecture Formed by Self-Assembly of 1‑(Diaminomethylene)thiourea and Aliphatic Dicarboxylic Acids

A family of supramolecular complexes of 1-(diaminomethylene)­thiourea with aliphatic dicarboxylic acids, HOOC­(CH₂)_<i>n</i>COOH, with odd and even numbers of methylene groups in the carbon chain of the acids has been characterized. Using solvent-assisted and evaporation-based techniques, crystallization of 1-(diaminomethylene)­thiourea with aliphatic dicarboxylic acids from water solutions yielded ionic supramolecular complexes with base to acid ratio of 2:1 or 1:1. Malonic, succinic, adipic, and sebacic acids with 1-(diaminomethylene)­thiourea form supramolecular complexes of 2:1 ratio (<b>1</b>, <b>2</b>, <b>4</b>, and <b>8</b>), whereas glutaric, pimelic, azelaic, and suberic acids form supramolecular complexes of 1:1 ratio (<b>3</b>, <b>5</b>, <b>6</b>, and <b>7</b>). Within all supramolecular complexes only one with adipic acid crystallizes as a hydrate containing water molecules of crystallization. In the hydrated crystal with adipic acid, the O–H···O chains of water molecules interact with adipiate­(2-) anions forming anionic layers, and the charge is compensated by 1-(diaminomethylene)­thiouron-1-ium cations. The 2:1 supramolecular complexes further interact each other via N–H···O hydrogen bonds forming two- or three-dimensional supramolecular structure. Within 1:1 supramolecular complexes, the singly deprotonated aliphatic dicarboxylic acids are linked together via strong symmetrical O···H···O hydrogen bonds into infinitive chains. The chains are further linked by 1-(diaminomethylene)­thiouron-1-ium cations to form a two- or three-dimensional hydrogen bonding network. Interaction between the 1-(diaminomethylene)­thiouron-1-ium and the singly or doubly deprotonated aliphatic dicarboxylic acid units in solid of <b>1</b>–<b>8</b> supramolecular complexes were also analyzed by vibrational spectroscopy

Diversity in Supramolecular Solid-State Architecture Formed by Self-Assembly of 1‑(Diaminomethylene)thiourea and Aliphatic Dicarboxylic Acids

A family of supramolecular complexes of 1-(diaminomethylene)­thiourea with aliphatic dicarboxylic acids, HOOC­(CH₂)_<i>n</i>COOH, with odd and even numbers of methylene groups in the carbon chain of the acids has been characterized. Using solvent-assisted and evaporation-based techniques, crystallization of 1-(diaminomethylene)­thiourea with aliphatic dicarboxylic acids from water solutions yielded ionic supramolecular complexes with base to acid ratio of 2:1 or 1:1. Malonic, succinic, adipic, and sebacic acids with 1-(diaminomethylene)­thiourea form supramolecular complexes of 2:1 ratio (<b>1</b>, <b>2</b>, <b>4</b>, and <b>8</b>), whereas glutaric, pimelic, azelaic, and suberic acids form supramolecular complexes of 1:1 ratio (<b>3</b>, <b>5</b>, <b>6</b>, and <b>7</b>). Within all supramolecular complexes only one with adipic acid crystallizes as a hydrate containing water molecules of crystallization. In the hydrated crystal with adipic acid, the O–H···O chains of water molecules interact with adipiate­(2-) anions forming anionic layers, and the charge is compensated by 1-(diaminomethylene)­thiouron-1-ium cations. The 2:1 supramolecular complexes further interact each other via N–H···O hydrogen bonds forming two- or three-dimensional supramolecular structure. Within 1:1 supramolecular complexes, the singly deprotonated aliphatic dicarboxylic acids are linked together via strong symmetrical O···H···O hydrogen bonds into infinitive chains. The chains are further linked by 1-(diaminomethylene)­thiouron-1-ium cations to form a two- or three-dimensional hydrogen bonding network. Interaction between the 1-(diaminomethylene)­thiouron-1-ium and the singly or doubly deprotonated aliphatic dicarboxylic acid units in solid of <b>1</b>–<b>8</b> supramolecular complexes were also analyzed by vibrational spectroscopy

Synthesis and characterization a new polyoxomolybdate C₃₄H₁₁₄Fe₂Mo₁₂N₁₈Na₂O₆₆ and study of its catalytic activity in the production of 1,2,3-triazoles

A new polyoxomolybdate, [(C6H12N4-CH3)2Na2(H2O)8](C6H12N4-CH3)2[(H0.5)N(CH2O)3FeMo6O18.5(OH)2.5]2·10H2O (1), was synthesized. The structure of the synthesized polyoxomolybdate was investigated by single-crystal X-ray diffraction analysis and several other identification techniques such as FTIR and EDX analysis. Each unit cell of 1 contains one cation [(C6H12N4-CH3)2Na2(H2O)8]4+ and two hexamethylenetetramine cations (C6H12N4-CH3)+, and two polyanions [(H0.5)N(CH2O)3FeMo6O18.5(OH)2.5]3– with ten water molecules in the crystal lattice. In the polyanion, molybdenum ions are bonded to two terminal oxygen atoms and two μ2- (Mo-Mo) and μ3- (Mo-Fe-Mo) bridging oxygen atoms. Iron in the center of the polyanion 1 is also surrounded by three deprotonated oxygens of trimethanolamine ligand and three μ3- (Mo-Fe-Mo) bridging oxygen atoms. This new polyoxomolybdate was used as an efficient catalyst in the azide–alkyne cycloaddition reaction to produce various 1,2,3-triazoles with high yields. Additional investigations reveal this catalytic system can be refreshed and utilized for up to six successive applications.</p

Bacterial Cellulose–Based MOF Hybrid as a Sensitive Switch Off–On Luminescent Sensor for the Selective Recognition of l‑Histidine

In this study, a stable and luminescent UiO-66-NH2 (UN) and its derivative Cu2+@UN were prepared and utilized successfully as an Off–On luminescent sensing platform for effective, selective, as well as rapid (5 min) detection of l-Histidine (l-His). The UN reveals efficient quenching in the presence of Cu2+ ions through photoinduced electron transition (PET) mechanism as a dynamic quenching process (in the range of 0.01–1 mM) forming Cu2+@UN sensing platform. However, due to the remarkable affinity between l-His and Cu2+, the luminescence of Cu2+@UN is recovered in the presence of l-His indicating Turn-On behavior via a quencher detachment mechanism (QD). A good linear relationship between the l-His concentration and luminescence intensity was observed in the range of 0.01–40 μM (R2 = 0.9978) with a detection limit of 7 nM for l-His sensing. The suggested method was successfully utilized for l-His determination in real samples with good recoveries and satisfying consequences. Moreover, the result indicates that only l-His induces a significant luminescence restoration of Cu2+@UN and that the signal is significantly greater than that of the other amino acids. Also, the portable test paper based on bacterial cellulose (BC) as the Cu2+@UNBC sensing platform was developed to conveniently evaluate the effective detection of l-His

Chains, Layers, Channels, and More: Supramolecular Chemistry of Potent Diphosphonic Tectons with Tuned Flexibility. The Generation of Pseudopolymorphs, Polymorphs, and Adducts

Naphthalene-1,5-diphosphonic acid [C₁₀H₆(PO₃H₂)₂, H₄NDP­(1,5), <b>1</b>] and its more flexible counterpart, naphthalene-1,5-bis­(methylphosphonic) acid [C₁₀H₆(CH₂PO₃H₂)₂, H₄NDP­(1C,5C), <b>2</b>], have been synthesized, characterized, and used as building blocks in supramolecular assemblies with 4-(<i>N</i>,<i>N</i>-dimethylamino)­pyridine (DMAP) and morpholine. The two acids generate two distinct solvatomorphs each, with and without dimethyl sulfoxide (DMSO) molecules. The two adducts of H₄NDP­(1,5) with DMAP (<b>3A</b> and <b>3B</b>) reveal conformational polymorphism caused by the rotation of phosphonic groups. The two adducts of H₄NDP­(1C,5C) show unexpected structural diversity, generating a symmetric hydrogen bond and creating a layered structure, <b>4A</b>, or a channel structure, <b>4B</b>. The adducts of both acids with morpholine (<b>5A</b> and <b>5B</b>) allow for observing the influence of the conformational flexibility of the acids on the dimensionality of a final hydrogen bond network, which is in general higher for H₄NDP­(1C,5C). The structural motifs and trends are analyzed in terms of the geometric criteria of these interactions. For the first time, Hirshfeld surface analysis has also been applied for the investigation of supramolecular interactions of phosphonic acids in different protonation states

New Heterometallic Hybrid Polymers Constructed with Aromatic Sulfonate-Carboxylate Ligands: Synthesis, Layered Structures, and Properties

Three novel alkali metal–cadmium coordination polymers [K₂Cd­(Hsb)₄(H₂O)₆]_3<i>n</i> <b>1</b>, [NaCd­(sip)­(DMF)₂(H₂O)₂]_2<i>n</i> <b>2</b>, and [NaCd₂(sip)₂(DMF)₂(H₂O)₂]_2<i>n</i>·2<i>n</i>Hdeta·2<i>n</i>H₂O <b>3</b> (H₂sb = 4-sulfobenzoic acid, H₃sip = 5-sulfoisophthalic acid) have been synthesized and characterized by single crystal X-ray diffraction and spectroscopic and thermogravimetric methods. The solid state structure of <b>1</b> consists of inorganic layers, formed from Na₂O₁₀ and CdO₆, polyhedral units, bridged via the sulfonate site of the ligand. The layers are pillared by the organic portions of the ligands to form a three-dimensional framework classified as I²O¹. Compounds <b>2</b> and <b>3</b> display inorganic–organic hybrid layers arranged in 3D via nonspecific (hydrophobic) interactions between the DMF ligands. The two-dimensional frameworks of the layers are classified as I¹O¹ (in <b>2</b>) and I⁰O² (in <b>3</b>). The guest diethylammonium ions in <b>3</b> are arranged in hydrophobic channels along the [011] crystallographic direction and circumvented by the DMF ligands

Extending the Family of Tetrahedral Tectons: Phenyl Embraces in Supramolecular Polymers of Tetraphenylmethane-based Tetraphosphonic Acid Templated by Organic Bases

A missing member of the tetraphenylmethane-based family of supramolecular tectons, tetrakis­(4-phosphonophenyl)­methane, TPPM (<b>1</b>), has been obtained, characterized, and reacted with organic amines that possess modulated conformational flexibility. The obtained adducts serve as a diverse platform for the investigation of the amine templating effect on phenyl embraces, the resulting supramolecular network, and its topology. Hirshfeld surface (HS) analysis has been employed for the investigation of phenyl embraces, which led to the indication of characteristic HS features of 4PE and 6PE phenyl embraces. One can also observe a new subtype of phenyl embrace, namely, HBA-PE (hydrogen bond-assisted phenyl embrace), which constitutes the cooperation of two interactions: strong hydrogen bonding and a phenyl embrace. A topological insight into TPPM hydrogen-bonded networks is also provided. As a result, we found a connection of the amine template type with the periodicity of the underlying supramolecular network. Additionally, we report three previously unknown topologies. The obtainment of an unusual example of a phosphonic acid cocrystal with base (adduct <b>3</b>) allowed for the determination of specific 2D fingerprint plot patterns for acid–base structures, with and without proton transfer

Design and Synthesis of a Biocompatible 1D Coordination Polymer as Anti-Breast Cancer Drug Carrier, 5‑Fu: In Vitro and in Vivo Studies

Designable coordination polymers with suitable chemical diversities and biocompatible structures have been proposed as a promising class of vehicles for drug delivery systems. Here, we hydrothermally synthesized a novel one-dimensional (1D) coordination polymer, [Zn­(H₂O)₆K₂(H₂BTC)₂(H₂O)₄]­(H₂BTC)₂·2H₂O, where H₃BTC = benzene-1,3,5-tricarboxylic acid (trimesic acid), <b>cp.1</b>. As the hydrogen bonds stabilized 1D chains in three dimensions, the <b>cp.1</b> could be a good candidate for delivering small-molecule chemotherapeutics such as 5-fluorouracil (5-Fu). The synthesized <b>cp.1</b> showed a remarkable 5-Fu loading of 66% with encapsulation efficiency of 98% and almost complete release process. The 5-Fu-loaded <b>cp.1</b> displayed a time-dependent cytotoxicity effect against breast cancer cell lines MCF-7 and 4T1. The cellular uptake of <b>cp.1</b> particles was investigated via confocal laser scanning microscopy using fluorescein isothiocyanate and LysoTracker Red staining. Furthermore, the in vivo antitumor impact of 5-Fu-loaded <b>cp.1</b> was studied on 4T1 breast cancer BALB/c mice model. The intratumor treatment of 5-Fu-loaded <b>cp.1</b> demonstrated beneficial antitumor efficacy by postponing tumor growth. These results suggest that the 5-Fu-loaded <b>cp.1</b> microparticles with a great locoregional delivery can be efficient anticancer drug carriers for further clinical treatments

Design and Synthesis of a Biocompatible 1D Coordination Polymer as Anti-Breast Cancer Drug Carrier, 5‑Fu: In Vitro and in Vivo Studies

Designable coordination polymers with suitable chemical diversities and biocompatible structures have been proposed as a promising class of vehicles for drug delivery systems. Here, we hydrothermally synthesized a novel one-dimensional (1D) coordination polymer, [Zn­(H₂O)₆K₂(H₂BTC)₂(H₂O)₄]­(H₂BTC)₂·2H₂O, where H₃BTC = benzene-1,3,5-tricarboxylic acid (trimesic acid), <b>cp.1</b>. As the hydrogen bonds stabilized 1D chains in three dimensions, the <b>cp.1</b> could be a good candidate for delivering small-molecule chemotherapeutics such as 5-fluorouracil (5-Fu). The synthesized <b>cp.1</b> showed a remarkable 5-Fu loading of 66% with encapsulation efficiency of 98% and almost complete release process. The 5-Fu-loaded <b>cp.1</b> displayed a time-dependent cytotoxicity effect against breast cancer cell lines MCF-7 and 4T1. The cellular uptake of <b>cp.1</b> particles was investigated via confocal laser scanning microscopy using fluorescein isothiocyanate and LysoTracker Red staining. Furthermore, the in vivo antitumor impact of 5-Fu-loaded <b>cp.1</b> was studied on 4T1 breast cancer BALB/c mice model. The intratumor treatment of 5-Fu-loaded <b>cp.1</b> demonstrated beneficial antitumor efficacy by postponing tumor growth. These results suggest that the 5-Fu-loaded <b>cp.1</b> microparticles with a great locoregional delivery can be efficient anticancer drug carriers for further clinical treatments

Chiral 2 + 3 Keto-Enamine Pseudocyclophanes Derived from 1,3,5-Triformylphloroglucinol

The reactions of 1,3,5-triformyl­phloro­glucinol with (1<i>R</i>,2<i>R</i>)-1,2-diamino­cyclo­hexane, (1<i>R</i>,2<i>R</i>)-1,2-diphenyl­ethylene­diamine, or (<i>R</i>)-2,2′-diamino-1,1′-binaphthyl result in the formation of enantiopure [2 + 3] keto-enamine condensation products, in contrast to analogous reactions of 1,3,5-triformylbenzene, where [4 + 6] Schiff base cages are formed. The X-ray crystal structure of the diamino­cyclohexane 2 + 3 derivative as well as modeled structures of other compounds of this type show cyclophane-like molecules with close contact between the phloroglucinol rings. Density Functional Theory (DFT) calculations confirm that there is a sizable π–π interaction between these rings influencing the conformation of these molecules