Foldamer-Based Mechanoresponsive Materials: Molecular Nanoarchitectonics to Advanced Functions.

Artificial molecules that respond to external stimuli such as light, heat, chemical signals, and mechanical force have garnered significant interest due to their tunable functions, variable optical properties, and mechanical responses. Particularly, mechanoresponsive materials featuring molecules that respond to mechanical stress or show force-induced optical changes have been intriguing due to their extraordinary functions. Despite the promising potential of many such materials reported in the past, practical applications have remained limited, primarily because their functions often depend on irreversible covalent bond rupture.

Generation and characterization of bio-oil obtained from the slow pyrolysis of cooked food waste at various temperatures.

Bio-oil was generated from slow pyrolysis of cooked food waste (CFW) at various temperatures (300-500 °C). Then NMR analysis was used as a qualitative means to characterize the bio-oil for its nature (aliphatic or aromatic), and then the compounds were confirmed and quantified using the GC-MS. This analysis indicated that the pyrolysis at low temperature (300 °C) mainly generated carbonyl compounds (Aldehydes, Ketones, Esters, and Oxo groups), Levoglucosans, and Furans (17%, 24%, and 38%, respectively) considered as typical pyrolysis chemicals.

Selective and Cooperative Photocycloadditions within Multistranded Aromatic Sheets.

A series of aromatic helix-sheet-helix oligoamide foldamers composed of several different photosensitive diazaanthracene units have been designed and synthesized. Molecular objects up to 7 kDa were straightforwardly produced on a 100 mg scale. Nuclear magnetic resonance and crystallographic investigations revealed that helix-sheet-helix architectures can adopt one or two distinct conformations.

Scaffold-Induced Diketopyrrolopyrrole Molecular Stacks in a Covalent Organic Framework.

In recent years, covalent organic frameworks (COFs) have attracted considerable attention due to their crystalline and porous nature, which positions them as intriguing candidates for diverse applications such as catalysis, sensing, or optoelectronics. The incorporation of dyes or semiconducting moieties into a rigid two-dimensional COF can offer emergent features such as enhanced light harvesting or charge transport. However, this approach can be challenging when dealing with dye molecules that exhibit a large aromatic backbone, since the steric demand of solubilizing side chains also needs to be integrated into the framework.

Light-Controlled Conformational Switch of an Aromatic Oligoamide Foldamer.

An aromatic oligoamide sequence composed of a light-responsive diazaanthracene-based aromatic β-sheet flanked by two variable diameter helical segments was prepared. Structural investigations revealed that such oligomers adopt two distinct conformations: a canonical symmetrical conformation with the two helices stacked above and below the sheet, and an unanticipated unsymmetrical conformation in which one helix has flipped to directly stack with the first helix. Photoirradiation of the foldamer led to the quantitative, and thermally reversible, formation of a single photoproduct resulting from the [4+4] cycloaddition of two diazaanthracenes within the aromatic β-sheet.

Covalent Organic Frameworks and Cage Compounds: Design and Applications of Polymeric and Discrete Organic Scaffolds.

Porous organic materials are an emerging class of functional nanostructures with unprecedented properties. Dynamic covalent assembly of small organic building blocks under thermodynamic control is utilized for the intriguingly simple formation of complex molecular architectures in one-pot procedures. In this Review, we aim to analyze the basic design principles that govern the formation of either covalent organic frameworks as crystalline porous polymers or covalent organic cage compounds as shape-persistent molecular objects.

Microtubular Self-Assembly of Covalent Organic Frameworks.

Despite significant progress in the synthesis of covalent organic frameworks (COFs), reports on the precise construction of template-free nano- and microstructures of such materials have been rare. In the quest for dye-containing porous materials, a novel conjugated framework DPP-TAPP-COF with an enhanced absorption capability up to λ=800 nm has been synthesized by utilizing reversible imine condensations between 5,10,15,20-tetrakis(4-aminophenyl)porphyrin (TAPP) and a diketopyrrolopyrrole (DPP) dialdehyde derivative. Surprisingly, the obtained COF exhibited spontaneous aggregation into hollow microtubular assemblies with outer and inner tube diameters of around 300 and 90 nm, respectively.

High Loading of Pd Nanoparticles by Interior Functionalization of MOFs for Heterogeneous Catalysis.

In this report, the issue related to nanoparticle (NP) agglomeration upon increasing their loading amount into metal-organic frameworks (MOFs) has been addressed by functionalization of MOFs with alkyne groups. The alkynophilicity of the Pd(2+) (or other noble metals) ions has been utilized successfully for significant loading of Pd NPs into alkyne functionalized MOFs. It has been shown here that the size and loading amount of Pd NPs are highly dependent on the surface area and pore width of the MOFs.

A smart approach to achieve an exceptionally high loading of metal nanoparticles supported by functionalized extended frameworks for efficient catalysis.

The problem associated with metal nanoparticle (NP) agglomeration when trying to achieve a high loading amount has been solved by a new method of functionalization of MOFs' pores with terminal alkyne moieties. The alkynophilicity of the Au(3+) ions has been utilized successfully for an exceptionally high loading (∼50 wt%) of Au-NPs on supported functionalized MOFs.

Explosives sensing by using electron-rich supramolecular polymers: role of intermolecular hydrogen bonding in significant enhancement of sensitivity.

We demonstrate here that supramolecular interactions enhance the sensitivity towards detection of electron-deficient nitro-aromatic compounds (NACs) over discrete analogues. NACs are the most commonly used explosive ingredients and are common constituents of many unexploded landmines used during World War II. In this study, we have synthesised a series of pyrene-based polycarboxylic acids along with their corresponding discrete esters.

Multicomponent assembly of fluorescent-tag functionalized ligands in metal-organic frameworks for sensing explosives.

Detection of trace amounts of explosive materials is significantly important for security concerns and pollution control. Four multicomponent metal-organic frameworks (MOFs-12, 13, 23, and 123) have been synthesized by employing ligands embedded with fluorescent tags. The multicomponent assembly of the ligands was utilized to acquire a diverse electronic behavior of the MOFs and the fluorescent tags were strategically chosen to enhance the electron density in the MOFs.

Ferrocenyl-L-amino acid copper(II) complexes showing remarkable photo-induced anticancer activity in visible light.

Ferrocene-conjugated copper(ii) complexes [Cu(Fc-aa)(aip)](ClO4) () and [Cu(Fc-aa)(pyip)](ClO4) () of l-amino acid reduced Schiff bases (Fc-aa), 2-(9-anthryl)-1H-imidazo[4,5-f][1,10]phenanthroline (aip) and 2-(1-pyrenyl)-1H-imidazo[4,5-f][1,10]phenanthroline (pyip), where Fc-aa is ferrocenylmethyl-l-tyrosine (Fc-Tyr in , ), ferrocenylmethyl-l-tryptophan (Fc-Trp in , ) and ferrocenylmethyl-l-methionine (Fc-Met in , ), were prepared and characterized, and their photocytotoxicity was studied (Fc = ferrocenyl moiety). Phenyl analogues, viz. [Cu(Ph-Met)(aip)](ClO4) () and [Cu(Ph-Met)(pyip)](ClO4) (), were prepared and used as control compounds.

Carbohydrate-appended tumor targeting iron(III) complexes showing photocytotoxicity in red light.

Glucose-appended photocytotoxic iron(III) complexes of a tridentate Schiff base phenolate ligand [Fe(bpyag)(L)](NO3) (1-3), where bpyag is N,N-bis(2-pyridylmethyl)-2-aminoethyl-β-D-glucopyranoside and H2L is 3-(2-hydroxyphenylimino)-1-phenylbutan-1-one (H2phap) in 1, 3-(2-hydroxyphenylimino)-9-anthrylbutan-1-one (H2anap) in 2, and 3-(2-hydroxyphenylimino)-1-pyrenylbutan-1-one (H2pyap) in 3, were synthesized and characterized. The complex [Fe(dpma)(anap)](NO3) (4), having bis-(2-pyridylmethyl)benzylamine (dpma), in which the glucose moiety of bpyag is substituted by a phenyl group, was used as a control, and the complex [Fe(dpma)(anap)](PF6) (4a) was structurally characterized by X-ray crystallography. The structure shows a FeN4O2 core in a distorted octahedral geometry.

Modification of extended open frameworks with fluorescent tags for sensing explosives: competition between size selectivity and electron deficiency.

Three new electron-rich metal-organic frameworks (MOF-1-MOF-3) have been synthesized by employing ligands bearing aromatic tags. The key role of the chosen aromatic tags is to enhance the π-electron density of the luminescent MOFs. Single-crystal X-ray structures have revealed that these MOFs form three-dimensional porous networks with the aromatic tags projecting inwardly into the pores.

An electron rich porous extended framework as a heterogeneous catalyst for Diels-Alder reactions.

An electron rich porous metal-organic framework (MOF) has been synthesized, which acts as an effective heterogeneous catalyst for Diels-Alder reactions through encapsulation of the reactants in confined nano-channels of the framework.

Photocytotoxicity of copper(II) complexes of curcumin and N-ferrocenylmethyl-L-amino acids.

Copper(II) complexes [Cu(Fc-aa)(cur)] (1-3) of curcumin (Hcur) and N-ferrocenylmethyl-L-amino acids (Fc-aa), viz., ferrocenylmethyl-L-tyrosine (Fc-TyrH), ferrocenylmethyl-L-tryptophan (Fc-TrpH) and ferrocenylmethyl-L-methionine (Fc-MetH), were prepared and characterized. The DNA photocleavage activity, photocytotoxicity and cellular localization in HeLa and MCF-7 cancer cells of these complexes were studied.

Fluorescent tris-imidazolium sensors for picric acid explosive.

Two new anthracene-functionalized fluorescent tris-imidazolium salts have been synthesized, characterized, and proven to be selective sensors for picric acid, which is a common constituent of many powerful explosives. Theoretical studies revealed an unusual ground-state electron transfer from picrate anion to the sensor molecules.

Fluorescent metal-organic framework for selective sensing of nitroaromatic explosives.

Highly luminescent micrometre-sized fine particles of a Zn(II) metal-organic framework (MOF) of a new π-electron rich tricarboxylate dispersed in ethanol is demonstrated as a selective sensory material for the detection of nitroaromatic explosives via a fluorescence quenching mechanism.

Coordination-driven self-assembly of 2D-metallamacrocycles using a shape-selective Pt(II)2-organometallic 90° acceptor: design, synthesis and sensing study.

Synthesis of a series of two-dimensional metallamacrocycles via coordination-driven self-assembly of a shape-selective Pt(II)(2)-molecular building unit incorporating carbazole-ethynyl functionality is described. An equimolar (1 : 1) combination of a Pt(II)(2)-organometallic 90° acceptor, 1, with rigid linear ditopic donors (L(a) and L(b)) afforded [4 + 4] self-assembled octanuclear molecular squares, 2 and 3, in quantitative yields, respectively [L(a) = 4,4'-bipyridine; L(b) = trans-1,2-bis(4-pyridyl)ethylene]. Conversely, a similar treatment of 1 with an amide-based unsymmetrical flexible ditopic donor, L(c), resulted in the formation of a [2 + 2] self-sorted molecular rhomboid (4a) as a single product [L(c) = N-(4-pyridyl)isonicotinamide].

Supramolecular polymer for explosives sensing: role of H-bonding in enhancement of sensitivity in the solid state.

A π-electron rich supramolecular polymer as an efficient fluorescent sensor for electron deficient nitroaromatic explosives has been synthesized, and the role of H-bonding in dramatic amplification of sensitivity/fluorescence quenching efficiency in the solid state has been established.

Synthesis, structures, and magnetic behavior of a series of copper(II) azide polymers of Cu4 building clusters and isolation of a new hemiaminal ether as the metal complex.

Four new neutral copper azido polymers, [Cu(4)(N(3))(8)(L(1))(2)](n) (1), [Cu(4)(N(3))(8)(L(2))(2)](n) (2), [Cu(4)(N(3))(8)(L(3))(2)](n) (3), and [Cu(9)(N(3))(18)(L(4))(4)](n) (4) [L(1-4) are formed in situ by reacting pyridine-2-carboxaldehyde with 2-[2-(methylamino)ethyl]pyridine (mapy, L(1)), N,N-dimethylethylenediamine (N,N-dmen, L(2)), N,N-diethylethylenediamine (N,N-deen, L(3)), and N,N,2,2-tetramethylpropanediamine (N,N,2,2-tmpn, L(4))], have been synthesized by using 0.5 mol equiv of the chelating tridentate ligands with Cu(NO(3))(2)·3H(2)O and an excess of NaN(3). Single-crystal X-ray structures show that the basic unit of these complexes, especially 1-3, contains very similar Cu(II)(4) building blocks.

Use of 2-pyrimidineamidoxime to generate polynuclear homo-/heterometallic assemblies: synthesis, crystal structures and magnetic study with theoretical investigations on the exchange mechanism.

Three new transition metal complexes using 2-pyrimidineamidoxime (pmadH(2)) as multidentate chelating and/or bridging ligand have been synthesized and characterized. The ligand pmadH(2) has two potential bridging functional groups [μ-O and μ-(N-O)] and consequently shows several coordination modes. While a polymeric 1D Cu(II) complex [Cu(pmadH(2))(2)(NO(3))](NO(3)) (1) was obtained upon treatment of Cu(NO(3))(2)·3H(2)O with pmadH(2) at room temperature in the absence of base, a high temperature reaction in the presence of base yielded a tetranuclear Cu(II)-complex [Cu(4)(pmad)(2)(pmadH)(2)(NO(3))](NO(3))(H(2)O) (2).

A series of transition metal-azido extended complexes with various anionic and neutral co-ligands: synthesis, structure and their distinct magnetic behavior.

The crystal structures and magnetic properties of five new transition metal-azido complexes with two anionic [pyrazine-2-carboxylate (pyzc) and p-aminobenzoate (paba)] and two neutral [pyrazine (pyz) and pyridine (py)] coligands are reported. All five complexes were synthesized by solvothermal methods. The complex [Co2(pyzc)2(N3)2(H2O)2]n (1) is 1D and exhibit canted antiferromagnetism, while the 3D complex [MnNa(pyzc)(N3)2(H2O)2]n (2) has a complicated structure and is weakly ferromagnetic in nature.

Cu(II)-azide polymers of Cu3 and Cu6 building units: synthesis, structures, and magnetic exchange mechanism.

Two new neutral copper-azido polymers [Cu(3)(N(3))(6)(tmen)(2)](n) (1) and [Cu(6)(N(3))(12)(deen)(2)](n) (2) [tmen = N,N,N',N'-tetramethylethylenediamine and deen = N,N'-diethylethylenediamine] have been synthesized by using lower molar equivalents of the chelating diamine ligands with Cu(NO(3))(2).3H(2)O and an excess of NaN(3). The single crystal X-ray structure shows that in the basic unit of the 1D complex 1, the three Cu(II) ions are linked by double end-on azido bridges with Cu-N(EO)-Cu angles on both sides of the magnetic exchange critical angle of 108 degrees.