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Metal–organic frameworks (MOFs) offer disruptive potential in micro- and optoelectronics because of the unique properties of these microporous materials. Nanoscale patterning is a fundamental step in the implementation of MOFs in miniaturized solid-state devices. Conventional MOF patterning methods suffer from low resolution and poorly defined pattern edges. Here, we demonstrate the resist-free, direct X-ray and electron-beam lithography of MOFs. This process avoids etching damage and contamination and leaves the porosity and crystallinity of the patterned MOFs intact. The resulting high-quality patterns have excellent sub-50-nm resolution, and approach the mesopore regime. The compatibility of X-ray and electron-beam lithography with existing micro- and nanofabrication processes will facilitate the integration of MOFs in miniaturized devices. The low dielectric constants and high porosity of MOFs are of interest for applications in electronics and sensors, but patterning techniques for these materials are in their infancy. Here, direct X-ray and electron-beam lithography at sub-50-nm resolution are reported that leave porosity and crystallinity intact.

The 1:1 stoichiometric reactions of α-amino isobutyric acid (H2Aib) and diaminosilanes of the type SiRR′(NR1R2)2 (SiMe2(imidazol-1-yl)2, SiMe2(NHnPr)2, and SiRR′(pyrrolidin-1-yl)2 with R,R′ = Me,Me, Me,H, Me,Vi, and Et,Et) afforded the pentacoordinate silicon complexes (Aib)SiRR′(HNR1R2) with the release of one equivalent of HNR1R2. Single-crystal X-ray diffraction analyses confirmed the coordination of the N-donor Lewis base (i.e., imidazole, n-propylamine, and pyrrolidine, respectively) in an axial position of the distorted trigonal-bipyramidal Si-coordination sphere, trans to the carboxylate O atom of the Si-chelating Aib-dianion. The N–H moieties of the adduct-forming Lewis bases are involved in N–H⋯O hydrogen bonds with carboxylate groups of adjacent complex molecules, thus supporting the supramolecular structures of these adducts. The equatorially bound NH group of the Aib-dianion is involved in N–H⋯O hydrogen bonds in most cases, and it gives rise to residual dipolar coupling of the 14N nucleus with its directly bound atoms C and Si, thus causing characteristic shapes of both the 29Si and 13C NMR signals of these two atoms in the solid-state spectra. In contrast to the adduct-formation reactions, the analogous conversion of H2Aib and SiMe2(NHtBu)2 did not afford an amine adduct. Instead, a second equivalent of H2Aib entered the reaction, and the ionic silicon complex [tBuNH3]+[(Aib)2SiMe]− was obtained and characterized by crystallography and solution NMR spectroscopy.

The preparation and characterization of two novel europium–azobenzene complexes that demonstrate the effectiveness of this ligand for stabilizing reactive, redox-active metals are reported. With the family of rare earth metals receiving attention due to their potential as catalysts, critical components in electronic devices, and, more recently, in biomedical applications, a detailed understanding of factors contributing to their coordination chemistry is of great importance for customizing their stability and reactivity. This study introduces azobenzene as an effective nonprotic ligand system that provides novel insights into rare earth metal coordination preferences, including factors contributing to the coordinative saturation of the large, divalent europium centers. The two compounds demonstrate the impact of the solvent donors (tetrahydrofuran (THF) and dimethoxyethane (DME)) on the overall coordination chemistry of the target compounds. Apart from the side-on coordination of the doubly-reduced azobenzene and the anticipated N-N bond elongation due to decreased bond order, the two compounds demonstrate the propensity of the europium centers towards limited metal-π interactions. The target compounds are available by direct metallation in a straightforward manner with good yields and purity. The compounds demonstrate the utility of the azobenzene ligands, which may function as singly- or doubly-reduced entities in conjunction with redox-active metals. An initial exploration into the computational modeling of these and similar complexes for subsequent property prediction and optimization is performed through a methodological survey of structure reproduction using density functional theory.

A novel series of mononuclear five-coordinated pseudohalido-Cu(II) complexes displaying distorted square bipyramidal: [Cu(L1)(NCS)2] (1), [Cu(L2)(NCS)2] (2) and [Cu(L3)(NCS)]ClO4 (5) as well as distorted trigonal bipyramidal: [Cu(isp3tren)(N3)]ClO4 (3), [Cu(isp3tren)(dca)]ClO4 (4) and [Cu(tedmpza)(dca)]ClO4·0.67H2O (6) geometries had been synthesized and structurally characterized using X-ray single crystal crystallography, elemental microanalysis, IR and UV-vis spectroscopy, and molar conductivity measurements. Different N-donor amine skeletons including tridentate: L1 = [(2-pyridyl)-2-ethyl)-(3,4-dimethoxy)-2-methylpyridyl]methylamine and L2 = [(2-pyridyl)-2-ethyl)-(3,5-dimethyl-4-methoxy)-2-methyl-pyridyl]methylamine, and tetradentate: L3 = bis(2-ethyl-di(3,5-dimethyl-1H-pyrazol-1-yl)-[2-(3,4-dimethoxy-pyridylmethyl)]amine, tedmpza = tris[(2-(3,5-dimethyl-1H-pyrazol-1-yl)ethyl]amine and isp3tren = tris[(2-isopropylamino)ethyl)]amine ligands were employed. Molecular structural parameters such as nature of coligand, its chelate ring size and steric environment incorporated into its skeleton, which lead to adopting one of the two limiting geometries in these complexes and other reported compounds are analyzed and correlated to their assigned geometries in solutions. Similar analysis were extended to other five-coordinated halido-Cu(II) complexes.

Three new tripod tetradentate phenolate-amines (H2L1, H2L4 and H2L9), together with seven more already related published ligands, were synthesized, and characterized. With these ligands, two new dinuclear doubly-bridged-phenoxido copper(II) complexes (3, 4), and six more complexes (1, 2, 5–8), a new trinuclear complex (9) with an alternative doubly-bridged-phenoxido and –methoxido, as well as the 1D polymer (10) were synthesized, and their molecular structures were characterized by spectroscopic methods and X-ray single crystal crystallography. The Cu(II) centers in these complexes exhibit distorted square-pyramidal arrangement in 1–4, mixed square pyramidal and square planar in 5, 6, and 9, and distorted octahedral (5+1) arrangements in 7 and 8. The temperature dependence magnetic susceptibility study over the temperature range 2–300 K revealed moderate–relatively strong antiferromagnetic coupling (AF) (|J| = 289–145 cm−1) in complexes 1–6, weak-moderate AF (|J| = 59 cm−1) in the trinuclear complex 9, but weak AF interactions (|J| = 3.6 & 4.6 cm−1) were obtained in 7 and 8. No correlation was found between the exchange coupling J and the geometrical structural parameters of the four-membered Cu2O2 rings.

A series of novel and previously published organoantimony compounds (RnSbX3−n, X = Cl, Br; R = o-tolyl, 2,6-xylyl, 1-naphthyl, and 9-anthracenyl), were synthesized and characterized. In addition, single-crystal X-ray diffraction was employed to elucidate the molecular structures of all solid species. These compounds display non-covalent intermolecular interactions in the form of edge-to-face, π···π stacking, and CH3···π interactions, and the effects of the substituent type and substituent bulk on the nature of these interactions present will be highlighted and discussed.

AbstractSix mixed metal complexes with 3-aminopyridine (3-ampy) as a co-ligand have been synthesized: catena-[M(μ2-3-ampy)(H2O)4]SO4·H2O (M=Ni (1) and Co (2)), [Co(3-ampy)4(NCS)2] (3), [Co(3-ampy)2(NCS)2] (4), [Co(3-ampy)4(N3)2] (5) and mer-[Co(3-ampy)3(N3)3] (6), (NCS−=isothiocyanate ion, N3− azide ion), and characterized by physio-chemical and spectroscopic methods as well as single crystal X-ray and powder diffraction. In the isostructural complexes 1 and 2 single μ2-3-ampy links the Ni(II) and Co(II) centers into polymeric chains. The mononuclear Co(II) and Co(III) pseudohalide complexes 3–6 reveal only terminal 3-ampy ligands. The 3-ampy ligands form supramolecular hydrogen bonded systems via their NH2-groups and non-covalent π-π ring-ring interactions via their pyridine moieties. Thermoanalytical properties were investigated for 1–3.Graphic abstract

Glycosidase inhibitors have shown great potential as pharmacological chaperones for lysosomal storage diseases. In light of this, a series of new cyclopentanoid β-galactosidase inhibitors were prepared and their inhibitory and pharmacological chaperoning activities determined and compared with those of lipophilic analogs of the potent β-d-galactosidase inhibitor 4-epi-isofagomine. Structure-activity relationships were investigated by X-ray crystallography as well as by alterations in the cyclopentane moiety such as deoxygenation and replacement by fluorine of a “strategic” hydroxyl group. New compounds have revealed highly promising activities with a range of β-galactosidase-compromised human cell lines and may serve as leads towards new pharmacological chaperones for GM1-gangliosidosis and Morquio B disease.

Ten mononuclear rare earth complexes of formula [La(btfa)3(H2O)2] (1), [La(btfa)3(4,4′-Mt2bipy)] (2), [La(btfa)3(4,4′-Me2bipy)2] (3), [La(btfa)3(5,5′-Me2bipy)2] (4), [La(btfa)3(terpy)] (5), [La(btfa)3(phen)(EtOH)] (6), [La(btfa)3(4,4′-Me2bipy)(EtOH)] (7), [La(btfa)3(2-benzpy)(MeOH)] (8), [Tb(btfa)3(4,4′-Me2bipy)] (9) and (Hpy)[Eu(btfa)4] (10), where btfa = 4,4,4-trifuoro-1-phenylbutane-1,3-dionato anion, 4,4′-Mt2bipy = 4,4′-dimethoxy-2,2′-bipyridine, 4,4′-Me2bipy = 4,4′-dimethyl-2,2′-bipyridine, 5,5′-Me2bipy = 5,5′-dimethyl-2,2′-bipyridine, terpy = 2,2′:6′,2′-terpyridine, phen = 1,10-phenathroline, 2-benzpy = 2-(2-pyridyl)benzimidazole, Hpy = pyridiniumH+ cation) have been synthesized and structurally characterized. The complexes display coordination numbers (CN) eight for 1, 2, 9, 10, nine for 5, 6, 7, 8 and ten for 3 and 4. The solid-state luminescence spectra of Tb-9 and Eu-10 complexes showed the same characteristic bands predicted from the Tb(III) and Eu(III) ions. The Overall Quantum Yield measured (ϕTOT) at the excitation wavelength of 371 nm for both compounds yielded 1.04% for 9 and up to 34.56% for 10.

The synthesis and structural characterization of six dicyanamido-cadmium(II) complexes are reported: catena-[Cd(μ1,3-dca)(μ1,5-dca)(3-ampy)] (1), catena-[Cd3(μ1,3,5-dca)2(μ1,5-dca)4(pyNO)2(H2O)2] (2), catena-Cd(H2O)2(μ1,5-dca)2](2,6-lut-NO) (3), catena-[Cd(Me2en)(μ1,5-dca)2] (4), catena-[Cd(Me4en)(μ1,5-dca)2] (5), and [Cd(1,8-damnp)2(dca)2] (6), where dca = dicyanamide anion, 3-ampy = 3-aminopyridine, pyNO = pyridine-N-oxide, 2,6-lut-NO = 2,6-lutidine-N-oxide, Me2en = N,N-dimethyl-ethylenediamine, Me4en = N,N,N′,N′-tetramethyl-ethylenediamine, and 1,8-damnp = 1,8-diaminonaphthaline. The coordination polymers have different dimensionalities: 1 and 5 form 3D networks structures; 3 and 4 form polymeric 1D chains and 1DD double chains, respectively. Ribbons of three fused polymeric chains are observed in 2. In 6, the mononuclear complex units form a hydrogen-bonded supramolecular 3D network. In the coordination polymer compounds, the dca linkers display three bonding modes: the most common μ1,5-dca and the least popular μ1,3- and μ1,3,5-dca bonding. The luminescence emission and thermal properties of the complexes were investigated.