LIST OF ABBREVIATIONS0D = zero-dimensional 1,4-DHPs = 1,4-dihydropyridine 1D = one-dimensional 2,4-DNP = 2,4-nitrophenol 2D = two-dimensional 2L-H2asp = N-(2-pyridylmethyl)-L-aspartic acid 3D = three-dimensional 3L-val = N-(3-pyridylmethyl)-L-valine aq. = aqueous bbbi = 1,1'-(1,4-butanediyl)bis-1H-benzimidazole) bbmb = 1,2-bis((1H-benzo[d][1,2,3]triazol-1-yl)methyl)benzene bdob = 1,4-bis(4,5-dihydro-2-oxazolyl)benzene bipy = 4,4'-bipyridine bm = benzimidazole [(bmim)(BF4)] = 1-butyl-3-methylimidazolium tetrafluoroborate BMPyr = 1-butyl-1-methylpyrrolidinium btSe = benzene-1,2,4,5-tetraselenolate btt = benzene-1,2,4,5-tetrathiol CP = coordination polymer CR = Congo Red Cy = cyclohexane dfbi = 1,1'-(9,9-dimethyl-9H-fluorene-2,7-diyl)bis(1H-imidazole) D-H2pen = D-penicillamine DMF = N,N-dimethylformamide DMSO = Dimethylsulfoxide dped = 1,2-bis(diphenylphosphino)ethane dioxide dpppda = 1,4-N,N,N′,N′-tetra(diphenylphosphanylmethyl) benzene diamine ee = enantiomeric excess ESI-MS = electrospray ionization mass spectrometry EtOH = ethanol FTIR = Fourier-transform infrared spectroscopy Hbmmp = 4-ethyl-2,6-bis((E)-((3-morpholinopropyl)imino)methyl)phenol HPNP = 2-hydroxypropyl-p-nitrophenylphosphate Htbba = 4-((4-([2,2':6',2''-terpyridin]-4'-yl)benzyl)oxy)benzoic acid H2aipa = 5-acetamidoisophthalic acid H2bipa = 5-benzamidoisophthalic acid H2bpdc = 4,4'-biphenyldicarboxylic acid H2cybps = 1,2-cyclohexanediamino-N,N'-bis(3-tert-butyl-5-(4-pyridyl)salicylidene H2dtda = 3,3′′-dipropoxy-[1,1′:4′,1′′-terphenyl]-4,4′′-dicarboxylic acid H2hmb = 2-[(2-hydroxy-3-methoxyphenyl)methylideneamino]benzenesulfonic acid H2icyd = N,N'-bis-[(imidazol-4-yl)methylene]cyclohexane-1,2diamine H2ntp = 2-nitroterephthalic acid H2phba = 4-hydroxybenzoic acid H2ppd = bis(pyridin-2-ylmethylene)pyridine-2,6-dicarbohydrazide H2pydca = pyridine-2,6-dicarboxylate H2tae = 1,1,2,2-tetraacetylethane H3bes = N,N-bis(2-hydroxyethyl)-2-aminoethanesulfonic acid H3btc = 1,2,4-trimellitic acid H3ccb = 3-(carboxymethyl-amino)-4-chlorobenzoic acid H3cia = N-(4-carboxybenzyl) iminodiacetic acid H3dhia = 5-(2-(4,4-dimethyl-2,6-dioxocyclohexylidene)hydrazinyl)isophthalic acid H3dht = 2-(2-(4,4-dimethyl-2,6-dioxocyclo-hexylidene)hydrazinyl)terephthalic acid H3dmb = 2-[(2,3-dihydroxyphenyl)methylideneamino]benzenesulfonic acid H3tea = triethanolamine H4bccy = N,N′-bis(4-carboxysalicylidene)cyclohexanediamine H4bced = N,N'-bis(4-carboxysalicylidene)ethylenediamine H4hpd = bis(2-hydroxybenzylidene)pyridine-2,6-dicarbohydrazide H4pdada = 4,4'-((pyridine-2,6-dicarbonyl)bis(azanediyl))dibenzoic acid H4pma = pyromellitic acid H6bmt = (benzene-1,3,5-triyltris(methylene))triphosphonic acid H6nmp = nitrilotris(methylenephosphonic acid) IL = ionic liquid iPrOH = 2-propanol MB = methylene blue MeCN = acetonitrile MeOH = methanol MO = Methyl Orange MOF = metal-organic framework MW = microwave NB = nitrobenzene NMF = N-Methylformamide NTf2 = bis(trifluoromethanesulfonyl)imide PhIO = iodosobenzene pmba = 2-(2-pyridylmethyleneamino)benzenesulfonic acid PNP = paranitrophenol RhB = Rh...

A family of benzotriazole based coordination compounds, obtained in two steps and good yields from commercially available materials, formulated as [Cu(L)(MeCN)]·2ClO·MeCN (1), [Cu(L)(NO)]·MeCN (2), [Zn(L)(HO)]·2ClO·2MeCN (3), [Cu(L)Cl] (4), [Cu(L)Cl] (5), [Cu(L)Br]·4MeCN·CuBr (6), [Cu(L)(MeCN)]·2BF (7), [Cu(L)(CFSO)] (8), [Zn(L)(MeCN)]·2CFSO (9), [Cu(L)(HO)]·4CFSO·4MeCO (10), and [Cu(L)(CFSO)]·2CFSO·MeCO (11), are reported. These air-stable compounds were tested as homogeneous catalysts for the A coupling synthesis of propargylamine derivatives from aldehyde, amine, and alkyne under a noninert atmosphere. Fine tuning of the catalyst resulted in a one-dimensional (1D) coordination polymer (CP) (8) with excellent catalytic activity in a wide range of substrates, avoiding any issues that would inhibit its performance.

Guest responsive porous materials represent an important and fascinating class of multifunctional solids that have attracted considerable attention in recent years. An understanding of how these structures form is essential toward their rational design, which is a prerequisite for the development of tailor-made materials for advanced applications. We herein report a novel series of stable rare-earth (RE) MOFs that show a rare continuous breathing behavior and an unprecedented gas-trapping property. We used an asymmetric 4-c tetratopic carboxylate-based organic ligand that is capable of affording highly crystalline materials upon controlled reaction with RE cations. These MOFs, denoted as RE-thc-MOF-1 (RE: Y3+, Sm3+, Eu3+, Tb3+, Dy3+, Ho3+, and Er3+), feature hexanuclear RE6 clusters that display a highly unusual connectivity and serve as unique 8-c hemi-cuboctahedral secondary building block, resulting in a new (3,3,8)-c thc topology. Extensive single-crystal to single-crystal structural analyses coupled with detailed gas (N2, Ar, Kr, CO2, CH4, and Xe) and vapor (EtOH, CH3CN, C6H6, and C6H14) sorption studies, supported by accurate theoretical calculations, shed light onto the unique swelling behavior. The results reveal a synergistic action involving steric effects, associated with coordinated solvent molecules and 2-fluorobenzoate (2-FBA) nonbridging ligands, as well as cation–framework electrostatic interactions. We were able to probe the individual role of the coordinated solvent molecules and 2-FBA ligands and found that both cooperatively control the gas-breathing and -trapping properties, while 2-FBA controls the vapor adsorption selectivity. These findings provide unique opportunities toward the design and development of tunable RE-based flexible MOFs with tailor-made properties.

As eries of new (N'-substituted)-hydrazo-4-aryl-1,4-dihydropyridinesw as successfully synthesized via af acile one-pot catalytic pathwayu tilizing azines andp ropiolate esters as starting materialsa nd ao ne-dimensional copper benzotriazole-based coordination polymer as catalyst. In the absence of catalyst, the corresponding 5-substituted 4,5-dihydropyra-zoles were formed in moderate to high yields.F inetuning of the catalysts allowed us to gain more insights regarding the plausible reactionmechanism.Scheme2.Plausible mechanism for the synthesis of the (N'substituted)-hydrazo-4-aryl-1,4-dihydropyridines throught he hydrazine and propiolate Cu-catalyzed coupling.

The facile copper-catalyzed synthesis of polysubstituted pyrroles from aldehydes, amines, and β-nitroalkenes is reported. Remarkably, the use of α-methyl-substituted aldehydes provides efficient access to a series of tetra- and pentasubstituted pyrroles via an overwhelming 1,2-phenyl/alkyl migration. The present methodology is also accessible to non α-substituted aldehydes, yielding the corresponding trisubstituted pyrroles. On the contrary, the use of ketones, in place of aldehydes, does not promote the organic transformation, signifying the necessity of α-substituted aldehydes. The reaction proceeds under mild catalytic conditions with low catalyst loading (0.3-1 mol %), a broad scope, very good functional-group tolerance, and high yields and can be easily scaled up to more than 3 mmol of product, thus highlighting a useful synthetic application of the present catalytic protocol. Based on formal kinetic studies, a possible radical pathway is proposed that involves the formation of an allylic nitrogen radical intermediate, which in turn reacts with the nitroalkene to yield the desired pyrrole framework via a radical 1,2-phenyl or alkyl migration.

This diagnostic study aims to shed light on the catalytic activity of a library of Cu(ii) based coordination compounds with benzotriazole-based ligands. We report herein the synthesis and characterization of five new coordination compounds formulated as [Cu(L)(MeCN)(CFSO)] (1), [Cu(L)(CFSO)] (2), [Cu(L)(MeCN)(CFSO)]·(CFSO) (3), [Cu(L)(HO)(CFSO)]·(CFSO)·2(MeCO) (4), and [Cu(L)(L)(CFSO)]·4(CFSO)·8(MeCO) (5), derived from similar nitrogen-based ligands. The homogeneous catalytic activity of these compounds along with our previously reported coordination compounds (6-13), derived from similar ligands, is tested against the well-known Cu(i)-catalysed azide-alkyne cycloaddition reaction. The optimal catalyst [Cu(L)(CFSO)] (10) activates the reaction to afford 1,4-disubstituted 1,2,3-triazoles with yields up to 98% and without requiring a reducing agent. Various control experiments are performed to optimize the method and examine parameters such as ligand variation, metal coordination geometry and environment, in order to elucidate the behaviour of the catalytic system.

Highly connected metal organic frameworks (MOFs) in which at least one building block has connectivity higher than twelve are very rare and much desirable. We report here the first examples of isostructural 14-connected MOFs, RE-frt-MOF-1, constructed from the assembly of 14-c hexanuclear rare-earth clusters, [RE6(μ3-X)8(COO)12]2– (RE: Y3+, Tb3+, Dy3+, Ho3+, Er3+, Yb3+ and X: OH–/F–) with a tritopic carboxylate-based organic linker. This linker serves as a 3-c and 4-c organic node resulting in the formation of a unique, trinodal (3,4,14)-c framework. RE-frt-MOF-1 are stable in air and alkaline aqueous solutions and show an intriguingly continuous, reversible breathing behavior, between a wide and a narrow-pore phase, upon guest removal. Crystallinity is retained during breathing, and single-crystal X-ray diffraction shed light into the associated structural transformation. Vapor sorption studies performed on Y-frt-MOF-1 revealed a high affinity for non-polar vapors such as n-hexane, cyclohexane, and benzene, displaying type I isotherms with high uptake at low relative pressures (<10–3 p/p 0), associated with the hydrophobic nature of the 1D channels and also with their rhombic shape. In contrast, polar vapors such as acetonitrile and ethanol show type V isotherms due to favorable vapor–vapor interactions. Notably these vapors, except cyclohexane, trigger the transition from the narrow to the wide pore phase, accompanied by a remarkable increase in uptake, reaching 70.6, 109, 100.4, and 87.7% for n-hexane, benzene, acetonitrile, and ethanol, respectively.

The employment of (E)‐4‐(2‐hydroxy‐3‐methoxybenzylideneamino)‐2,3‐dimethyl‐1‐phenyl‐1,2‐dihydropyrazol‐5‐one (HL) for the first time in 3d/4f chemistry, without any co‐ligand, provides access to a disk‐like heptanuclear CoII3DyIII4 coordination cluster displaying single molecule magnetism (SMM) behavior. The topology of this compound has hitherto not been observed in CoII/DyIII chemistry.