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Thin films of crystalline and porous metal-organic frameworks (MOFs) have great potential in membranes, sensors, and microelectronic chips. While the morphology and crystallinity of MOF films can be evaluated using widely available techniques, characterizing their pore size, pore volume, and specific surface area is challenging due to the low amount of material and substrate effects. Positron annihilation lifetime spectroscopy (PALS) is introduced as a powerful method to obtain pore size information and depth profiling in MOF films. The complementarity of this approach to established physisorption-based methods such as quartz crystal microbalance (QCM) gravimetry, ellipsometric porosimetry (EP), and Kr physisorption (KrP) is illustrated. This comprehensive discussion on MOF thin film porosimetry is supported by experimental data for thin films of ZIF-8. ispartof: ADVANCED MATERIALS vol:33 issue:17 ispartof: location:Germany status: published

A vapor-assisted synthesis method was developed for the metal-organic framework (MOF) HKUST-1 in both powder and film format. The use of a solvent template supplied from the vapor phase is essential to form the framework under these conditions. Chemical vapor deposition of HKUST-1 films (MOF-CVD) results in smooth films that show the expected adsorption behavior. Interestingly, the HKUST-1 films obtained this way show a (111) preferred crystallographic orientation.

ispartof: ACS APPLIED NANO MATERIALS vol:5 issue:4 pages:5006-5016 status: published

Metal?organic frameworks (MOFs) can provide a variety of nanocompartments for the confinement of guest molecules. Furthermore, the emissions of fluorescent molecules can be tuned by confinement. In this study, a solvent-free ?bottle-around-ship? method is used to encapsulate perylene and 9,10-dimethylanthracene, two polycyclic aromatic hydrocarbons, in the MOF ZIF-8. Luminescence color tuning is achieved, including white-light emission, when controlling the loading of only a single type of guest. Photophysical analysis suggests that the variations in luminescence result from various guest arrangements in the nanocompartments, as well as host?guest interactions. Because of the tight confinement of the guests, this host?guest system displays excellent luminescence thermal stability. ispartof: Advanced Optical Materials vol:11 issue:3 status: published

Copper dicarboxylate metal-organic framework films are deposited via chemical vapour deposition. Uniform films of CuBDC and CuCDC with an out-of-plane orientation and accessible porosity are obtained from the reaction of Cu and CuO with vaporised dicarboxylic acid linkers. ispartof: CHEMICAL COMMUNICATIONS vol:55 issue:55 pages:10056-10059 ispartof: location:England status: Published online

We report design and structural characterization of six new coordination polymers fabricated from PbCl2 and a series of closely related bis-pyridyl ligands LI and HLII–HLVI, namely, [Pb2(LI)Cl4]n, [Pb(HLII)Cl2]n·nMeOH, [Pb(HLIII)Cl2]n·0.5 nMeOH, [Pb2(LIV)Cl3]n, [Pb(HLV)Cl2]n, and [Pb3(LVI)2Cl4]n·nMeOH. The topology of the obtained networks is dictated by the geometry of the organic ligand. The structure of [Pb2(LI)Cl4]n is constructed from the [PbCl2]n two-dimensional (2D) sheets, linked through organic linkers into a three-dimensional framework, which exhibits a unique binodal 4,7-connected three-periodic topology named by us as sda1. Topological analysis of the 2D metal–organic sheet in [Pb(HLII)Cl2]n·nMeOH discloses a binodal 3,4-connected layer topology, regardless of the presence of tetrel bonds. A one-dimensional (1D) coordination polymer [Pb(HLIII)Cl2]n·0.5 nMeOH is considered as a uninodal 2-connected chain. The overall structure of [Pb2(LIV)Cl3]n is constructed from dimeric tetranuclear [Pb4(μ3-L...

Because of their molecular sieving properties, metal–organic frameworks have a high potential for application in gas storage, separation, and sensing. However, their real-world implementation will require robust and low-cost synthetic approaches. We herein report the solvent-free synthesis of ultramicroporous α-magnesium formate (α-MgFm) based on the solid–vapor reaction of magnesium oxide (MgO) and formic acid and establish the requirement for a structure-directing agent. Translated into a chemical vapor deposition protocol, this method enables the fabrication of high-quality, pinhole-free films of α-MgFm.

Robust and scalable thin film deposition methods are key to realize the potential of metal-organic frameworks (MOFs) in electronic devices. Here, we report the first integration of the chemical vapor deposition (CVD) of MOF coatings in a custom reactor within a cleanroom setting. As a test case, the MOF-CVD conditions for ZIF-8 are optimized to enable smooth, pinhole-free, and uniform thin films on full 200 mm wafers under mild conditions. The single-chamber MOF-CVD process and the impact of the deposition parameters are elucidated via a combination of in situ monitoring and ex situ characterization. The resulting process guidelines will pave the way for new MOF-CVD formulations and a plethora of MOF-based devices.

Covalent postsynthetic modification (PSM) of metal-organic frameworks (MOFs) has attracted much attention due to the possibility of tailoring the properties of these porous materials. Schiff-base condensation between an amine and an aldehyde is one of the most common reactions in the PSM of MOFs. Here, we report the use of the spray drying technique to perform this class of organic reactions, either between discrete organic molecules or on the pore surfaces of MOFs, in a very fast (1-2 s) and continuous way. Using spray drying, we show the PSM of two MOFs, the amine-terminated UiO-66-NH2 and the aldehyde-terminated ZIF-90, achieving conversion efficiencies up to 20 and 42%, respectively. Moreover, we demonstrate that it can also be used to postsynthetically cross-link the aldehyde groups of ZIF-90 using a diamine molecule with a conversion efficiency of 70%.

Chemical vapor deposition of MOFs (MOF-CVD) has been used to coat solid-phase microextraction (SPME) fibers with ZIF-8, by exposing ZnO layers to the linker vapor (2-methylimidazole). This ZIF-8 coating has been used as a seed layer in a following solvothermal MOF growth step in order to increase the ZIF-8 thickness. The combined MOF-CVD and solvothermal growth of ZIF-8 on the fibers result in a thickness of ~3 μm, with adequate thermal stability, and mechanical integrity when tested with methanol and acetonitrile ultrasonic treatments. The fibers have been evaluated in direct immersion mode using gas chromatography and flame ionization detection (GC-FID), for a group of target analytes including three polycyclic aromatic hydrocarbons (PAHs) and five personal care products (PCPs). The optimized conditions of the SPME-GC-FID methods include low amount of aqueous sample (5 mL), stirring for 45 min at 35 °C, and desorption at 280 °C for 5 min. The method presents limits of detection down to 0.6 μg L−1; intra-day, inter-day and inter-batch relative standard deviation values lower than 16%, 19%, and 23%, respectively; and a lifetime higher than 70 cycles.

Chemistry of materials XX(XX), acs.chemmater.9b03435 (2019). doi:10.1021/acs.chemmater.9b03435, Robust and scalable thin film deposition methods are key to realize the potential of metal-organic frameworks (MOFs) in electronic devices. Here, we report the first integration of the chemical vapor deposition (CVD) of MOF coatings in a custom reactor within a cleanroom setting. As a test case, the MOF-CVD conditions for ZIF-8 are optimized to enable smooth, pinhole-free, and uniform thin films on full 200 mm wafers under mild conditions. The single-chamber MOF-CVD process and the impact of the deposition parameters are elucidated via a combination of in situ monitoring and ex situ characterization. The resulting process guidelines will pave the way for new MOF-CVD formulations and a plethora of MOF-based devices., Published by American Chemical Society, Washington, DC

Metal-organic frameworks (MOFs) enable the design of host-guest systems with specific properties. In this work, we show how the confinement of anthracene in a well-chosen MOF host leads to reversible yellow-to-purple photoswitching of the fluorescence emission. This behavior has not been observed before for anthracene, either in pure form or adsorbed in other porous hosts. The photoresponse of the host-guest system is caused by the photodimerization of anthracene, which is greatly facilitated by the pore geometry, connectivity, and volume as well as the structural flexibility of the MOF host. The photoswitching behavior was used to fabricate photopatternable and erasable surfaces that, in combination with data encryption and decryption, hold promise in product authentication and secure communication applications. ispartof: ANGEWANDTE CHEMIE-INTERNATIONAL EDITION vol:58 issue:8 pages:2423-2427 ispartof: location:Germany status: published

A chiral Zn

This work bases on the solid‐state study of a chiral ZnII‐porphyrin derivative (5,10,15,20‐tetra[(4‐R,R,R,R)‐methyl‐2‐phenoxy‐propanoate, 1) building block and its achiral analogous (2). Here, foreseen the rich molecular recognition of the designed metallo‐porphyrins (1 and 2) and tendency to crystallize, we recrystallized both using two sets of solvents (CH2Cl2/CH3OH and CH2Cl2/hexane). As a result, four different crystalline arrangements (1a‐b, 2a‐b, from 0D to 2D) were successfully achieved. We performed solid state studies for all the species, analysing the role played by chirality, solvent mixtures and surfaces (mica and HOPG), on the supramolecular arrangements. As for the combination of solvents and substrates we obtained a variety of micro‐sized species, from vesicles to flower‐shaped arrays, including geometrical microcrystals. Overall, our results emphasize the environmental susceptibility of metallo‐porphyrins and how this feature must be taken into account in their design.

Here, we show that the well-known hydrophobic leucine (Leu) zipper motif (also known as the coiled-coil or Leu scissors motif), typically found in proteins, can be used as a source of inspiration in coordination polymers built from Leu-containing dipeptides or tripeptides. We demonstrate that this motif can be extended to form Velcro-like layers of Leu, and that the hydrophobicity of these layers is transferred to coordination polymers, thereby enabling the development of a new type of hydrophobic materials.

We report design and structural characterization of six new coordination polymers fabricated from PbCl

Four new coordination compounds have been obtained by the reaction of copper(II) acetate with SCS [bis(4-pyridylthio)methane], namely, [Cu2(AcO)4(SCS)] (1), [Cu2(AcO)4(SCS)]·solv (2), [Cu4(AcO)8(SCS)5(H2O)6]·4H2O (3), and [Cu4(OH)2(AcO)6(SCS)2]·10H2O (4). Structural diversity is achieved by the copper acetate moiety in combination with the flexibility of the SCS ligand. X-ray structural analysis revealed that the compounds have different structural motifs: linear chains in 1, zigzag chains in 2, undulated tetramers in 3, and ladder-like chains in 4. The structures are further connected through hydrogen-bonding interactions with trapped solvent molecules in the crystal lattices (2–4). Guest molecules have a decisive influence on the final crystal system for 2–4. Compound 2 exhibits a temperature-induced single-crystal to single-crystal (SC–SC) transformation, and phase transitions from 2 and 3 to 1 have been found in an irreversible desolvation or recrystallization process.

The reaction of the ditopic bis(benzoylhydrazone) of isophthalaldehyde (H2L) with copper(II) acetate in methanol under aerobic conditions afforded a green solid that contains the tetranuclear complex [Cu4L*2(OCH3)2] (1). The ligand L*, a bis(benzoylhydrazone) of 2,6-diformylphenol, resulted from hydroxylation of the corresponding isophthalaldehyde derivative. H2L and 1 were characterized by different spectroscopic techniques, and their molecular structures were confirmed by single-crystal X-ray diffraction. The reaction of H2L with copper(II) under argon, on the other hand, resulted in a brown diamagnetic solid [Cu2L]·H2O (2) containing copper(I), which was readily transformed into 1 when exposed to air. In contrast, the reaction with [Cu(CH3CN)4][BF4] afforded a mononuclear complex [Cu(H2L)][BF4]·H2O (3), and single crystals of [Cu(H2L)2][BF4] (4) were isolated from its dichloromethane solution. H2L cleaved plasmid DNA in the presence of copper(II) independently of any reducing agent, but more efficiently when ascorbate was present. The cleavage process is likely oxidative because the enzyme catalase, which decomposes hydrogen peroxide, quenched the reaction. In the absence of ascorbate, the ligand H2L presumably acts as the reductant in the redox reaction, as exploited also in the synthesis of 1. As a consequence, a variety of reactive oxygen species were generated, eventually also leading to the cleavage of DNA (“self-activating” chemical nuclease).

We report the synthesis and characterization of six novel coordination polymers (CPs) based on M(II) (M: Zn and Co), di-, tri-, and tetracarboxylate linkers and two novel bis-pyridylalcohol 1,7-bis{(pyridin-n′-yl)methanol}-1,7-dicarba-closo-dodecaboranes (n′ = 3, L1; n′ = 4, L2) ligands. The polycarboxylates are terephthalic acid (H2BDC), 1,3,5-benzenetricarboxylic acid (H3BTB), and 1,2,4,5-tetrakis(4-carboxyphenyl)benzene (H4TCPB). Structural description of CPs reveals the flexibility of the carborane ligands and their ability to construct extended structures. The CP containing Co(II), BTB, and L2 behaves as a crystalline sponge for a variety of guests, showing a higher affinity for aromatic guest molecules. Single-crystal nanoindentation experiments indicate that a high number of specific interactions between the guests and the CP framework result in a high elastic modulus and hardness values., This work was supported by the EU FP7 ERC-Co 615954. M.Y.T., T.F., F.T., C.V. and J.G.P. acknowledge MEC grants CTQ2013-44670-R and the Generalitat de Catalunya (2014/ SGR/149) for financial support. J.S. thanks the Generalitat de Catalunya 2014/SGR/1015 for financial support and MAT2014-57960-C3-1-R for partial financial support and associated FEDER is acknowledged. The Intramural CSIC (201530E011) provided X-ray structural facilities for this work. ICMAB and ICN2 acknowledge the support of the Spanish MINECO through the Severo Ochoa Centers of Excellence Program, under Grants SEV-2015-0496 and SEV-2013-0295. F.T. is enrolled in the UAB Ph.D. program and acknowledges the China Scholarship Council (CSC) for her Ph.D. grant (201506060171).

Four hydrogen-bonded assemblies of formula [M(dpds)2(OH2)2]A2·nH2O (A = anion) are described. These assemblies result from the second-sphere coordination interactions between the 1D coordination polymers [M(dpds)2(OH2)2]2+, M = Zn(II) and Cu(II), dpds = 4,4′-dipyridyldisulfide, and the pyridine-3-sulfonate (3pySO3−) or hydrogenfumarate (Hfum−) anions. Significantly, supramolecular structural variations are observed depending on the presence of water lattice molecules, which formed discrete aggregates when the Hfum− anion was used. The effects of geometrical variations in the building blocks are also evident on using Jahn–Teller-distorted divalent Cu(II) ions or regular octahedral species based on Zn(II) ions. The second-sphere effects on the stabilization of the compounds are illustrated by TGA experiments.

Recrystallization from dmso of the previously prepared compound [Co(chel)(H 2 O) 4 ] (chel = 4-oxo-4 H -pyran-2,6-dicarboxylate), led to the new one-dimensional coordination polymers 1a and 1b , which are linkage isomers of formula [Co(chel)(dmso)(OH 2 ) 3 ]·H 2 O. Also the recrystallization from dmso of the previously prepared [Zn(chel)(H 2 O) 2 ] allow the isolation of the one-dimensional coordination polymer [Zn(chel)(dmso) 2 ] ( 2 ). [Co(chel)(H 2 O) 4 ] was characterized by elemental analysis, IR and electronic spectroscopy, magnetic measurements at room temperature and thermogravimetric analysis. X-ray single crystal diffraction of 1a , 1b and 2 showed the coordinative behavior of the chelidonate ligand in each compound as well as the different participation of this ligand in the corresponding metallosupramolecular organization.

Tricarbonylrhenium(I) and -technetium(I) halide (halide = Cl and Br) complexes of ligands derived from 4,5-diazafluoren-9-one (df) and 1,10-phenanthroline-5,6-dione (phen) derivatives of benzoic and 2-hydroxybenzoic acid hydrazides have been prepared. The complexes have been characterized by elemental analysis, MS, IR, 1 H NMR and absorption and emission UV/Vis spectroscopic methods. The metal centres (Re I and Tc I ) are coordinated through the nitrogen imine atoms and establish five-membered chelate rings, whereas the hydrazone groups stand uncoordinated. The 1 H NMR spectra suggest the same behaviour in solution on the basis of only marginal variations in the chemical shifts of the hydrazine protons.

Materials with surfaces that can be switched from high/superhydrophobicity to superhydrophilicity are useful for myriad applications. Herein, we report a metal–organic framework (MOF) assembled from Zn ions, 1,4-benzenedicarboxylate, and a hydrophobic carborane-based linker. The MOF crystal-surface can be switched between hydrophobic and superhydrophilic through a chemical treatment to remove some of the building blocks., This work was supported by the EU FP7 ERC-Co 615954.M.Y.T., F.T. , C.V., and J.G.P. thank MINECO grants CTQ2013-44670-R and the Generalitat de Catalunya (2014/SGR/149) for financial support. The Intramural CSIC (201530E011) provided X-ray structural facilities for this work. I.I. thanks the MINECO for a RyC fellowship and V. G. is grateful to the Generalitat de Catalunya for a Beatriu de Pinos Fellowship. ICMAB and ICN2 acknowledge the support of the Spanish MINECO through the Severo Ochoa Centers of Excellence Program, under Grant SEV-2015-0496 and SEV-2013-0295

Here we report the use of a pillaring strategy for the design and synthesis of three novel amide-functionalized metal-organic frameworks (MOFs), TMUs-22/-23/-24, isoreticular to the recently reported imine-functionalized TMU-6 and TMU-21 MOFs. An extensive study of their CO sorption properties and selectivity for CO over N, from single gas sorption isotherms to breakthrough measurements, revealed that not only the incorporation of amide groups but also their accessibility is crucial to obtain enhanced CO sorption and CO/N selectivity. Therefore, the MOF with more accessible amide groups (TMU-24) shows a CO/N selectivity value of ca. 10 (as revealed by breakthrough experiments), which is ca. 500% and 700% of the selectivity values observed for the other amide-containing (TMU-22 and TMU-23) and imine-containing (TMU-6 and TMU-21) MOFs., This work was supported by the Spanish MINECO (projects PN MAT2015-65354-C2-1-R and MAT2013-45008-P), the Catalan AGAUR (project 2014 SGR 80), and the ERC under the EU FP7 (ERC-Co 615954). I.I. and E.V.R.F. thank the MINECO for their RyC fellowships RYC-2010-06530 and RyC-2012-11427 and V.G. is grateful to the Generalitat de Catalunya for a Beatriu de Pinos Fellowship (2014 BP-B00155). ICN2 acknowledges the support of the Spanish MINECO through the Severo Ochoa Centers of Excellence Program, under Grant SEV-2013-0295. E.V.R.F. and J.S.A. acknowledge the Generalitat Valenciana for PROMETEOII/2014/004. Support of this investigation by Tarbiat Modares University is gratefully acknowledged.

The synthesis, X-ray crystallographic structure, and water uptake measurements of the first coordination polymer made of a cyclodextrin and a transition metal ion (in this case, Cu) are shown. This coordination polymer is made by connecting paddle-wheel Cu units through a γ-cyclodextrin functionalized with eight carboxylate groups, is stable in water, and shows selective water-induced reversible structural transformations., This work was supported by the Spanish MINECO (project PN MAT2012-30994) and the Catalan AGAUR (project 2014 SGR 80). I.I. thanks the MINECO for a RyC grant (RYC-2010-06530). H.X. thanks the Generalitat de Catalunya for an FI grant. ICN2 acknowledges the support of the Spanish MINECO through the Severo Ochoa Centers of Excellence Program, under Grant SEV-2013-0295.

Materials based on the cationic copper(II) hexanuclear 18-membered metallacrown [18-MCCuII-N(2ph) -6] (2phH=2-piconyl hydrazide) and tetrafluoroborate, perchlorate, nitrate, sulfate, and perrhenate anions were prepared by an easy method in aqueous medium. Single-crystal X-ray characterization of six members of this new family of complexes showed that the anions are attached to the metallacrown by direct coordination to a copper cation or by hydrogen-bonding interaction with the center of the hexamer. The stable cationic nature of the complexes and their ability to bind different anions allows them to adsorb and immobilize environmentally relevant anions such as MO (M=Tc, Re). The MO trapping capacities suggest that these materials would be useful in the treatment of oxoanionic contaminants in water., Financial support from ERDF (EU), Ministerio de Ciencia e Innovación (Spain), and the Xunta de Galicia (Spain) under research projects CTQ2010-19386/BQU and 10TMT314002PR is gratefully acknowledged. A.B.L. thanks the Xunta de Galicia for a postdoctoral contract under the “Ángeles Alvariño” program.

Herein we report a study on water adsorption/desorption-triggered single-crystal to single-crystal transformations in a MOF, by single-crystal and humidity-controlled powder X-ray diffraction and water-sorption measurements. We identified a gate-opening effect at a relative humidity of 85% upon water adsorption, and a gate-closure effect at a relative humidity of 55 to 77% upon water desorption. This reversible breathing effect between the "open" and the "closed" structures of the MOF involves the cleavage and formation of several coordination bonds., This work was supported by the Spanish MINECO through project PN MAT2015-65354-C2-1-R and by EU FP7 through ERC-Co grant agreement no. 615954. I. I. and J. A. thank the MINECO for a RyC grant (RYC-2010-06530) and a FPU predoctoral grant (AP2010-5934), respectively. J. A. also thanks the Chemistry PhD programme of the Universitat Autònoma de Barcelona. A. C. thanks MINECO and Junta de Andalucía through research projects MAT2013-41836-R and P12-FQM-1656, respectively. ICN2 acknowledges the support from the Spanish MINECO through the Severo Ochoa Centres of Excellence Programme, under Grant SEV-2013-0295.

Nine new coordination compounds have been synthesized by the reaction of salts of bivalent metal ions (a=Zn(II) , b=Cu(II) , c=Ni(II) , d=Co(II) ) with the bis(benzoylhydrazone) derivative of 4,6-diacetylresorcinol (H4 L). Three kinds of complexes have been obtained: homodinuclear compounds [M2 (H2 L)2 ]⋅nH2 O (1 a, 1 b, 1 c, and 1 d), homotetranuclear compounds [M4 (L)2 ]⋅n(solv) (2 a and 2 c), and heterotetranuclear compounds [Zn2 M2 (L)2 ]⋅n(solv) (2 ab, 2 ac, and 2 ad). The structures of the free ligand H4 L⋅2 DMSO and its complexes [Zn2 (H2 L)2 (DMSO)2 ] (1 a*), [Zn4 (L)2 (DMSO)6 ] (2 a*), and [Zn0.45 Cu3.55 (L)2 (DMSO)6 ]⋅2 DMSO (2 ab*) were elucidated by single-crystal X-ray diffraction. The ligand shows luminescence properties and its fluorimetric behavior towards M(II) metals (M=Zn, Cu, Ni and Co) has been studied. Furthermore, the solid-state luminescence properties of the ligand and compounds have been determined at room temperature. (1) H NMR spectroscopic monitoring of the reaction of H4 L with Zn(II) showed the deprotonation sequence of the OH/NH groups upon metal coordination. Heteronuclear reactions have also been monitored by using ESI-MS and spectrofluorimetric techniques., Financial support from the Spanish Ministry of Education and Science (project CTQ2010–19386/BQU) is gratefully acknowledged. A. B. L. thanks the Xunta de Galicia for a postdoctoral contract under the “ÁngelesAlvariño” program.

We report the synthesis of two new three-dimensional coordination polymers (CPs) based on Co(II), adenine, and aromatic tetracarboxylate linkers. Adenine exhibits bidentate binding modes in both CPs, coordinating through the N3 and N9 sites in a first compact CP and through the more rare N3 and N7 sites in a second open, flexible, and H2O-responsive CP. These differences together with an analysis of the extended coordination structures made of adenine reported in the Cambridge Structural Database illustrate the rich coordination versatility of adenine as a building block for CPs. Although the latter CP is nonporous to N2 or CO2, it shows a reversible and detectable color change from pink to purple, and vice versa, upon hydration and dehydration, respectively., I.B. thanks SENESCYT-Ecuador for a Ph.D. fellowship. I.I. and K.C.S. are grateful to MINECO, for a Ramon y Cajal grant, and to the EU, for a Marie Curie Fellowship (300390 NanoBioMOFs FP7-PEOPLE-2011-IEF), respectively. ICN2 acknowledges support of the Spanish MINECO through the Severo Ochoa Centers of Excellence Program under Grant SEV-2013-0295.

The potentially multidentate (O2N-NO) trianionic bis(bencylhydrazone) derived from 4-hydroxyisophthaldehyde (H3L) ligand has been synthesized and characterized. The coordinative behavior of the ligand has been explored toward different MII salts (M = Co, Ni, Zn, and Cu), and four complexes, of general formula [M(HL)]·solv (2·solv = molecules of water, dmf, or dmso), have been isolated and characterized. Furthermore, the species [M(H2L)2] ·solv (M = Co, 1a·solv; M = Ni, 1b·solv; solv = molecules of water and/or dmf), where the ligand is monodeprotonated and tridentate, has also been detected. The structures of H3L, four solvates of {[Cu(HL)]·solv}n (2c·solv), 1a·5H2O, and 1b·H2O·3dmf were determined by single-crystal X-ray diffraction. The effect of weak interactions on the crystal packing has also been analyzed. The thermal stability and the structural dynamics of the 2c·solv systems have also been investigated. © 2013 American Chemical Society., Financial support from Xunta de Galicia (Spain) is gratefully acknowledged (research project 10TMT314002PR). A. B. L. thanks the Xunta de Galicia for a postdoctoral contract under the “Ángeles Alvariño” Program.

The possibility of controlling the formation of copper(II) coordination polymers based on the rigid carboxylate ligand 1,3,5-benzenetricarboxylic acid (H3btc) and an N,N-divergent spacer with conformational flexibility, bis(4-pyridylthio)methane (SCS), was investigated. The new coordination polymers 1∞[Cu(H2btc)2(SCS)] (1) and 2∞[Cu(Hbtc)(SCS)2]·H2O (2) have been prepared and characterized. Compounds 1 and 2 were obtained as a mixture and optimization of the synthetic conditions allowed the isolation of pure phases in high yield. Topological analysis showed the interpenetration of three networks with a vcm-type topology in 2. The thermal stability and the structural dynamics of these systems have also been investigated.