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. 2024 Feb 9;63(8):3824–3834. doi: 10.1021/acs.inorgchem.3c04060

Fine Tuning the Hydrophobicity of a New Three-Dimensional Cu2+ MOF through Single Crystal Coordinating Ligand Exchange Transformations

Nikos Panagiotou †, Dimitrios A Evangelou ‡, Manolis J Manos ‡, John C Plakatouras ‡, Anastasios J Tasiopoulos †,*
PMCID: PMC10900299  PMID: 38335458

Abstract

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The synthesis, characterization, and single–crystal–to–single–crystal (SCSC) exchange reactions of a new 3D Cu2+ MOF based on 5-aminoisophthalic acid (H2AIP), [Cu6(μ3-ΟΗ)3(ΑΙΡ)4(HΑΙΡ)]n·6nDMF·nH2O - UCY-16·6nDMF·nH2O, are reported. It exhibits a 3D structure based on two [Cu4(μ3–OH)2]6+ butterfly–like secondary building units, differing in their peripheral ligation, bridged through HAIP–/AIP2– ligands. This compound displays the capability to exchange the coordinating ligand(s) and/or guest solvent molecules through SCSC reactions. Interestingly, heterogeneous reactions of single crystals of UCY-16·6nDMF·nH2O with primary alcohols resulted not only in the removal of the lattice DMF molecules but also in an unprecedented structural alteration that involved the complete or partial replacement of the monoatomic bridging μ3–OH– anion(s) of the [Cu4(μ3–OH)2]6+ butterfly structural core by various alkoxy groups. Similar crystal-to-crystal exchange reactions of UCY-16·6nDMF·nH2O with long-chain aliphatic alcohols (CxH2x+1OH, x = 8–10, 12, 14, and 16) led to analogues containing fatty alcohols. Notably, the exchanged products with the bulkier alcohols UCY-16/n-CxH2x+1OH·S′ (x = 6–10, 12, 14, and 16) do not mix with H2O being quite stable in this solvent, in contrast to the pristine MOF, and exhibit a hydrophobic/superhydrophobic surface as confirmed from the investigation of their water contact angles and capability to remove hydrophobic pollutants from aqueous media.

Short abstract

A 3D Cu2+ MOF is reported with a capability to exchange through single-crystal-to-single-crystal (SCSC) transformation reactions, with various primary alcohols (CxH2x+1OH, x = 1−7), the bridging μ3−OH− anion(s) of its secondary building units, by μ3-OR− groups. These SCSC exchange reactions as well as crystal-to-crystal ones with long-chain aliphatic alcohols (CxH2x+1OH, x = 8−10, 12, 14, and 16) led to analogues displaying hydrophobic/superhydrophobic surfaces, high stability in water, and affinity for hydrophobic pollutants.

Introduction

During the past couple of decades, materials based on metal organic frameworks (MOFs) are continuously being considered for several applications.1 Gas storage/separation,2−5 catalysis,6,7 sensing,8,9 removal of pollutants from the environment,10−12 and water harvesting13−15 are among the most prominent applications of MOFs in areas of global interest.

The exploding progress in the synthesis of functional MOFs allows the design of materials exhibiting the desired characteristics for targeted application. For example, by utilizing the molecular building block (MBB) approach, MOFs with varying network topologies and structural characteristics can be readily designed and synthesized16 giving rise to materials with a plethora of different metal ions, organic ligands, secondary building units (SBUs), functional groups, network topologies, and so forth. Among the various building blocks appearing in MOF chemistry, the Cu2+ paddle - wheel secondary building unit (SBU) consisting of two Cu2+ ions adopting a square pyramidal coordination geometry is one of the most common ones.17 In fact, some of the most well–known MOFs including HKUST-1 ([Cu3(btc)2(H2O)3]; btc3–: 1,3,5-benzenetricarboxylate) are based on this dinuclear SBU.1,18 For this reason, several groups19−23 including ours24,25 have been involved in the synthesis of Cu2+ paddle wheel-based MOFs exhibiting interesting structural characteristics and promising gas sorption properties. However, it is well–known that Cu2+ MOFs including HKUST-118,26−28 as well as other MOFs suffer from limited hydrolytic stability. One method to enhance the hydrolytic stability of MOFs is to increase the hydrophobicity of their pore surface and/or external crystal surface.29−33 Such hydrophobic MOFs have attracted significant interest not only because of their stability in water but also due to their diverse potential applications including humid CO2 capture,34−36 alcohol/water, organic molecules/water and oil/water separations,37,38 removal of pollutants from air or water,39,40 substrate-selective catalysis,41 and anticorrosion/self-cleaning coatings.42,43 As a result of this interest, several synthetic methods have been reported that lead to MOFs with enhanced hydrophobicity. These synthetic methods include the de novo synthesis of MOFs using ligands containing hydrophobic functional groups29,30,32,34,35,39−42,44,45 and also postsynthesis modifications (PSM)29,31,33,46−50 of well–known MOFs. Some examples of the latter include external coating with octadecylamine on MIL-101(Cr), UiO-66, HKUST-1, and ZIF-67 MOFs31 and functionalization with aliphatic alkane groups in IRMOF-3 and MIL-53(Al)–NH2 through amide bond formation upon reaction of the −NH2 group of the 2-amino-1,4-benzenedicarboxylate ligand with various alkyl anhydrides.33 Moreover, the fabrication of MOF-based composites is another PSM strategy to encapsulate and immobilize MOF particles in a hydrophobic matrix.51,52

Single–crystal–to–single–crystal (SCSC) transformations are a subcategory of the PSM method that has attracted a significant interest because it allows the acquisition of direct structural information for the achieved modifications through single crystal X-ray crystallography. Such transformations can take place from the heterogeneous reactions of single crystals of a MOF with chemical species being in the liquid or gas phase or from their exposure to an external stimuli and can lead to the targeted modification of their structure53−61 and the fine-tuning of their properties.55,56,59 Several SCSC transformations have been reported in the literature which can be summarized in the following three groups: (a) insertion/removal of guest molecules,57,58,60,62−66 (b) modifications of the parent structure including the coordination mode of organic ligands, or metal ion exchange (transmetalation)/insertion,59,60,67−69 and (c) changes in the coordination environment of the metal ions.53−56,67,68,70,71 Interestingly, such SCSC transformations have allowed not only the improvement of the magnetic,60,61 photoluminescence,55 sorption,62,63,69,72,73 and catalytic73,74 properties of MOFs but also the elucidation of the exact mechanisms of these processes. Although significant progress has been realized in the investigation of a series of SCSC transformations of various types, such exchange reactions leading to the increase of the hydrophobicity of MOFs are very uncommon.

We herein report a new 3D Cu2+ MOF based on 5-aminoisophthalic acid (H2AIP) and tetranuclear, butterfly-like SBUs with the molecular formula [Cu6(μ3-ΟΗ)3(ΑΙΡ)4(ΗΑΙΡ)]n·6nDMF·nH2O - UCY-16·6nDMF·nH2O. This compound exhibited exceptional SCSC transformation properties that involved either the exchange of only guest solvent molecules or both guest solvents and coordinating ligand(s). The latter took place from heterogeneous reactions of single crystals of UCY-16·6nDMF·nH2O with normal and primary alcohols which led to the complete/partial replacement of the guest solvent molecules and the monoatomic μ3-ΟΗ– anion(s) of the [Cu4(μ3–OH)2]6+ butterfly–like core by the corresponding alcohol/alkoxy groups leading to UCY-16/n-CxH2x+1OH·S′ (x = 1, 2, 3, 4, 5, 6, and 7; S′ = lattice solvents). Interestingly, such SCSC transformations involving a triply bridging anion of the structural core of the SBU of a MOF have not been observed previously. Crystal-to-crystal exchange reactions involving long-chain aliphatic alcohols (CxH2x+1OH, x = 8–10, 12, 14, and 16) were also investigated resulting in analogues containing fatty alcohols. The synthesized exchanged analogues display hydrophobic/superhydrophobic surfaces as indicated by the determination of their water contact angles and high stability in water, in contrast to the pristine MOF which is unstable in water. Overall, the reported SCSC transformations provide an alternative, unprecedented strategy for fine-tuning the hydrophobicity of MOFs.

Experimental Section

Materials

Reagent grade chemicals were obtained from commercial sources (Aldrich, Merck, Alfa Aesar, TCI, etc.) and used without further purification. All synthetic procedures were carried out in air.

Synthesis

Synthesis of [Cu6(μ3-ΟΗ)3(ΑΙΡ)4(ΗΑΙΡ)]n·6nDMF·nH2O - UCY-16·6nDMF·nH2O

Solid Cu(NO3)2·2.5H2O (0.08g, 0.34 mmol) was added in one portion to a clear solution of H2AIP (0.1 g, 0.55 mmol) in DMF/H2O (8 mL/2 mL) in a 20 mL glass vial, and the reaction mixture was sonicated until complete dissolution of the reactants. The vial was sealed, placed in an oven at 100 °C, and left undisturbed for ∼4 to 6 h. Then, it was cooled to room temperature, and X-ray quality green plates of UCY-16·6nDMF·nH2O were isolated by filtration, washed with DMF (3 × 5 mL), and dried in air. The reaction yield was ∼82% based on Cu(NO3)2·2.5H2O. Anal. Calcd UCY-16·6nDMF·nH2O: C58H73N11O30Cu6, C 39.02, H 4.12, N 8.63; Found: C 38.87, H 4.27, N 8.39.

Preparation of UCY-16/S (S = Benzene (Bz), Toluene (Tol), Chlorobenzene (PhCl))

In 5 mL of the corresponding solvent, in a 23 mL Teflon lined Parr acid digestion bomb, were added single crystals of the pristine UCY-16·6nDMF·nH2O (0.1 g, 0.075 mmol). The bomb was sealed, placed in an oven at 100 °C, left undisturbed for 3 days for Bz and Tol and 5 days for PhCl and then was removed from the oven and remained for ∼3 h at room temperature to cool down. The crystals of the corresponding modified product, UCY-16/S, were isolated by filtration and dried in air or placed in the corresponding pure solvent for further studies. Anal. Calcd: UCY-16/Bz: (UCY-16·3Bz·DMF·2H2O C61H58N6O26Cu6), Calc.: C 43.81, H 3.50, N 5.02; Found: C 43.52, H 3.63, N 5.19. UCY-16/Tol: (UCY-16·3Tol·DMF·2H2O C64H64N6O26Cu6), Calc.: C 44.94, H 3.54, N 4.91; Found: C 44.67, H 3.71, N 4.63. UCY-16/PhCl: (UCY-16·3PhCl·H2O C58H46N5O24Cl3Cu6), Calc.: C 41.35, H 2.75, N 4.16; Found: C 41.65, H 2.87, N 4.34.

Preparation of UCY-16/MeCN

Single crystals of the pristine UCY-16·6nDMF·nH2O (0.1 g, 0.075 mmol) were suspended in 5 mL of MeCN in a glass vial. The vial was left at room temperature for 7 days. The solvent was decanted and exchanged with fresh solvent (5 mL) every day. The crystals of the modified product, UCY-16/MeCN, were isolated by filtration, dried in air, or placed in MeCN for further studies. Anal. Calcd: UCY-16/MeCN: (UCY-16·6MeCN·2H2O: C52H51N11O25Cu6), Calc.: C 38.76, H 3.19, N 9.56; Found: C 38.84, H 3.36, N 9.73.

Preparation of (UCY-16/n-CxH2x+1OH)·S′ (x = 1, 2, 3, 4, 5, 6, 7; S′ = Lattice Solvents)

In 10 mL of the corresponding primary alcohol, to a 23 mL Teflon lined Parr acid digestion bomb, were added single crystals of the pristine UCY-16·6nDMF·nH2O (0.1 g, 0.075 mmol). The bomb was sealed and placed in an oven at 60 °C for 2, 3, and 5 days for CH3OH, C2H5OH, and n-C3H7OH, respectively, at 100 °C for 4 and 5 days for n-C4H9OH and n-C5H11OH, respectively, at 130 °C for 7 days for n-C6H13OH and at 150 °C for 7 days for n-C7H15OH and then was removed from the oven and kept for ∼3 h at room temperature to cool down. The crystals of the corresponding modified product, (UCY-16/n-CxH2x+1OH)·S′ (x = 1, 2, 3, 4, 5, 6, 7; S′ = lattice solvents), were isolated by filtration, washed with the corresponding primary alcohol, and dried in air or placed in the corresponding pure solvent for further studies. Anal. Calcd: UCY-16/CH3OH: ((UCY-16/CH3OH)·7CH3OH·3.5H2O, C49.5H69N5O33.5Cu6), Calc.: C 36.00, H 4.21, N 4.24; Found: C 36.13, H 4.04, N 4.33; UCY-16/C2H5OH: ((UCY-16/C2H5OH)·7C2H5OH·2H2O, C56H79N5O32Cu6), Calc.: C 39.21, H 4.64, N 4.08; Found: C 39.37, H 4.81, N 3.95; UCY-16/n-C3H7OH: ((UCY-16/n-C3H7OH)·5n-C3H7OH, C58H75N5O28Cu6), Calc: C 41.68, H 4.52, N 4.19; Found: C 41.83, H 4.89, N 4.36; UCY-16/n-C4H9OH: ((UCY-16/n-C4H9OH)·5n-C4H9OH·0.5DMF, C63.5H86.5N5.5O28.5Cu6), Calc.: C 43.23, H 4.94, N 4.37; Found: C 43.46, H 4.79, N 4.64; UCY-16/n-C5H11OH: ((UCY-16/n-C5H11OH)·5n-C5H11OH, C70H99N5O28Cu6), Calc: C 45.70, H 5.42, N 3.81; Found: C 45.47, H 5.72, N 4.05; UCY-16/n-C6H13OH: ((UCY-16/n-C6H13OH)·3n-C6H13OH, C64H83N5O26Cu6), Calc: C 44.70, H 4.86, N 4.07; Found: C 44.58, H 4.72, N 4.18; UCY-16/n-C7H15OH: ((UCY-16/n-C7H15OH)·3n-C7H15OH, C68H91N5O26Cu6), Calc: C 45.99, H 5.17, N 3.94; Found: C 46.17, H 5.06, N 3.89.

Preparation of UCY-16/n-CxH2x+1OH·S′ (x = 8–10, 12, 14, and 16; S′: Lattice Solvents)

In 15 mL of the corresponding liquid primary (n = 8–10) alcohol or 15g of the corresponding solid primary alcohol (n = 12, 14, and 16), in a 23 mL Teflon lined Parr acid digestion bomb, were added single crystals of the pristine UCY-16·6nDMF·nH2O (0.1 g, 0.075 mmol). The bomb was sealed and placed in an oven operating at 150 °C, left undisturbed for 10 days, and then was removed from the oven and left at room temperature for 4 h to cool down. The crystals of the corresponding modified product, UCY-16/n-CxH2x+1OH (x = 8–10, 12, 14 and 16), were isolated by filtration, washed with the corresponding liquid primary alcohol and hexane or only with hexane (in the case of solid primary alcohols), and dried in air. Anal. Calcd: UCY-16/n-C8H17OH: ((UCY-16/n-C8H17OH)·2n-C8H17OH, C64H81N5O25Cu6), Calc: C 45.17, H 4.80, N 4.12; Found: C 44.85, H 4.92, N 4.01; UCY-16/n-C9H19OH: ((UCY-16/n-C9H19OH)·2n-C9H19OH, C67H87N5O25Cu6), Calc: C 46.15, H 5.03, N 4.02; Found: C 46.32, H 5.26, N 3.97; UCY-16/n-C10H21OH: ((UCY-16/n-C10H21OH)·1.5n-C10H21OH·DMF, C68H89N6O25.5Cu6), Calc: C 45.89, H 5.04, N 4.72; Found: C 46.05, H 5.17, N 4.69; UCY-16/n-C12H25OH: ((UCY-16/n-C12H25OH)·1.5n-C12H25OH·DMF, C73H99N6O25.5Cu6), Calc: C 47.40, H 5.39, N 4.54; Found: C 47.57, H 5.63, N 4.49; UCY-16/n-C14H29OH: ((UCY-16/n-C14H29OH)·1n-C14H29OH·DMF, C71H94N6O25Cu6), Calc: C 47.04, H 5.23, N 4.64; Found: C 47.32, H 5.01, N 4.89; UCY-16/n-C16H33OH: ((UCY-16/n-C16H33OH)·1n-C16H33OH·DMF, C75H102N6O25Cu6), Calc: C 48.20, H 5.50, N 4.50; Found: C 48.36, H 5.78, N 4.29.

Preparation of MOF Films for Water Contact Angle Measurements

30 mg of UCY-16/n-CxH2x+1OH·S′ (x = 6, 8–10, 12, 14, and 16) was dispersed in 1.5 mL of CH2Cl2 in a glass vial. The mixture was subjected to ultrasonication for 10 min and kept under stirring. A small portion of the resulting suspension was spread on a microscope coverslip using a Pasteur pipet and dried in air. This step was repeated several times until the slip was covered with a dense film of the MOF.

Isolation of the Magnetic superhydrophobic Composite UCY-16/n-C16H33OH-Fe3O4

90 mg of UCY-16/n-C16H33OH and 30 mg of Fe3O4 were mixed in a 10 mL glass vial containing 4 mL of acetone. The mixture was stirred for 15 min, and the magnetic composite was isolated via centrifugation and dried in the air.

Stability Tests

Stability in organic solvents was investigated as follows: in 10 mL of the corresponding organic solvent were suspended 50 mg of the MOF and the mixture was stirred for ∼72 h, while the solvent was replenished every 24 h. The powder was then isolated by filtration and analyzed by pXRD. Stability in aqueous solutions was investigated following the below procedure: 50 mg of each compound was added in 5 mL of water and the suspension was stirred for 24 h. The powder was then isolated by filtration and analyzed by pXRD.

Physical Measurements

Elemental analyses (C, H, and N) were performed by the in-house facilities of the University of Cyprus, Chemistry Department. IR spectra were recorded on ATR in the 4000–700 cm–1 range using a Shimadzu Prestige −21 spectrometer. pXRD patterns were recorded on a Shimazdu 6000 Series X-ray diffractometer (Cu Kα radiation, λ = 1.5418 Å). Thermal stability studies were performed with a Shimadzu TGA 50 thermogravimetric analyzer. Water contact angles were determined from digital images obtained with the use of smartphone equipped with macro-lens, by using the drop shape analysis utility of the ImageJ software, particularly the low-bond axisymmetric drop shape analysis (LBADSA) method.75,76 The contact angles were further verified using an Attension Theta Flex (Biolin Scientific) contact angle meter.

Single Crystal X-ray Crystallography

Single crystal X-ray diffraction data were collected on a Rigaku Supernova A diffractometer equipped with a CCD area detector utilizing Cu–Kα (λ = 1.5418 Å) radiation. A suitable crystal was mounted on a Hampton cryoloop with Paratone-N oil and transferred to a goniostat, where it was cooled for data collection. The structures were solved by direct methods using SHELXT and refined on F2 using full-matrix least-squares using SHELXL14.1.77 Software packages used are as follows: CrysAlis CCD for data collection, CrysAlis RED for cell refinement and data reduction,78 WINGX/Olex2 for geometric calculations,79,80 and DIAMOND for molecular graphics.81 The non-H atoms were treated anisotropically, whereas the aromatic hydrogen atoms were placed in calculated, ideal positions and refined as riding on their respective carbon atoms. Several restraints (DFIX, SIMU, RIGU, and DELU) were used to fix the thermal ellipsoids and geometry of the aliphatic alcohols and the corresponding bridging alkoxy groups. Electron density contributions from disordered guest molecules were handled using the SQUEEZE procedure from the PLATON software suit.82 Selected crystal data for the pristine MOF UCY-16·6nDMF·nH2O and the exchanged analogues are summarized in Table S1 in SI. CCDC 2301078–2301089 contain the supplementary crystallographic data for this paper.

Results and Discussion

Structure Description

Compound UCY-16·6nDMF·nH2O was synthesized under solvothermal conditions from the reaction of Cu(NO3)2·2.5H2O with H2AIP in DMF/H2O (8/2 mL) in a 1: ∼ 1.6 molar ratio at 100 °C. UCY-16·6nDMF·nH2O was obtained as light green bladed crystals in ∼82% yield based on Cu(NO3)2·2.5H2O. The isolation of compound UCY-16·6nDMF·nH2O highlights the ability of the widely used, in Cu2+ MOF chemistry,83−85ligand H2AIP to afford new compounds, probably due to its significant bridging capability (vide infra). Structure elucidation of compound UCY-16·6nDMF·nH2O revealed that it crystallizes in the orthorhombic Pbca space group.

The asymmetric unit of UCY-16·6nDMF·nH2O consists of six copper(II) cations, three hydroxide anions, five 5-aminoisophthalate ligands, as well as six DMF and one water lattice solvent molecules. The secondary building units (SBUs) of this compound are two tetranuclear clusters in which the four Cu2+ cations are held together through two monoatomic triply bridging hydroxides (μ3–OH–) giving rise to [Cu4(μ3–OH)2]6+ butterfly–like subunits. The peripheral ligation of one of these [Cu4(μ3–OH)2]6+ subunits (containing atoms Cu(1)–Cu(4) and O(1)/O(2)) is completed by seven carboxylate ligands and two terminal −NH2 groups from nine different 5-aminoisophthalate anions, whereas this of the second one (containing atoms Cu(5), Cu(6) and O(3)) by 6 carboxylate ligands and two terminal −NH2 groups from eight different 5-aminoisophthalate groups (Figure 1a).

Figure 1.

Figure 1

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(a) [Cu4(μ3–OH)2(COO)7/6(NH2)2]−1/0 butterfly–like SBUs of UCY-16·6nDMF·nH2O. Symmetry operation to generate equivalent atoms: #1, −x + 2, −y + 1, −z, (b) Coordination modes of the ligands found in UCY-16·6nDMF·nH2O.

The AIP ligands can be separated in two groups (Figure 1b): (a) ligands B, C and E, which connect five Cu2+ ions (i.e., μ5-ligands), using all their donor atoms; their carboxylates bridge two Cu2+ ions adopting the common syn-syn mode and the amino group acts as a terminal ligand and (b) ligands A and D which connect three Cu2+ ions (i.e., μ3-ligands) using their two carboxylate groups (the amino group remains unbound); one of their carboxylates bridges two metal ions in the common syn-syn mode whereas the other one is terminally ligated to Cu2+ ion either in a syn fashion (ligand A) or in an anti-fashion (ligand D) (Figure 1b). Charge balance considerations indicate that one of the aminoisophthalate ligands exhibits −1 charge; this may happen either because one of the terminally ligated carboxylate groups of ligands A or D is not deprotonated or because one of the unbound amino groups of the same ligands is protonated.

The tetranuclear butterfly–like SBUs are located on a thick layer with an approximate thickness of 7 Å running parallel to the ac plane of the unit cell. The neighboring butterfly–like SBUs are connected on the ac plane through the AIP2– ligands B, C, and E; each butterfly is connected to six ligands via four bridging carboxylates and two amino nitrogen atoms, being 6 connected nodes while the AIP2– ligands are three connected nodes leading to the formation of a binodal kagome dual plane net (kgd, point symbol: {43}2{46.66.83}) (Figure 2a). The connection of the kgd dual plane nets is achieved by the linkers A and D resulting in the formation of a 3D framework. The structural description of UCY-16·6nDMF·nH2O, however, is getting complicated when ligands A and D are considered; those in addition to the different coordination modes of the two butterflies above and below the ac plane lead to a unique and complex topological network which is discussed in detail in the SI (Figures S1 and S2).

Figure 2.

Figure 2

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(a) Connectivity of the butterfly-like SBUs and B, C, and E ligands on the ac plane of the unit cell and the underlying kgd topology. Color code: butterfly centroid, sky blue; AIP aromatic ring centroid, pink. (b) Representation of the 3D framework of UCY-16·6nDMF·nH2O emphasizing the lattice solvent molecules (space-filling model) occupying the solvent accessible volume of UCY-16·6nDMF·nH2O (ball and stick model). (c) Space-filling representation of the framework of UCY-16·6nDMF·nH2O along the c-axis emphasizing the rectangular channels with an approximate diameter ∼6 Å.

The framework pores accommodate guest solvent molecules (water and DMF) that are involved in hydrogen bonding interactions with the amine and the carboxylate groups of the AIP2–/HAIP– ligands as well as the bridging μ3–OH– groups of the SBUs (Figures 2b and S3). The solvent accessible volume was calculated by PLATON not considering the lattice solvent molecules and was found to be ∼6682 Å3, which corresponds to 48.5% of the unit cell volume. The 3D structure contains rectangular channels along the c-axis with an approximate diagonal of ∼6 Å as found by PLATON (considering the van der Waals radii of the atoms and excluding all solvents of the pores)82 (Figure 2c).

Chemical and Thermal Stability

The stability of the compound was studied in various common organic solvents as well as in water. Suspensions of compound UCY-16·6nDMF·nH2O (50 mg) in each solvent (10 mL) were left under magnetic stirring for 3 days (concerning the stability studies in organic solvents) or 1 day (stability studies in water). The solid was collected by filtration and analyzed by pXRD. The resulting diffractograms showed that compound UCY-16·6nDMF·nH2O is stable in the organic solvents tested but decomposes in water (Figures S5 and S6).

The thermal stability of compound UCY-16·6nDMF·nH2O was studied by means of thermogravimetric analysis (20–600 °C) (Figure S7) and variable temperature (VT) pXRD (20–300 °C) measurements (Figure S8). The decomposition of UCY-16·6nDMF·nH2O is a multistep process which begins almost at room temperature. The first step is attributed to the removal of the lattice solvent molecules and is completed at ∼250 °C (calculated loss ≈25.6%; found ≈25%). The initial lattice solvent molecule loss is followed by the decomposition of the framework, which is completed at ∼450 °C (calculated loss ≈47.7%; found ≈48%). The residue at 600 °C corresponds to CuO (calculated residue ≈26.7%; found ≈27%). VT-pXRD measurements of the compound UCY-16·6nDMF·nH2O indicate that the framework collapses above 250 °C (Figure S8).

SCSC Guest Solvent Exchange Transformations

Considering the relatively large solvent accessible volume, the suitable pore size for the insertion of solvent molecules (∼6 Å), the presence of various functionalities (i.e., −NH2, −OH– and aromatic sites of the ligands), and the excellent quality of the single crystals of compound UCY-16·6nDMF·nH2O, it was decided to explore its SCSC transformation properties. In particular, the reactions of UCY-16·6nDMF·nH2O with selected aromatic and aliphatic solvent molecules S (S = Bz, Tol, PhCl, and MeCN) were investigated since their kinetic diameters are close to the pore size of UCY-16·6nDMF·nH2O.86 Heterogeneous SCSC transformation reactions of single crystals of UCY-16·6nDMF·nH2O with the aromatic organic solvents were conducted under autogenous pressure at 100 °C, whereas the reaction with MeCN took place at room temperature (Figures 3 and S9–S12).

Figure 3.

Figure 3

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Representations of the 3D frameworks of UCY-16·6nDMF·nH2O and UCY-16/S (S = Bz, Tol, PhCl, and MeCN). The framework is represented in the ball and stick model, whereas the lattice solvent molecules are represented in the spacefill model. Color code: C gray; O red; N blue; Cu green; Bz orange; Tol yellow; PhCl green; MeCN burgundy.

These reactions resulted in single crystals which were macroscopically very similar in size and shape to those of the pristine compound, and X-ray structural determination of the exchanged analogues revealed that compounds UCY-16/S (S = Bz, Tol, PhCl, and MeCN) have very similar structures to that of the pristine UCY-16·6nDMF·nH2O (Figure 3). Note that for compounds UCY-16/S (S = Bz, Tol, PhCl, and MeCN), several single crystals were examined and proven to have identical unit cell parameters. These exchange reactions led to the insertion of six MeCN, three Bz or PhCl, and two Tol solvent molecules giving rise to the formation of compounds UCY-16·3Bz·DMF·2H2O, UCY-16·3Tol·DMF·2H2O, UCY-16·3PhCl·H2O, and UCY-16·6MeCN·2H2O. Note that in the case of UCY-16/Tol, a third Tol molecule was also located during the structure solution which was severely disordered and could not be modeled properly, and for this reason, it was removed using the SQUEEZE routine of the PLATON package.82 The Bz, Tol, and PhCl molecules of compounds UCY-16/S are in close proximity with AIP2–/HAIP– ligands displaying edge to face π···π stacking (as well as CH3···π interactions in the case of Tol) interactions (Figures S9–S11). On the other hand, MeCN was expected to behave differently than the aromatic organic molecules in these SCSC reactions because it exhibits a significant capability to be involved in hydrogen bonding interactions. This was also proven experimentally since the structure of UCY-16/MeCN features several MeCN and H2O molecules interacting through relatively strong H-bonds with the framework (2.81–3.08 Å) (Figure S12). In particular, the MeCN molecules are hydrogen bonded with the μ3-ΟΗ– bridges as well as with the nitrogen atoms of the AIP2–/HAIP– ligands. In addition, the two lattice water molecules of UCY-16/MeCN are also involved in hydrogen bonding interactions (Figure S12).

A close inspection of the unit cell parameters of the pristine compound UCY-16·6nDMF·nH2O and the exchanged analogues UCY-16/S (S = Bz, Tol, PhCl, and MeCN) revealed that the unit cell of the framework slightly contracts upon insertion of the solvent molecules into the framework. The main modification of the unit cell parameters in the exchanged analogues is a decrease of the b-axis dimension of the unit cell by up to ∼3%, which is responsible for the overall decrease of the unit cell volume. The contraction of the framework upon the insertion of solvent molecules is also reflected on the solvent accessible volume of the exchanged analogues which are (∼6–11%) smaller than that of the pristine compound. (Table S2) Other significant structural modifications also appear in the structures of the exchanged analogues including the decrease of selected bond lengths compared to the corresponding ones of the pristine compound, mainly along the b–axis. Specifically, the Cu–O distances of the monodentate carboxylate groups of ligands A (Cu4–O22) and D (Cu2–O4) in UCY-16/S display average values of 2.04 and 2.55 Å, which are shorter than the corresponding ones of the pristine compound which are 2.21 and 2.68 Å, respectively.

pXRD studies and IR spectra of the exchanged analogues confirmed that the crystallinity and structural integrity of compounds UCY-16/S (S = Bz, Tol, PhCl, MeCN) is retained after the SCSC reactions (Figures S13 and S14). TG analysis revealed that the decomposition of UCY-16/S (S = Bz, Tol, PhCl, MeCN) is completed in two steps (Figure S15). The first one is attributed to the release of lattice solvent molecules and is completed at 255–275 °C, whereas the second one is completed at 435–465 °C and is attributed to the combustion of AIP2–/HAIP– ligands. Finally, the residue at 600 °C corresponds to CuO. (Table S3) The SCSC transformations discussed so far included insertion in the framework of UCY-16 of guest aromatic molecules and a polar aprotic solvent (i.e., MeCN) which illustrated the stability of UCY-16·6nDMF·nH2O in different organic solvents as well as the ability to sorb selected organic molecules.

SCSC Bridging Ligand Exchange Transformations

Further study of the SCSC properties of UCY-16·6nDMF·nH2O included the investigation of reactions with polar protic solvents such as primary alcohols. Indeed, single crystals of UCY-16·6nDMF·nH2O were employed in heterogeneous reactions with primary alcohols at elevated temperatures (60–150 °C). These crystals remained almost unchanged in size and shape and were of sufficient quality for crystallographic analysis. Specifically, the reaction of UCY-16·6nDMF·nH2O with MeOH at 60 °C revealed that not only the DMF lattice solvent molecules were exchanged by MeOH but also the μ3-ΟΗ– monoatomic bridges of the butterfly-like [Cu4(μ3–OH)2]6+ structural core of the SBUs were replaced by bridging μ3-ΟMe– groups (Figure 4).

Figure 4.

Figure 4

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Representations of the SBUs of UCY-16·6nDMF·nH2O. and UCY-16/CH3OH emphasizing on the exchange of the monoatomic μ3–OH– bridges by μ3-ΟMe– groups. The metal ions and μ3- bridges are represented in the ball and stick model, whereas the remaining atoms of the SBUs are in the wireframe model.

This type of transformation, which involves the SCSC exchange of a bridging ligand that contributes to the formation of the SBU and not necessarily to the formation of the framework is quite rare in MOF chemistry. There are a series of SCSC ligand exchange/installation transformations reported including the replacement of terminal solvent molecules by various organic ligands,54−56 or polytopic ligands by other ones,60,87,88 or installation of bridging polytopic ligands.60,68,69 However, to the best of our knowledge, there are only two examples involving the exchange of a monoatomic bridging ligand of the SBU of a MOF, an In3+ MOF where a monoatomic μ–ΟΗ– bridge is exchanged by a μ–ΟMe– group89 and a Cu2+ MOF where a bridging solvent molecule (μ-H2O) is replaced by other ones (μ-DMSO or μ-MeOH).90

Similar reactions of UCY-16·6nDMF·nH2O with additional primary alcohols n-CxH2x+1OH (x = 2–7) were also investigated and resulted in the formation of compounds UCY-16/n-CxH2x+1OH (x = 2–7). In all these compounds, only one μ3-ΟΗ– monoatomic bridge of the butterfly-like SBUs was replaced by a bridging μ3-OR– group in contrast to the situation in UCY-16/CH3OH (Figure 5). Specifically, the μ3–OH– bridge that is replaced by a μ3-OR– group in the exchanged analogues UCY-16/n-CxH2x+1OH (x = 2–7) is the one connecting the Cu2+ ions Cu(1)–Cu(3). The replacement of only this group could be possibly attributed to steric hindrance in the other positions since the monoatomic bridges that connect Cu(2)/Cu(3)/Cu(4) and Cu(5)(two symmetry–related metal ions)/Cu(6) ions contain above and in close proximity AIP–/HAIP– ligands. Moreover, the coordination modes of the AIP2–/HAIP– ligands of the 3D framework of UCY-16/n-CxH2x+1OH (x = 2–7) remain almost identical upon the SCSC exchange reactions. Notably, the decrease of the bond lengths of the monodentate carboxylate groups of ligands A and D is also observed (the distance Cu(4)–O(22) is decreased from 2.21 to2.07 Å and for the Cu(2)–O(4) one from 2.68 to 2.54 Å) as discussed for compounds UCY-16/S (S = Bz, Tol, PhCl, and MeCN). In addition, the contraction of unit cell dimensions (mainly of b-axes) and unit cell volume is also observed in the family of UCY-16/n-CxH2x+1OH (x = 1–7) exchanged analogues. A close examination of the crystal structures of UCY-16/n-CxH2x+1OH (x = 1–7) revealed the existence of different types of interactions between the lattice solvent molecules and the framework of UCY-16 in the various exchanged analogues. Specifically, the alcohols n-CxH2x+1OH (x = 1–5) of the corresponding exchanged MOFs interact mainly through hydrogen bonding interactions (Figures S16–S20), whereas the longer chain alcohols n-CxH2x+1OH (x = 6–7) are not involved in significant H-bonding interactions (Figures S21 and S22). In fact, the existence of longer chain alcohols such as 1-pentanol, 1-hexanol, and 1-heptanol in the structures of UCY-16/n-CxH2x+1OH (x = 5–7) (Figures S20–S22) is another uncommon structural feature of these compounds. Interestingly, the analogue UCY-16/n-C7H15OH represents the first example where lattice 1-heptanol molecules are observed in the pores of a MOF, whereas 1-pentanol and 1-hexanol have appeared only once previously in the structure of MOFs.91,92

Figure 5.

Figure 5

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Representations of the SBUs of UCY-16·6nDMF·nH2O and UCY-16/n-CxH2x+1OH (x = 2–7) emphasizing on the exchange of a monoatomic μ3–OH– bridge by the corresponding μ3-OR– group. The μ3- bridges involved in the exchange reactions and the metal ions are represented in the ball and stick model, whereas the remaining atoms of the SBUs are represented in the wireframe model.

pXRD and IR studies of the exchanged analogues UCY-16/n-CxH2x+1OH (x = 1–7) confirmed that they retain their crystallinity and structural integrity after the SCSC reactions. (Figures S23 and S24) Stability studies of the exchanged analogues containing longer–chain alcohols UCY-16/n-CxH2x+1OH (x = 6–7) revealed an increased stability in water compared to the one of the pristine MOF (Figure S25). However, there is a loss of crystallinity of the UCY-16/n-C6H13OH analogue upon treatment with water, something that is also observed for UCY-16/n-C7H15OH but to a significantly smaller extent.

Further efforts to enhance the hydrophobicity of UCY-16 included investigation of postsynthesis modification reactions of UCY-16·6nDMF·nH2O with longer - chain primary alcohols. Thus, heterogeneous reactions of the pristine MOF UCY-16·6nDMF·nH2O with the primary alcohols n-CxH2x+1OH (x = 8–10, 12, 14, and 16) were carried out at elevated temperatures and resulted in the isolation of microcrystalline powders (Figures S23 and S24). Although we were unable to obtain the crystal structures of the UCY-16/n-CxH2x+1OH (x = 8–10, 12, 14, and 16) exchanged analogues, it was confirmed from the powder diffractograms that they retain their crystallinity and structural integrity (Figure S23). In addition, infrared spectra obtained for these exchanged analogues are in line with this of the pristine material and contain the expected bands in the range 2700–3000 cm–1 due to the presence of the C–H bonds of the long–chain fatty alcohols (Figure S24). From this characterization, it is clear that the long–chain fatty alcohols are present in the UCY-16/n-CxH2x+1OH (x = 8–10, 12, 14, and 16) exchanged analogues; however, it is impossible to conclude whether they appear in the structure of the SBU (replacing one or more μ3–OH– anions) or in the lattice of the MOF or even in the outer surface of the materials. Stability studies of the exchanged analogues UCY-16/n-CxH2x+1OH (x = 8–10, 12, 14 and 16) indicated that their crystallinity is retained upon treatment in water for 24 h (Figure S26). The thermal stability of the exchanged compounds UCY-16/n-CxH2x+1OH (x = 1–10, 12, 14, and 16) was studied by means of TGA which revealed that their decomposition is completed in two steps (Figures S27 and S28). The first step is attributed to the release of lattice alcohol molecules and residual water or DMF lattice solvents and is completed at 250–270 °C, whereas the second step is completed at 500 °C and is attributed to the combustion of AIP2–/HAIP– ligands as well as the bridging μ3-OCxH2x+1– (x = 1–10, 12, 14 and 16) groups. Finally, the residue at 600 °C corresponds to CuO (Table S4).

Tuning the Hydrophobicity–Application

SCSC transformation and PSM exchange reactions of UCY-16·6nDMF·nH2O with long-chain fatty alcohols were proven to be successful approaches for the tuning of its wetting properties. The use of organic linkers with extended aliphatic or fluorinated functional groups in MOF synthesis typically results in materials with low surface energy that interact weakly with water. Consequently, such materials present hydrophobic or even superhydrophobic properties.93−95 The series of MOFs discussed and in particular the microcrystalline powder of the analogues with long-chain alcohols UCY-16/n-CxH2x+1OH·S′ (x = 6, 8, 9, 10, 12, 14, 16) were floating on the water surface which was the first evidence of their hydrophobic/superhydrophobic properties (Figures 6a ad S29). In addition, the hydrophobic materials easily disperse in nonpolar solvents (such as CHCl3), while being immiscible with water (Figure 6b). Water contact angle (WCA) studies indicated that the MOFs with alkyl chains CxH2x+1 (x = 6, 8–10, 12, and 14) were hydrophobic with WCA values >140 ± 5° (Figures 6c, S30, and S31), while UCY-16/n-C16H33OH was superhydrophobic with a WCA of 156 ± 5° (Figures 6d, S30, and S31). The hydrophobic/superhydrophobic MOFs were converted into a form that could be easily retrieved after an oil–water separation procedure by synthesizing a magnetic superhydrophobic MOF composite. This was prepared by mixing UCY-16/n-C16H33OH and Fe3O4 (mass ratio of 3:1) in acetone at ambient temperature. The magnetic superhydrophobic MOF composite UCY-16/n-C16H33OH/Fe3O4 was then investigated for its capability to remove crude oil from water. As shown in Figures 6e and S32, and Video S1, the MOF-based magnetic composite was able to quickly sorb oil from the surface of a water sample, and the oil-laden material could be easily recovered using a magnet.

Figure 6.

Figure 6

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Images of microcrystalline powder of UCY-16/n-C16H33OH (a) floating on the water surface and (b) dispersing in chloroform. (c) Distilled water droplet (10 μL) on a thin film of UCY-16/n-C16H33OH. (d) Digital photograph of the water contact angle for UCY-16/n-C16H33OH measured by a contact angle goniometer. (e) Crude oil removal from the water surface using the magnetic composite UCY-16/n-C16H33OH/Fe3O4.

Conclusions

SCSC exchange reactions have gained significant attention in the past few years as a versatile method to achieve targeted structural alterations and fine tune the properties of functional MOFs. A new Cu2+ 3-dimensional MOF with the formula [Cu6(μ3-ΟΗ)3(ΑΙΡ)4(ΗΑΙΡ)]n·6nDMF·nH2O - UCY-16·6nDMF·nH2O is reported exhibiting interesting SCSC transformation properties. The pristine material UCY-16·6nDMF·nH2O was isolated in high yield using low-cost starting materials and is based on two different SBUs displaying the same [Cu4(μ3–OH)2]6+ butterfly-like structural cores which are connected through five ΑΙΡ2–/ΗΑΙΡ– ligands. Thermal, chemical, and hydrolytic stability studies of UCY-16·6nDMF·nH2O indicated that it is thermally stable up to 250 °C and remains intact in most organic solvents but not in water. This compound displayed a significant capability to exchange in a SCSC fashion its lattice solvent molecules as well as coordinated groups as confirmed by the isolation of 11 new exchanged products. Some of the obtained modifications exhibited significant elements of novelty including the replacement of the monoatomic bridging μ3–OH– anion of the [Cu4(μ3–OH)2]6+ butterfly-like core of the SBU which has not been shown previously. In addition, the SCSC insertion of long–chain alcohols (n-CxH2x+1OH; x = 5–7) in the structure of a MOF is another uncommon structural feature and reactivity feature. Further investigation of exchange reactions of the pristine MOF with long-chain fatty alcohols allowed the preparation of a series of postsynthetically modified analogues UCY-16/n-CxH2x+1OH (x = 8–10, 12, 14, and 16), which are immiscible with water and display significant hydrolytic stability. Water contact angle measurements of UCY-16/n-CxH2x+1OH·S′ (x = 6, 8–10, 12, 14, and 16) indicated their hydrophobic/superhydrophobic nature. The magnetic superhydrophobic MOF composite UCY-16/n-C16H33OH/Fe3O4 was synthesized and demonstrated to be very efficient in removing crude oil from water under static conditions. Furthermore, it could be readily recovered, along with the organic pollutant, using an external magnet. This result indicated that the series of functionalized UCY-16/n-CxH2x+1OH·S′ analogues might be promising for multiple applications related to oil–water separation processes, including wastewater purification in crude oil production and oil spill cleanup. Thus, a detailed investigation of the SCSC transformation properties of UCY-16·6nDMF·nH2O allowed the development of a facile method for the fine-tuning of the hydrophobicity of MOFs. Overall, this work demonstrates an unprecedented SCSC transformation method for the fine-tuning of the hydrophobicity of MOFs and its use for the development of materials capable of removing hydrophobic pollutants from aqueous media.

Acknowledgments

This work was supported by the Cyprus Research and Innovation Foundation Research Grant “EXCELLENCE/1216/0076″ which is co-funded by the Republic of Cyprus and the European Regional Development Fund.

Supporting Information Available

The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acs.inorgchem.3c04060.

  • Crystallography details, pXRD, IR, TGA graphs and analysis, structural figures, and physical measurements and characterization (PDF)

  • Crude oil removal by UCY-16/n-C16H33OH/Fe3O4 (mass ratio of 3:1) and recovery of the oil-laden material using an external magnet (MP4)

Author Contributions

N.P.: Investigation, Methodology, Writing–original draft. D.A.E.: Investigation, Methodology. M.J.M.: Methodology, Writing–original draft, Reviewing and Editing. J.C.P.: Methodology, Writing–original draft, Reviewing and Editing, A.J.T.: Project supervision, manuscript writing–reviewing and editing.

The authors declare no competing financial interest.

Supplementary Material

ic3c04060_si_001.pdf (4.9MB, pdf)
ic3c04060_si_002.mp4 (16.5MB, mp4)

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