Metal-ligand Lability and Ligand Mobility Enables Framework Transformation via Ligand Release in a Family of Crystalline 2D Coordination Polymers.

A family of seven silver(I)-perfluorocarboxylate-quinoxaline coordination polymers, [Ag4 (O2 CRF )4 (quin)4 ] 1-5 (RF =(CF2 )n-1 CF3 )4 , n=1 to 5); [Ag4 (O2 C(CF2 )2 CO2 )2 (quin)4 ] 6; [Ag4 (O2 CC6 F5 )4 (quin)4 ] 7 (quin=quinoxaline), denoted by composition as 4 : 4 : 4 phases, was synthesised from reaction of the corresponding silver(I) perfluorocarboxylate with excess quinoxaline. Compounds 1-7 adopt a common 2D layered structure in which 1D silver-perfluorcarboxylate chains are crosslinked by ditopic quinoxaline ligands. Solid-state reaction upon heating, involving loss of one equivalent of quinoxaline, yielding new crystalline 4 : 4 : 3 phases [Ag4 (O2 C(CF2 )n-1 CF3 )4 (quin)3 ]n (8-10, n=1 to 3), was followed in situ by PXRD and TGA studies. Crystal structures were confirmed by direct syntheses and structure determination. The solid-state reaction converting 4 : 4 : 4 to 4 : 4 : 3 phase materials involves cleavage and formation of Ag-N and Ag-O bonds to enable the structural rearrangement. One of the 4 : 4 : 3 phase coordination polymers (10) shows the remarkably high dielectric constant in the low electric field frequency range.

Multi-stimulus linear negative expansion of a breathing M(O2CR)4-node MOF.

The metal-organic framework (Me2NH2)2[Cd(NO2BDC)2] (SHF-81) comprises flattened tetrahedral Cd(O2CR)42- nodes, in which Cd(ii) centres are linked via NO2BDC2- ligands (2-nitrobenzene-1,4-dicarboxylate) to give a doubly interpenetrated anionic network, with charge balanced by two Me2NH2+ cations per Cd centre resident in the pores. The study establishes that this is a twinned α-quartz-type structure (trigonal, space group P3x21, x = 1 or 2), although very close to the higher symmetry ß-quartz arrangement (hexagonal, P6x22, x = 2 or 4) in its as-synthesised solvated form [Cd(NO2BDC)2]·2DMF·0.5H2O (SHF-81-DMF). The activated MOF exhibits very little N2 uptake at 77 K, but shows significant CO2 uptake at 273-298 K with an isosteric enthalpy of adsorption (ΔHads) at zero coverage of -27.4 kJ mol-1 determined for the MOF directly activated from SHF-81-DMF. A series of in situ diffraction experiments, both single-crystal X-ray diffraction (SCXRD) and powder X-ray diffraction (PXRD), reveal that the MOF is flexible and exhibits breathing behaviour with observed changes as large as 12% in the a- and b-axes (|Δa|, |Δb| < 1.8 Å) and 5.5% in the c-axis (|Δc| < 0.7 Å). Both the solvated SHF-81-DMF and activated/desolvated SHF-81 forms of the MOF exhibit linear negative thermal expansion (NTE), in which pores that run parallel to the c-axis expand in diameter (a- and b-axis) while contracting in length (c-axis) upon increasing temperature. Adsorption of CO2 gas at 298 K also results in linear negative expansion (Δa, Δb > 0; Δc < 0; ΔV > 0). The largest change in dimensions is observed during activation/desolvation from SHF-81-DMF to SHF-81 (Δa, Δb < 0; Δc > 0; ΔV < 0). Collectively the nine in situ diffraction experiments conducted suggest the breathing behaviour is continuous, although individual desolvation and adsorption experiments do not rule out the possibility of a gating or step at intermediate geometries that is coupled with continuous dynamic behaviour towards the extremities of the breathing amplitude.

Post-Synthetic Modification Unlocks a 2D-to-3D Switch in MOF Breathing Response: A Single-Crystal-Diffraction Mapping Study.

Post-synthetic modification (PSM) of the interpenetrated diamondoid metal-organic framework (Me2 NH2 )[In(BDC-NH2 )2 ] (BDC-NH2 =aminobenzenedicarboxylate) SHF-61 proceeds quantitatively in a single-crystal-to-single-crystal manner to yield the acetamide derivative (Me2 NH2 )[In(BDC-NHC(O)Me)2 ] SHF-62. Continuous breathing behaviour during activation/desolvation is retained upon PSM, but pore closing now leads to ring-flipping to avert steric clash of amide methyl groups of the modified ligands. This triggers a reduction in the amplitude of the breathing deformation in the two dimensions associated with pore diameter, but a large increase in the third dimension associated with pore length. The MOF is thereby converted from predominantly 2D breathing (in SHF-61) to a distinctly 3D breathing motion (in SHF-62) indicating a decoupling of the pore-width and pore-length breathing motions. These breathing motions have been mapped by a series of single-crystal diffraction studies.

Benchmarking of Halogen Bond Strength in Solution with Nickel Fluorides: Bromine versus Iodine and Perfluoroaryl versus Perfluoroalkyl Donors.

The energetics of halogen bond formation in solution have been investigated for a series of nickel fluoride halogen bond acceptors; trans-[NiF(2-C5 NF4 )(PEt3 )2 ] (A1), trans-[NiF{2-C5 NF3 (4-H)}(PEt3 )2 ] (A2), trans-[NiF{2-C5 NF3 (4-NMe2 )}(PEt3 )2 ] (A3) and trans-[NiF{2-C5 NF2 H(4-CF3 )}(PCy3 )2 ] (A4) with neutral organic halogen bond donors, iodopentafluorobenzene (D1), 1-iodononafluorobutane (D2) and bromopentafluorobenzene (D3), in order to establish the significance of changes from perfluoroaryl to perfluoroalkyl donors and from iodine to bromine donors. 19 F NMR titration experiments have been employed to obtain the association constants, enthalpy, and entropy for the halogen bond formed between these donor-acceptor partners in protiotoluene. For A2-A4, association constants of the halogen bonds formed with iodoperfluoroalkane (D2) are consistently larger than those obtained for analogous complexes with the iodoperfluoroarene (D1). For complexes formed with A2-A4, the strength of the halogen bond is significantly lowered upon modification of the halogen donor atom from I (in D1) to Br (in D3) (for D1: 5≤K285 ≤12 m-1 , for D3: 1.0≤K193 ≤1.6 m-1 ). The presence of the electron donating NMe2 substituent on the pyridyl ring of acceptor A3 led to an increase in -ΔH, and the association constants of the halogen bond complexes formed with D1-D3, compared to those formed by A1, A2 and A4 with the same donors.

Increasing Alkyl Chain Length in a Series of Layered Metal-Organic Frameworks Aids Ultrasonic Exfoliation to Form Nanosheets.

Metal-organic framework nanosheets (MONs) are attracting increasing attention as a diverse class of two-dimensional materials derived from metal-organic frameworks (MOFs). The principles behind the design of layered MOFs that can readily be exfoliated to form nanosheets, however, remain poorly understood. Here we systematically investigate an isoreticular series of layered MOFs functionalized with alkoxy substituents in order to understand the effect of substituent alkyl chain length on the structure and properties of the resulting nanosheets. A series of 2,5-alkoxybenzene-1,4-dicarboxylate ligands (O2CC6H2(OR)2CO2, R = methyl-pentyl, 1-5, respectively) was used to synthesize copper paddle-wheel MOFs. Rietveld and Pawley fitting of powder diffraction patterns for compounds Cu(3-5)(DMF) showed they adopt an isoreticular series with two-dimensional connectivity in which the interlayer distance increases from 8.68 Å (R = propyl) to 10.03 Å (R = pentyl). Adsorption of CO2 by the MOFs was found to increase from 27.2 to 40.2 cm3 g-1 with increasing chain length, which we attribute to the increasing accessible volume associated with increasing unit-cell volume. Ultrasound was used to exfoliate the layered MOFs to form MONs, with shorter alkyl chains resulting in higher concentrations of exfoliated material in suspension. The average height of MONs was investigated by AFM and found to decrease from 35 ± 26 to 20 ± 12 nm with increasing chain length, with the thinnest MONs observed being only 5 nm, corresponding to five framework layers. These results indicate that careful choice of ligand functionalities can be used to tune nanosheet structure and properties, enabling optimization for a variety of applications.

Fe(III) Protoporphyrin IX Encapsulated in a Zinc Metal-Organic Framework Shows Dramatically Enhanced Peroxidatic Activity.

Two MOFs, [H2N(CH3)2][Zn3(TATB)2(HCOO)]·HN(CH3)2·DMF·6H2O (1) and Zn-HKUST-1 (2), were investigated as potential hosts to encapsulate Fe(III) heme (Fe(III) protoporphyrin IX = Fe(III)PPIX). Methyl orange (MO) adsorption was used as an initial model for substrate uptake. MOF 1 showed good adsorption of MO (10.3 ± 0.8 mg g-1) which could undergo in situ protonation upon exposure to aqueous HCl vapor. By contrast, MO uptake by 2 was much lower (2 ± 1 mg g-1), and PXRD indicated that structural instability on exposure to water was the likely cause. Two methods for Fe(III)PPIX-1 preparation were investigated: soaking and encapsulation. Encapsulation was verified by SEM-EDS and showed comparable concentrations of Fe(III)PPIX on exposed interior surfaces and on the original surface of fractured crystals. SEM-EDS results were consistent with ICP-OES data on bulk material (1.2 ± 0.1 mass % Fe). PXRD data showed that the framework in 1 was unchanged after encapsulation of Fe(III)PPIX. MO adsorption (5.8 ± 1.2 mg g-1) by Fe(III)PPIX-1 confirmed there is space for substrate diffusion into the framework, while the UV-vis spectrum of solubilized crystals confirmed that Fe(III)PPIX retained its integrity. A solid-state UV-vis spectrum of Fe(III)PPIX-1 indicated that Fe(III)PPIX was not in a µ-oxo dimeric form. Although single-crystal XRD data did not allow for full refinement of the encapsulated Fe(III)PPIX molecule owing to disorder of the metalloporphyrin, the Fe atom and pyrrole N atoms were located, enabling rigid-body modeling of the porphine core. Reaction of 2,2'-azino-bis(3-ethylbenzothiazoline)-6-sulfonic acid (ABTS) with H2O2, catalyzed by Fe(III)PPIX-1 and -2, showed that Fe(III)PPIX-1 is significantly more efficient than Fe(III)PPIX-2 and is superior to solid Fe(III)PPIX-Cl. Fe(III)PPIX-1 was used to catalyze the oxidation of hydroquinone, thymol, benzyl alcohol, and phenyl ethanol by tert-butyl-hydroperoxide with t1/2 values that increase with increasing substrate molecular volume.

Coordination change, lability and hemilability in metal-organic frameworks.

Metal-organic frameworks (MOFs) are some of the most exciting materials in current science. Their utility and diversity of applications depends on a combination of their chemistry, their framework topology and the spatial dimensions of their pores. In this review we concentrate on the chemistry of MOFs. Specifically we bring together many aspects of MOFs that underpin their stability, reactivity and dynamic behaviour within a common theme related to (changes in) metal-ligand bonding. In each area we provide examples to illustrate the behaviour and discuss it in the context of metal lability and coordination changes. Starting with flexible behaviour in which metal-linker bonds undergo deformation rather than cleavage, we then consider coordination changes that lead to open metal sites, changes in framework topology, framework dimensionality or degree of network interpenetration. We show how these changes are linked to development of new properties, including changes in magnetic behaviour, gas adsorption characteristics, construction of composite MOFs and amorphous MOFs, as well as providing new synthetic routes for MOF preparation. We discuss how the lability of the species that make up the MOFs can affect aspects from their synthesis to the possibility of metal and linker exchange reactions that may lead to defects and disorder. The final section reviews hemilability in MOFs, where regions of different chemical behaviour within MOFs can lead to unusual properties, such as self-accelerating and ultraselective adsorption.

Encapsulation of Crabtree's Catalyst in Sulfonated MIL-101(Cr): Enhancement of Stability and Selectivity between Competing Reaction Pathways by the MOF Chemical Microenvironment.

Crabtree's catalyst was encapsulated inside the pores of the sulfonated MIL-101(Cr) metal-organic framework (MOF) by cation exchange. This hybrid catalyst is active for the heterogeneous hydrogenation of non-functionalized alkenes either in solution or in the gas phase. Moreover, encapsulation inside a well-defined hydrophilic microenvironment enhances catalyst stability and selectivity to hydrogenation over isomerization for substrates bearing ligating functionalities. Accordingly, the encapsulated catalyst significantly outperforms its homogeneous counterpart in the hydrogenation of olefinic alcohols in terms of overall conversion and selectivity, with the chemical microenvironment of the MOF host favouring one out of two competing reaction pathways.

Halogen bonding, chalcogen bonding, pnictogen bonding, tetrel bonding: origins, current status and discussion.

The role of the closing lecture in a Faraday Discussion is to summarise the contributions made to the Discussion over the course of the meeting and in so doing capture the main themes that have arisen. This article is based upon my Closing Remarks Lecture at the 203rd Faraday Discussion meeting on Halogen Bonding in Supramolecular and Solid State Chemistry, held in Ottawa, Canada, on 10-12th July, 2017. The Discussion included papers on fundamentals and applications of halogen bonding in the solid state and solution phase. Analogous interactions involving main group elements outside group 17 were also examined. In the closing lecture and in this article these contributions have been grouped into the four themes: (a) fundamentals, (b) beyond the halogen bond, (c) characterisation, and (d) applications. The lecture and paper also include a short reflection on past work that has a bearing on the Discussion.

Binding CO2 by a Cr8 Metallacrown.

The {Cr8 } metallacrown [CrF(O2 Ct Bu)2 ]8 , containing a F-lined internal cavity, shows high selectivity for CO2 over N2 . DFT calculations and absorption studies support the multiple binding of F-groups to the C-center of CO2 (C⋅⋅⋅F 3.190(9)-3.389(9) Å), as confirmed by single-crystal X-ray diffraction.

Arene Selectivity by a Flexible Coordination Polymer Host.

The coordination polymers [Ag4 (O2 CCF3 )4 (phen)3 ]⋅ phen⋅arene (1⋅phen⋅arene) (phen=phenazine; arene=toluene, p-xylene or benzene) have been synthesised from the solution phase in a series of arene solvents and crystallographically characterised. By contrast, analogous syntheses from o-xylene and m-xylene as the solvent yield the solvent-free coordination polymer [Ag4 (O2 CCF3 )4 (phen)2 ] (2). Toluene, p-xylene and benzene have been successfully used in mixed-arene syntheses to template the formation of coordination polymers 1⋅phen⋅arene, which incorporate o- or m-xylene. The selectivity of 1⋅phen⋅arene for the arene guests was determined, through pairwise competition experiments, to be p-xylene>toluene≈benzene>o-xylene>m-xylene. The largest selectivity coefficient was determined as 14.2 for p-xylene:m-xylene and the smallest was 1.0 for toluene:benzene.

The Contrasting Character of Early and Late Transition Metal Fluorides as Hydrogen Bond Acceptors.

The association constants and enthalpies for the binding of hydrogen bond donors to group 10 transition metal complexes featuring a single fluoride ligand (trans-[Ni(F)(2-C5NF4)(PR3)2], R = Et 1a, Cy 1b, trans-[Pd(F)(4-C5NF4)(PCy3)2] 2, trans-[Pt(F){2-C5NF2H(CF3)}(PCy3)2] 3 and of group 4 difluorides (Cp2MF2, M = Ti 4a, Zr 5a, Hf 6a; Cp*2MF2, M = Ti 4b, Zr 5b, Hf 6b) are reported. These measurements allow placement of these fluoride ligands on the scales of organic H-bond acceptor strength. The H-bond acceptor capability ß (Hunter scale) for the group 10 metal fluorides is far greater (1a 12.1, 1b 9.7, 2 11.6, 3 11.0) than that for group 4 metal fluorides (4a 5.8, 5a 4.7, 6a 4.7, 4b 6.9, 5b 5.6, 6b 5.4), demonstrating that the group 10 fluorides are comparable to the strongest organic H-bond acceptors, such as Me3NO, whereas group 4 fluorides fall in the same range as N-bases aniline through pyridine. Additionally, the measurement of the binding enthalpy of 4-fluorophenol to 1a in carbon tetrachloride (-23.5 ± 0.3 kJ mol(-1)) interlocks our study with Laurence's scale of H-bond basicity of organic molecules. The much greater polarity of group 10 metal fluorides than that of the group 4 metal fluorides is consistent with the importance of pπ-dπ bonding in the latter. The polarity of the group 10 metal fluorides indicates their potential as building blocks for hydrogen-bonded assemblies. The synthesis of trans-[Ni(F){2-C5NF3(NH2)}(PEt3)2], which exhibits an extended chain structure assembled by hydrogen bonds between the amine and metal-fluoride groups, confirms this hypothesis.

Coordination polymer flexibility leads to polymorphism and enables a crystalline solid-vapour reaction: a multi-technique mechanistic study.

Despite an absence of conventional porosity, the 1D coordination polymer [Ag4 (O2 C(CF2 )2 CF3 )4 (TMP)3 ] (1; TMP=tetramethylpyrazine) can absorb small alcohols from the vapour phase, which insert into AgO bonds to yield coordination polymers [Ag4 (O2 C(CF2 )2 CF3 )4 (TMP)3 (ROH)2 ] (1-ROH; R=Me, Et, iPr). The reactions are reversible single-crystal-to-single-crystal transformations. Vapour-solid equilibria have been examined by gas-phase IR spectroscopy (K=5.68(9)×10(-5) (MeOH), 9.5(3)×10(-6) (EtOH), 6.14(5)×10(-5) (iPrOH) at 295 K, 1 bar). Thermal analyses (TGA, DSC) have enabled quantitative comparison of two-step reactions 1-ROH→1→2, in which 2 is the 2D coordination polymer [Ag4 (O2 C(CF2 )2 CF3 )4 (TMP)2 ] formed by loss of TMP ligands exclusively from singly-bridging sites. Four polymorphic forms of 1 (1-A(LT) , 1-A(HT) , 1-B(LT) and 1-B(HT) ; HT=high temperature, LT=low temperature) have been identified crystallographically. In situ powder X-ray diffraction (PXRD) studies of the 1-ROH→1→2 transformations indicate the role of the HT polymorphs in these reactions. The structural relationship between polymorphs, involving changes in conformation of perfluoroalkyl chains and a change in orientation of entire polymers (A versus B forms), suggests a mechanism for the observed reactions and a pathway for guest transport within the fluorous layers. Consistent with this pathway, optical microscopy and AFM studies on single crystals of 1-MeOH/1-A(HT) show that cracks parallel to the layers of interdigitated perfluoroalkyl chains develop during the MeOH release/uptake process.

Metal hydrides form halogen bonds: measurement of energetics of binding.

The formation of halogen bonds from iodopentafluorobenzene and 1-iodoperfluorohexane to a series of bis(η(5)-cyclopentadienyl)metal hydrides (Cp2TaH3, 1; Cp2MH2, M = Mo, 2, M = W, 3; Cp2ReH, 4; Cp2Ta(H)CO, 5; Cp = η(5)-cyclopentadienyl) is demonstrated by (1)H NMR spectroscopy. Interaction enthalpies and entropies for complex 1 with C6F5I and C6F13I are reported (ΔH° = -10.9 ± 0.4 and -11.8 ± 0.3 kJ/mol; ΔS° = -38 ± 2 and -34 ± 2 J/(mol·K), respectively) and found to be stronger than those for 1 with the hydrogen-bond donor indole (ΔH° = -7.3 ± 0.1 kJ/mol, ΔS° = -24 ± 1 J/(mol·K)). For the more reactive complexes 2-5, measurements are limited to determination of their low-temperature (212 K) association constants with C6F5I as 2.9 ± 0.2, 2.5 ± 0.1, <1.5, and 12.5 ± 0.3 M(-1), respectively.