Main Group Chemistry at the Interface with Molecular Magnetism.

Innovative synthetic coordination and, increasingly, organometallic chemistry are at the heart of advances in molecular magnetism. Smart ligand design is essential for implementing controlled modifications to the electronic structure and magnetic properties of transition metal and f-element compounds, and many important recent developments use nontraditional ligands based on low-coordinate main group elements to drive the field forward. This review charts progress in molecular magnetism from the perspective of ligands in which the donor atoms range from low-coordinate 2p elements-particularly carbon but also boron and nitrogen-to the heavier p-block elements such as phosphorus, arsenic, antimony, and even bismuth. Emphasis is placed on the role played by novel main group ligands in addressing magnetic anisotropy of transition metal and f-element compounds, which underpins the development of single-molecule magnets (SMMs), a family of magnetic materials that can retain magnetization in the absence of a magnetic field below a blocking temperature. Nontraditional p-block donor atoms, with their relatively diffuse valence orbitals and more diverse bonding characteristics, also introduce scope for tuning the spin-orbit coupling properties and metal-ligand covalency in molecular magnets, which has implications in areas such as magnetic exchange coupling and spin crossover phenomena. The chemistry encompasses transition metals, lanthanides, and actinides and describes recently discovered molecular magnets that can be regarded, currently, as defining the state of the art. This review identifies that main group chemistry at the interface molecular magnetism is an area with huge potential to deliver new types of molecular magnets with previously unseen properties and applications.

Coupling of Nitric Oxide and Release of Nitrous Oxide from Rare-Earth-Dinitrosyliron Complexes.

Addition of Lewis acidic [Cp*2M]+ (M = Y, Gd) to the dinitrosyliron complexes (DNICs) [(NacNacAr)Fe(NO)2]- (Ar = mesityl, 2,6-diisopropylphenyl) results in formation of the isonitrosyl-bridged DNICs [(Cp*)2M(µ-ON)2Fe(NacNacAr)]. When Ar = 2,6-diisopropylphenyl, coupling of the NO ligands and release of N2O occur. Two factors contribute to this previously unobserved DNIC reactivity mode. First, the oxophilic rare-earth elements drive the formation of isonitrosyl bonds, forcing the DNIC nitrogen atoms into proximity. Second, the bulky substituents further squeeze the DNIC, which ultimately overcomes the barrier to NO coupling, demonstrating that N2O elimination can occur from a single iron center.

Pentagonal Bipyramidal Ln(III) Complexes Containing an Axial Phosphine Oxide Ligand: Field-induced Single-ion Magnetism Behavior of the Dy(III) Analogues.

A series of neutral homologous complexes [(L)Ln(Cy3PO)Cl] {where Ln = Gd (1), Tb (2), Dy (3), and Er (5)} and [(L)Dy(Ph3PO)Cl] (4) [H2L = 2,6-diacetylpyridine bis-benzoylhydrazone] were isolated. In these complexes, the central lanthanide ion possesses a pentagonal bipyramidal geometry with an overall pseudo D5h symmetry. The coordination environment around the lanthanide ion comprises of three nitrogen and two oxygen donors in an equatorial plane. The axial positions are taken up by a phosphine oxide (O donor) and a chloride ion. Among these compounds, the Dy(III) (3 and 4) analogues were found to be field-induced single-ion magnets.

Achieving Amphibious Superprotonic Conductivity in a CuI Metal-Organic Framework by Strategic Pyrazinium Salt Impregnation.

Treatment of a pyrazine (pz)-impregnated CuI metal-organic framework (MOF) ([1⊃pz]) with HCl vapor renders an interstitial pyrazinium chloride salt-hybridized MOF ([1⊃pz⋅6 HCl]) that exhibits proton conductivity over 10-2  S cm-1 both in anhydrous and under humid conditions. Framework [1⊃pz⋅6 HCl] features the highest anhydrous proton conductivity among the lesser-known examples of MOF-based materials exhibiting proton conductivity under both anhydrous and humid conditions. Moreover, [1⊃pz] and corresponding pyrazinium sulfate- and pyrazinium phosphate-hybridized MOFs also exhibit superprotonic conductivity over 10-2  S cm-1 under humid conditions. The impregnated pyrazinium ions play a crucial role in protonic conductivity, which occurs through a Grotthuss mechanism.

Pentagonal-Bipyramid Ln(III) Complexes Exhibiting Single-Ion-Magnet Behavior: A Rational Synthetic Approach for a Rigid Equatorial Plane.

A pentadentate chelating ligand is employed for the facile synthesis of air-stable pentagonal-bipyramid Ln(III) complexes with a rigid equatorial plane. The Dy(III) analogue exhibits single-ion-magnet behavior with Ueff/ kB = 70 K under Hdc = 500 Oe.

Pentagonal Bipyramid FeII Complexes: Robust Ising-Spin Units towards Heteropolynuclear Nanomagnets.

Pentagonal bipyramid FeII complexes have been investigated to evaluate their potential as Ising-spin building units for the preparation of heteropolynuclear complexes that are likely to behave as single-molecule magnets (SMMs). The considered monometallic complexes were prepared from the association of a divalent metal ion with pentadentate ligands that have a 2,6-diacetylpyridine bis(hydrazone) core (H2 LN3O2R ). Their magnetic anisotropy was established by magnetometry to reveal their zero-field splitting (ZFS) parameter D, which ranged between -4 and -13 cm-1 and was found to be modulated by the apical ligands (ROH versus Cl). The alteration of the D value by N-bound axial CN ligands, upon association with cyanometallates, was also assessed for heptacoordinated FeII as well as for related NiII and CoII derivatives. In all cases, N-coordinated cyanide ligands led to large magnetic anisotropy (i.e., -8 to -18 cm-1 for Fe and Ni, +33 cm-1 for Co). Ab initio calculations were performed on three FeII complexes, which enabled one to rationalize the role of the ligand on the nature and magnitude of the magnetic anisotropy. Starting from the pre-existing heptacoordinated complexes, a series of pentanuclear compounds were obtained by reactions with paramagnetic [W(CN)8 ]3- . Magnetic studies revealed the occurrence of ferromagnetic interactions between the spin carriers in all the heterometallic systems. Field-induced slow magnetic relaxation was observed for mononuclear FeII complexes (Ueff /kB up to 53 K (37 cm-1 ), τ0 =5×10-9  s), and SMM behavior was evidenced for a heteronuclear [Fe3 W2 ] derivative (Ueff /kB =35 K and τ0 =4.6 10-10  s), which confirmed that the parent complexes were robust Ising-type building units. High-field EPR spectroscopic investigation of the ZFS parameters for a Ni derivative is also reported.

Modification of extended open frameworks with fluorescent tags for sensing explosives: competition between size selectivity and electron deficiency.

Three new electron-rich metal-organic frameworks (MOF-1-MOF-3) have been synthesized by employing ligands bearing aromatic tags. The key role of the chosen aromatic tags is to enhance the π-electron density of the luminescent MOFs. Single-crystal X-ray structures have revealed that these MOFs form three-dimensional porous networks with the aromatic tags projecting inwardly into the pores. These highly luminescent electron-rich MOFs have been successfully utilized for the detection of explosive nitroaromatic compounds (NACs) on the basis of fluorescence quenching. Although all of the prepared MOFs can serve as sensors for NACs, MOF-1 and MOF-2 exhibit superior sensitivity towards 4-nitrotoluene (4-NT) and 2,4-dinitrotoluene (DNT) compared to 2,4,6-trinitrotoluene (TNT) and 1,3,5-trinitrobenzene (TNB). MOF-3, on the other hand, shows an order of sensitivity in accordance with the electron deficiencies of the substrates. To understand such anomalous behavior, we have thoroughly analyzed both the steady-state and time-resolved fluorescence quenching associated with these interactions. Determination of static Stern-Volmer constants (KS) as well as collisional constants (KC) has revealed that MOF-1 and MOF-2 have higher KS values with 4-NT than with TNT, whereas for MOF-3 the reverse order is observed. This apparently anomalous phenomenon was well corroborated by theoretical calculations. Moreover, recyclability and sensitivity studies have revealed that these MOFs can be reused several times and that their sensitivities towards TNT solution are at the parts per billion (ppb) level.

Multicomponent assembly of fluorescent-tag functionalized ligands in metal-organic frameworks for sensing explosives.

Detection of trace amounts of explosive materials is significantly important for security concerns and pollution control. Four multicomponent metal-organic frameworks (MOFs-12, 13, 23, and 123) have been synthesized by employing ligands embedded with fluorescent tags. The multicomponent assembly of the ligands was utilized to acquire a diverse electronic behavior of the MOFs and the fluorescent tags were strategically chosen to enhance the electron density in the MOFs. The phase purity of the MOFs was established by PXRD, NMR spectroscopy, and finally by single-crystal XRD. Single-crystal structures of the MOFs-12 and 13 showed the formation of three-dimensional porous networks with the aromatic tags projecting inwardly into the pores. These electron-rich MOFs were utilized for detection of explosive nitroaromatic compounds (NACs) through fluorescence quenching with high selectivity and sensitivity. The rate of fluorescence quenching for all the MOFs follows the order of electron deficiency of the NACs. We also showed the detection of picric acid (PA) by luminescent MOFs is not always reliable and can be misleading. This attracts our attention to explore these MOFs for sensing picryl chloride (PC), which is as explosive as picric acid and used widely to prepare more stable explosives like 2,4,6-trinitroaniline from PA. Moreover, the recyclability and sensitivity studies indicated that these MOFs can be reused several times with parts per billion (ppb) levels of sensitivity towards PC and 2,4,6-trinitrotoluene (TNT).

Selective fluoride sensing by a novel series of lanthanide-based one-dimensional coordination polymers through intramolecular proton transfer.

A novel series of one-dimensional coordination polymers (CPs) is achieved via a facile one-pot synthesis strategy employing the nitrate salts of trivalent lanthanides, a pentadentate chelating ligand, and triphenylphosphine oxide at a controlled stoichiometry under ambient conditions. All the CPs are characterized comprehensively using spectroscopic, X-ray crystallographic and magnetometric studies. The CPs are found to be thermally stable up to a significantly high temperature and resistant to water for an indefinite time. They are photoactive and exhibit selective fluoride ion (F-) sensing with excellent efficiency both colorimetrically and fluorimetrically in the solid-state as well as in solution. The presence of F- concomitantly sensitizes the photoluminescence enhancement and visual decolourization of the CPs in solution owing to the ground-state intra-molecular proton transfer. The photophysical response of the CPs to F- in solution was found to be instantaneous (<30 s). The sensitivity of detection is observed to be significantly high over a wide range of F- concentrations, covering the beneficial and detrimental domains of F- concentrations in drinking water. The limit of detection (LoD) under ambient conditions was found to be in the micromolar (µM) range-the best being 0.22 µM found using UV-vis spectrometry and 7.5 µM using fluorimetry. In comparison, the USEPA standard cut-off for the upper limit of F- concentration in drinking water is 211 µM, and the LoD of measuring F- concentration using the USEPA standard method using a fluoride-selective electrode is 26.3 µM. The CPs display markedly high selectivity toward F- with negligible-to-no interference from the commonly abundant ions (Cl-, Br-, I-, CH3CO2-, CO32-, SO42-, HPO42-, NH4+, Na+, K+, Mg2+, and Ca2+) in terms of UV-vis spectral change. Moreover, they also exhibit solid-state IR-spectrometric sensitivity towards F- under ambient conditions.

Fluorescent tris-imidazolium sensors for picric acid explosive.

Two new anthracene-functionalized fluorescent tris-imidazolium salts have been synthesized, characterized, and proven to be selective sensors for picric acid, which is a common constituent of many powerful explosives. Theoretical studies revealed an unusual ground-state electron transfer from picrate anion to the sensor molecules.

Slow magnetic relaxation in a homoaxially phosphine oxide coordinated pentagonal bipyramidal Dy(III) complex.

We report the synthesis of [(L)DyIII(Cy3PO)2]·[BPh4] (1-Dy) (where H2L = 2,6-diacetylpyridine bis-benzoylhydrazone and Cy = cyclohexyl) which crystallized in the triclinic, P1̄ space group. The local geometry around Dy(III) in 1-Dy was found to be pentagonal bipyramidal (pseudo-D5h). The AC magnetic susceptibility measurements performed on 1-Dy and on its diluted 1-Y(Dy) samples showed a typical single-molecule magnet signature revealed by the appearance of AC-frequency dependent out-of-phase susceptibility signals in the absence of a static magnetic field. The out-of-phase AC susceptibility signals were well resolved on the application of a small magnetic field (HDC = 500 Oe) and yielded an energy barrier for magnetization flipping of Ueff/kB = 50 K for the diluted derivative. The magnetic studies on 1-Dy and 1-Y(Dy) and data analysis further confirm that Raman and QTM under-barrier magnetic relaxations play a crucial role in lowering Ueff despite the almost axial nature of the Dy(III) ion in 1-Dy. We have rationalized these observations through detailed ab initio calculations performed on the X-ray crystal structure of 1-Dy.

A series of trifacial Pd6 molecular barrels with porphyrin walls.

Three new nanoscopic trigonal prisms, [(tmen)(6) Pd(6) (H(2)L)(3)](NO(3))(12) (1), [(Meen)(6) Pd(6)(H(2) L)(3)](NO(3))(12) (2), and [(2,2'-bipy)(6)Pd(6) (H(2)L)(3)](NO(3))(12) (3), have been synthesized in excellent yields through single-step metal-ligand-coordination-driven self-assembly using 5,10,15,20-tetrakis(3-pyridyl)porphyrin (H(2)L) as a donor and cis-blocked Pd(II) 90° acceptors. These complexes were fully characterized by spectroscopic studies and single-crystal X-ray diffraction. All of these barrels quantitatively bind Zn(II) ions in the N(4) pockets of the porphyrin walls at room temperature. Their corresponding zinc-embedded complexes, [(tmen)(6)Pd(6)(ZnL)(3)](NO(3))(12) (1 a), [(Meen)(6) Pd(6)(ZnL)(3)](NO(3))(12) (2 a), and [(2,2'-bipy)(6)Pd(6)(ZnL)(3)](NO(3))(12) (3 a), were synthesized under ambient conditions by the post-synthetic binding of Zn(II) ions into the H(2)N(4) pockets of the porphyrin walls of these complexes. These zinc-embedded complexes were characterized by electronic absorption, fluorescence emission, (1)H NMR spectroscopy, as well as elemental analysis. Complexes 1-3 exhibited considerable microporosity in their solid state. Complex 1 was an efficient adsorbent for nitrogen gas and EtOH, MeOH, and water vapors.

Three-component self-assembly of a series of triply interlocked Pd12 coordination prisms and their non-interlocked Pd6 analogues.

Template-assisted formation of multicomponent Pd(6) coordination prisms and formation of their self-templated triply interlocked Pd(12) analogues in the absence of an external template have been established in a single step through Pd-N/Pd-O coordination. Treatment of cis-[Pd(en)(NO(3))(2)] with K(3) tma and linear pillar 4,4'-bpy (en=ethylenediamine, H(3) tma=benzene-1,3,5-tricarboxylic acid, 4,4'-bpy=4,4'-bipyridine) gave intercalated coordination cage [{Pd(en)}(6)(bpy)(3)(tma)(2)](2)[NO(3)](12) (1) exclusively, whereas the same reaction in the presence of H(3) tma as an aromatic guest gave a H(3) tma-encapsulating non-interlocked discrete Pd(6) molecular prism [{Pd(en)}(6)(bpy)(3)(tma)(2)(H(3)tma)(2)][NO(3)](6) (2). Though the same reaction using cis-[Pd(NO(3))(2)(pn)] (pn=propane-1,2-diamine) instead of cis-[Pd(en)(NO(3))(2)] gave triply interlocked coordination cage [{Pd(pn)}(6)(bpy)(3)(tma)(2)](2)[NO(3)](12) (3) along with non-interlocked Pd(6) analogue [{Pd(pn)}(6)(bpy)(3) (tma)(2)](NO(3))(6) (3'), and the presence of H(3) tma as a guest gave H(3) tma-encapsulating molecular prism [{Pd(pn)}(6)(bpy)(3)(tma)(2)(H(3) tma)(2)][NO(3)](6) (4) exclusively. In solution, the amount of 3' decreases as the temperature is decreased, and in the solid state 3 is the sole product. Notably, an analogous reaction using the relatively short pillar pz (pz=pyrazine) instead of 4,4'-bpy gave triply interlocked coordination cage [{Pd(pn)}(6) (pz)(3)(tma)(2)](2)[NO(3)](12) (5) as the single product. Interestingly, the same reaction using slightly more bulky cis-[Pd(NO(3))(2)(tmen)] (tmen=N,N,N',N'-tetramethylethylene diamine) instead of cis-[Pd(NO(3))(2)(pn)] gave non-interlocked [{Pd(tmen)}(6)(pz)(3)(tma)(2)][NO(3)](6) (6) exclusively. Complexes 1, 3, and 5 represent the first examples of template-free triply interlocked molecular prisms obtained through multicomponent self-assembly. Formation of the complexes was supported by IR and multinuclear NMR ((1)H and (13)C) spectroscopy. Formation of guest-encapsulating complexes (2 and 4) was confirmed by 2D DOSY and ROESY NMR spectroscopic analyses, whereas for complexes 1, 3, 5, and 6 single-crystal X-ray diffraction techniques unambiguously confirmed their formation. The gross geometries of H(3) tma-encapsulating complexes 2 and 4 were obtained by universal force field (UFF) simulations.

Rigid N3O2-Pentadentate Ligand-Assisted Octacoordinate Mononuclear Ln(III) Complexes: Syntheses, Characterization, and Slow Magnetization Relaxation.

A series of air-stable mononuclear octacoordinate Ln(III) complexes, [(L)Ln(TPPO)3]OTf (Ln = Y (1·Y); Gd (1·Gd); Tb (1·Tb); Dy (1·Dy); Ho (1·Ho); and Er (1·Er)) and [(L)Ln(TPPO)(NO3)] (Ln = Y (2·Y) and Dy (2·Dy)), are synthesized employing a rigid N3O2-pentadentate chelating ligand as the basis ligand and meridional ancillary ligands (where H2L = 2,6-diacetylpyridine bis-benzoylhydrazone, TPPO = triphenylphosphine oxide, and OTf- = trifluoromethanesulfonate). All the complexes are synthesized under aerobic conditions and characterized comprehensively by spectroscopic and X-ray crystallographic techniques. Magnetic property investigation on the polycrystalline solid samples of 1·Ln (Ln = Gd, Tb, Dy, Ho, and Er) and 2·Dy are reported. A field-induced single-molecule magnet behavior was observed for the Dy derivatives. 1·Dy exhibits the highest effective energy barrier of magnetization reversal, U eff/k B = 47 K under H dc = 1 kOe among the complexes presented herein.

Evidence of an nN(amide) → π*Ar Interaction in N-Alkyl-N,N'-diacylhydrazines.

1,2-Dibenzoyl-1-tert-butylhydrazine (RH-5849) and related N-alkyl-N,N'-diacylhydrazines are environmentally benign insect growth regulators. Herein, we show that an unusual nN(amide) → π*Ar interaction mediated by a hydrazide amide nitrogen atom plays a crucial role in stabilizing their biologically active trans-cis (t-c) rotameric conformations. We provide NMR and IR spectroscopic evidence for the presence of these interactions, which is also supported by X-ray crystallographic and computational studies.

Stabilization of Azapeptides by Namide···H-Namide Hydrogen Bonds.

An unusual Namide···H-Namide hydrogen bond (HB) was previously proposed to stabilize the azapeptide ß-turns. Herein we provide experimental evidence for the Namide···H-Namide HB and show that this HB endows a stabilization of 1-3 kcal·mol-1 and enforces the trans-cis-trans (t-c-t) and cis-cis-trans (c-c-t) amide bond conformations in azapeptides and N-methyl-azapeptides, respectively. Our results indicate that these Namide···H-Namide HBs can have stabilizing contributions even in short azapeptides that cannot fold to form ß-turns.

A Pd6 molecular cage via multicomponent self-assembly incorporating both neutral and anionic linkers.

A Pd(6) molecular cage [{(tmen)Pd}(6)(bpy)(3)(tma)(2)](NO(3))(6) [1; where tmen = N,N,N',N'-tetramethylethylene diamine, bpy = 4,4'-bipyridyl, and H(3)tma = trimesic acid] was prepared via the template-free three-component self-assembly of a cis-blocked palladium(II) acceptor in combination with a tricarboxylate and a dipyridyl donor. Complex 1 represents the first example of a 3D palladium(II) cage of defined shape incorporating anionic and neutral linkers. Guest-induced exclusive formation of this cage was also monitored by an NMR study.

Ruthenium-oxygen coordination-driven self-assembly of a Ru(II)8 incomplete prism: synthesis, structure, and shape-selective molecular recognition study.

Coordination-driven self-assembly of 1,3,5-benzenetricarboxylate (tma; 1) and oxalato-bridged p-cymeneruthenium(II) building block [Ru(2)(µ-η(4)-C(2)O(4))(MeOH)(2)(η(6)-p-cymene)(2)](O(3)SCF(3))(2) (2) affords an unusual octanuclear incomplete prism [Ru(8)(η(6)-p-cymene)(8)(tma)(2)(µ-η(4)-C(2)O(4))(2)(OMe)(4)](O(3)SCF(3))(2) (3), which exhibits a remarkable shape-selective binding affinity for neutral phenolic compounds via hydrogen-bonding interactions (p-cymene = p-(i)PrC(6)H(4)Me). Such a binding was confirmed by single-crystal X-ray diffraction analysis using 1,3,5-trihydroxybenzene as an analyte.

Conformational control of N-methyl-N,N'-diacylhydrazines by noncovalent carbon bonding in solution.

In recent years, some X-ray structural and computational evidence has emerged for noncovalent carbon bonding (C-bond). However, evidence of C-bonds in solution is limited. Herein, from the conformational analyses of strategically designed N-methyl-N,N'-diacylhydrazines, we for the first time show that C-bonds can be modulated to control the conformational preferences of small molecules in solution. We show that unusual N(amide)C-X noncovalent carbon bonding interactions stabilize the trans-cis (t-c) amide bond rotamers of N-methyl-N,N'-diacylhydrazines over the expected trans-trans (t-t) rotamers.

Self-assembly of a Pd6-molecular double-square and a Cu3-trigonalbipyramidal cage via a new tripodal flexible ligand.

A new tripodal flexible ligand (L) containing pyrazolyl functionality has been prepared and successfully used to obtain a pd(6) (1) molecular double-square and a cu(3) trigonalbipyramidal cage (2), where complex 1 represents the first example of a double-square obtained using a flexible tripodal ligand.