Observation of Slow Relaxation and Single‐Molecule Toroidal Behavior in a Family of Butterfly‐Shaped Ln4 Complexes

A family of five isostructural butterfly complexes with a tetranuclear [Ln₄] core of the general formula [Ln₄(LH)₂(μ₂‐η¹η¹Piv)(η²‐Piv)(μ₃‐OH)₂]?x H₂O?y MeOH?z CHCl₃ ( 1 : Ln=Dy^III, x=2, y=2, z=0; 2 : Ln=Tb^III, x=0, y=0, z=6; 3 : Ln=Er^III, x=2, y=2, z=0; 4 : Ln=Ho^III, x=2, y=2, z=0; 5 : Ln=Yb^III, x=2, y=2, z=0; LH₄=6‐{[bis(2‐hydroxyethyl)amino]methyl}‐N′‐(2‐hydroxy‐3‐methoxybenzylidene)picolinohydrazide; PivH=pivalic acid) was isolated and characterized both structurally and magnetically. Complexes 1 – 5 were probed by direct and alternating current (dc and ac) magnetic susceptibility measurements and, except for 1 , they did not display single‐molecule magnetism (SMM) behavior. The ac magnetic susceptibility measurements show frequency‐dependent out‐of‐phase signals with one relaxation process for complex 1 and the estimated effective energy barrier for the relaxation process was found to be 49 K. We have carried out extensive ab initio (CASSCF+RASSI‐SO+SINGLE_ANISO+POLY_ANISO) calculations on all the five complexes to gain deeper insights into the nature of magnetic anisotropy and the presence and absence of slow relaxation in these complexes. Our calculations yield three different exchange coupling for these Ln₄ complexes and all the extracted J values are found to be weakly ferro/antiferromagentic in nature (J₁=+2.35, J₂=?0.58, and J₃=?0.29 cm^?1 for 1 ; J₁=+0.45, J₂=?0.68, and J₃=?0.29 cm^?1 for 2 ; J₁=+0.03, J₂=?0.98, and J₃=?0.19 cm^?1 for 3 ; J₁=+4.15, J₂=?0.23, and J₃=?0.54 cm^?1 for 4 and J₁=+0.15, J₂=?0.28, and J₃=?1.18 cm^?1 for 5 ). Our calculations reveal the presence of very large mixed toroidal moment in complex 1 and this is essentially due to the specific exchange topology present in this cluster. Our calculations also suggest presence of single‐molecule toroics (SMTs) in complex 2 . For complexes 3 – 5 on the other hand, the transverse anisotropy was computed to be large, leading to the absence of slow relaxation of magnetization. As the magnetic field produced by SMTs decays faster than the normal spin moments, the concept of SMTs can be exploited to build qubits in which less interference and dense packing are possible. Our systematic study on these series of Ln₄ complexes suggest how the ligand design can help to bring forth such SMT characteristics in lanthanide complexes.     

Analysis of the Magnetic Coupling in a Mn(II)-U(V)-Mn(II) Single Molecule Magnet

[{Mn(TPA)I}{UO2(Mesaldien)}{Mn(TPA)I}]I formula (here TPA=tris(2-pyridylmethyl)amine and Mesaldien=N,N’-(2-aminomethyl)diethylenebis(salicylidene imine)) reported by Mazzanti and coworkers (Chatelain et al. Angew. Chem. Int. Ed. 2014 , 53, 13434) is so far the best Single Molecule Magnet (SMM) in the {3d–5f} class of molecules exhibiting barrier height of magnetization reversal as high as 81.0 K. In this work, we have employed a combination of ab initio CAS and DFT methods to fully characterize this compound and to extract the relevant spin Hamiltonian parameters. We show that the signs of the magnetic coupling and of the g-factors of the monomers are interconnected. The central magnetic unit [U^VO₂]⁺ is described by a Kramers Doublet (KD) with negative g-factors, due to a large orbital contribution. The magnetic coupling for the {Mn(II)-U(V)} pair is modeled by an anisotropic exchange Hamiltonian: all components are ferromagnetic in terms of spin moments, the parallel component J_Z twice larger as the perpendicular one J_⊥. The spin density distribution suggests that spin polarization on the U(V) center favors the ferromagnetic coupling. Further, the J_Z/J_⊥ ratio, which is related to the barrier height, was found to correlate to the corresponding spin contribution of the g-factors of the U(V) center. This correlation established for the first time offers a direct way to estimate this important ratio from the corresponding g^S-values, which can be obtained using traditional ab initio packages and hence has a wider application to other {3d–5f} magnets. It is finally shown that the magnetization barrier height is tuned by the splitting of the [U^VO₂]⁺ 5 f orbitals.     

Coordination and Hydroboration of Ru(II)-Borate Complexes: Dihydridoborate vs. Bis(dihydridoborate)

Treatment of [Cp*RuCl₂]₂, 1 , [(COD)IrCl]₂, 2 or [(p-cymene)RuCl₂]_2, 3 (Cp*=η⁵-C₅Me_5, COD= 1,5-cyclooctadiene and p-cymene=η⁶-ⁱPrC₆H₄Me) with heterocyclic borate ligands [Na[(H₃B)L], L₁ and L₂ ( L₁ : L=amt, L₂ : L=mp; amt=2-amino-5-mercapto-1,3,4-thiadiazole, mp=2-mercaptopyridine) led to the formation of borate complexes having uncommon coordination. For example, complexes 1 and 2 on reaction with L₁ and L₂ afforded dihydridoborate species [L^AM(μ-H)₂BHL] 4 – 6 ( 4 : L^A=Cp*, M=Ru, L=amt; 5 : L^A=Cp*, M=Ru, L=mp; 6 : L^A=COD, M=Ir, L=mp). On the other hand, treatment of 3 with L₂ yielded cis- and trans-bis(dihydridoborate) species, [Ru{(μ-H)₂BH(mp)}₂], cis- 7 and trans- 7 . The isolation and structural characterization of fac- and mer-[Ru{(μ-H)₂BH(mp)}{(μ-H)BH(mp)₂}], 8 from the same reaction offered an insight into the behaviour of these dihydridoborate species in solution. Fascinatingly, despite having reduced natural charges on Ru centres both at cis-and trans- 7 , they underwent hydroboration reaction with alkynes that yielded both Markovnikov and anti-Markovnikov addition products, 10 a – d .     

Sorptive elimination of fluoride from contaminated groundwater in a fixed bed column: A kinetic model validation based study

The current investigation involves a continuous adsorption experiment in a packed bed column for the sorptive elucidation of fluoride from contaminated groundwater using an activated soil-clay mixture. Through the combination of naturally accessible laterite soil with silica enriched clay (3:1 ratio), a low-cost Al–Si heterogeneous material has been developed. Following detailed characterization, the developed materials were employed in a long-time column process to achieve a high degree of fluoride separation from real-world groundwater. In a packed bed column investigation, the effect of bed height, initial fluoride concentration, and flow rate on the breakthrough properties of the adsorption system were investigated. By using a non-linear regression equation, three model kinetics, such as the Thomas Model, Adams-Bohart Model, and Yoon-Nelson Model, were fitted to validate the column-based experimental data, by analysing the breakthrough curves profiles, and distinct kinetic parameters. The Bed Depth Service Time Analysis (BDST) model was tested to express the effect of bed height on breakthrough curves, as well as to predict the time for breakthrough, and material depletion under optimal conditions. The Thomas and Yoon-Nelson models were identified to be the most appropriate ones for describing the entire breakthrough curve, whereas the Adams-Bohart model was only utilised to predict the first half of the dynamic process. With correlation coefficients (R²) 0.96, the experimental results were well suited to Thomas, Yoon-Nelson, and Adams-Bohart models. Finally, regeneration assessment was carried out where even after four cycles of operation, regenerated adsorbent showed a rejection efficacy of 78% to fluoride that proves the viability of the material and methodology.     

Synthesis of 3‐aminomethylidenechroman‐2‐carboxamides by a Sequential One‐pot Three Component Reaction and by Post‐Passerini Condensation Modification

3‐Arylaminomethylidenechroman‐2‐carboxamide has been synthesized by a one‐pot three component reaction among 3‐formylchromone, aromatic amine, and cyclohexyl isocyanide. 3‐(N‐alkylsubstitued/unsubstituted)aminomethylidenechroman‐2‐carboxamides were synthesized by heating Passerini products derived from chromone‐3‐carbaldehyde with different aliphatic primary amines. The products obtained from the reactions of aliphatic primary amines readily form chromeno[2,3‐c]pyrrole when heated in acetic acid. Bischromanones have also been synthesized using this methodology.     

Polyoxometalate-Engineered Building Blocks with Gold Cores for the Self-Assembly of Responsive Water-Soluble Nanostructures

The controlled assembly of gold nanoparticles (AuNPs) with the size of quantum dots into predictable structures is extremely challenging as it requires the quantitatively and topologically precise placement of anisotropic domains on their small, approximately spherical surfaces. We herein address this problem by using polyoxometalate leaving groups to transform 2 nm diameter gold cores into reactive building blocks with hydrophilic and hydrophobic surface domains whose relative sizes can be precisely tuned to give dimers, clusters, and larger micelle-like organizations. Using cryo-TEM imaging and ¹H DOSY NMR spectroscopy, we then provide an unprecedented “solution-state” picture of how the micelle-like structures respond to hydrophobic guests by encapsulating them within 250 nm diameter vesicles whose walls are comprised of amphiphilic AuNP membranes. These findings provide a versatile new option for transforming very small AuNPs into precisely tailored building blocks for the rational design of functional water-soluble assemblies.     

Attaining record-high magnetic exchange,magnetic anisotropy and blocking barriers in dilanthanofullerenes

While the blocking barrier (U_eff) and blocking temperature (T_B) for “Dysprocenium” SIMs have been increased beyond liquid N₂ temperature, device fabrication of these molecules remains a challenge as low-coordinate Ln³⁺ complexes are very unstable. Encapsulating the lanthanide ion inside a cage such as a fullerene (called endohedral metallofullerene or EMF) opens up a new avenue leading to several Ln@EMF SMMs. The ab initio CASSCF calculations play a pivotal role in identifying target metal ions and suitable cages in this area. Encouraged by our earlier prediction on Ln₂@C₇₉N, which was verified by experiments, here we have undertaken a search to enhance the exchange coupling in this class of molecules beyond the highest reported value. Using DFT and ab initio calculations, we have studied a series of Gd₂@C_2n (30 ≤ 2n ≤ 80), where an antiferromagnetic J_Gd⋯Gd of −43 cm⁻¹ was found for a stable Gd₂@C₃₈-D_3h cage. This extremely large and exceptionally rare 4f⋯4f interaction results from a direct overlap of 4f orbitals due to the confinement effect. In larger cages such as Gd₂@C₆₀ and Gd₂@C₈₀, the formation of two centre-one-electron (2c-1e⁻) Gd–Gd bonds is perceived. This results in a radical formation in the fullerene cage leading to its instability. To avoid this, we have studied heterofullerenes where one of the carbon atoms is replaced by a nitrogen atom. Specifically, we have studied Ln₂@C₅₉N and Ln₂@C₇₉N, where strong delocalisation of the electron yields a mixed valence-like behaviour. This suggests a double-exchange (B) is operational, and CASSCF calculations yield a B value of 434.8 cm⁻¹ and resultant J_Gd–rad of 869.5 cm⁻¹ for the Gd₂@C₅₉N complex. These parameters are found to be two times larger than the world-record J reported for Gd₂@C₇₉N. Further ab initio calculations reveal an unprecedented U_cal of 1183 and 1501 cm⁻¹ for Dy₂@C₅₉N and Tb₂@C₅₉N, respectively. Thus, this study offers strong exchange coupling as criteria for new generation SMMs as the existing idea of enhancing the blocking barrier via crystal field modulation has reached its saturation point.

Using ab initio calculations, we have made some robust predictions towards lanthanofullerene SMMs exhibiting remarkable characteristics.     

Tuning Ruthenium Carbene Complexes for Selective P−H Activation through Metal-Ligand Cooperation

The use of iminophosphoryl-tethered ruthenium carbene complexes to activate secondary phosphine P−H bonds is reported. Complexes of type [(p-cymene)-RuC(SO₂Ph)(PPh₂NR)] (with R = SiMe₃ or 4-C₆H₄−NO₂) were found to exhibit different reactivities depending on the electronics of the applied phosphine and the substituent at the iminophosphoryl moiety. Hence, the electron-rich silyl-substituted complex undergoes cyclometallation or shift of the imine moiety after cooperative activation of the P−H bond across the M=C linkage, depending on the electronics of the applied phosphine. Deuteration experiments and computational studies proved that cyclometallation is initiated by the activation process at the M=C bond and triggered by the high electron density at the metal in the phosphido intermediates. Consistently, replacement of the trimethylsilyl (TMS) group by the electron-withdrawing 4-nitrophenyl substituent allowed the selective cooperative P−H activation to form stable activation products.     

Activation and Conversion of Molecular Nitrogen to the Precursor of Ammonia on Silicon Substituted Cyclo[18]Carbon: a DFT Design

Recent synthesis of sp-hybridized cyclo[18]carbon allotrope has attracted immense curiosity. Since then, a generous amount of theoretical studies concerning aromaticity, adsorption, and spectra of the molecule have been performed. However, very few stuides have been carried out concerning its reactivities and catalytic behaviour. In this article, a DFT-based inquisition has been reported regarding the reactivity of Si substituted cyclo[18]carbon molecule towards molecular N₂. Results show that the Si substituted derivative is effective in producing adducts with molecular nitrogen. Charge calculations and IRC trapping methods indicate that only the Si center of C₁₇Si and its (HOMO-1) level participate in N₂ addition. The N-adduct so formed, is then found to spontaneously react with molecular H₂. The addition of two H₂ molecules to the activated nitrogen molecule to give respective amine derivatives have also been studied. The successful generation of the precursor of NH₃ by C₁₇Si lays a clear emphasis on its potentiality.