Ligand Field Strength Research Articles

The cooperative effects of ligand substituent positions and solvents on spin crossover in Mn(III) complexes based on hexadentate Schiff-base ligands

Spin crossover (SCO), as a molecular bistable phenomenon, has attracted extensive interest. In this paper, the syntheses, crystal structures and magnetic properties of three Mn(III) hexadentate Schiff-base complexes [Mn(3-OMe-sal-N-1,5,8,12)]AsF6·H2O (1), [Mn(4-OMe-sal-N-1,5,8,12)]AsF6·H2O (2) and [Mn(5-OMe-sal-N-1,5,8,12)]AsF6(3) have been reported. The substituent positions of ligands and solvent molecules have a cooperative effect on SCO behavior. Complex 1 shows a complete SCO between the high-spin (HS, S = 2) and low-spin (LS, S = 1) states without thermal hysteresis, and complex 2 shows a gradual incomplete SCO behavior. The transition temperatures of 2 (T1/2 = 241 K) is 98 K higher than that of 1 (T1/2 = 143 K), which indicates that the ligand field strength of (4-OMe-sal-N-1,5,8,12)2– is stronger than that of (3-OMe-sal-N-1,5,8,12)2–. Due to the absence of crystallizing solvent water molecule, complex 3 maintains a HS state in the test temperature range.

A theoretical study of the effect of phosphorus and nitrogen heteroatoms on pentahapto coordination of diazaphospholyl ligands in binuclear ruthenium and iron carbonyl derivatives

The structures and energies of the (Me2C2N2P)2Ru2(CO)n (n = 4, 3) complexes of the four isomeric diazaphospholyl ligands have been studied by density functional theory. Most of the low-energy structures in these systems have one or both diazaphospholyl rings bridging a central RuRu bond through RuN and/or RuP bonds without involvement of the other three ring atoms. A few higher energy structures are found in these systems having either terminal pentahapto η5-Me2C2N2P ligands or bridging η5,η1-Me2C2N2P ligands bonded to one ruthenium atom as a pentahapto ligand and to the other ruthenium atom through a P → Ru or N → Ru dative bond. The potential surfaces of the analogous iron systems (Me2C2N2P)2Fe2(CO)n (n = 4, 3) are complicated considerably by other triplet and even quintet structures of comparable energies to structures analogous to the low-energy ruthenium structures. This relates to the lower ligand field strengths of iron complexes as compared with their ruthenium analogues.

Mechanistic Insights into Nitrile Activation by Cobalt(III)-Hydroperoxo Intermediates: The Influence of Ligand Basicity.

The versatile applications of nitrile have led to the widespread use of nitrile activation in the synthesis of pharmacologically and industrially valuable compounds. We reported the activation of nitriles using mononuclear cobalt(III)-hydroperoxo complexes, [CoIII(Me3-TPADP)(O2H)(RCN)]2+ [R = Me (2) and Ph (2Ph)], to form cobalt(III)-peroxyimidato complexes, [CoIII(Me3-TPADP)(R-C(=NH)O2)]2+ [R = Me (3) and Ph (3Ph)]. The independence of the rate on the nitrile concentration and the positive Hammett value of 3.2(2) indicated that the reactions occur via an intramolecular nucleophilic attack of the hydroperoxide ligand to the coordinated nitrile carbon atom. In contrast, the previously reported cobalt(III)-hydroperoxo complex, [CoIII(TBDAP)(O2H)(CH3CN)]2+ (2TBDAP), exhibited the deficiency of reactivity toward nitrile. The comparison of pKa values and redox potentials of 2 and 2TBDAP showed that Me3-TPADP had a stronger ligand field strength than that of TBDAP. The density functional theory calculations for 2 and 2TBDAP support that the strengthened ligand field in 2 is mainly due to the replacement of two tert-butyl amine donors in TBDAP with methyl groups in Me3-TPADP, resulting in the compression of the Co-Nax bond lengths. These results provide mechanistic evidence of nitrile activation by the cobalt(III)-hydroperoxo complex and indicate that the basicity dependent on the ligand framework contributes to the ability of nitrile activation.

Electron paramagnetic resonance and luminescence properties of Eu2+ in oxyfluoride barium borate glasses

The Eu-doped xBaO-(100-x)B2O3 and xBaF2-(100-x)B2O3 glasses were prepared by melting method under a reducing atmosphere, exhibiting broadband luminescence peaks of 4f65 d1→4f7 in the excitation range of 300–400 nm. PL, EPR, and XPS were used to analyze the effects of the Ba2+, F−, and Eu ion content on the Eu2+/Eu3+ ratio and Eu2+ emission wavelength and intensity. An excess of Ba2+ ions with a high optical basicity reduced the Eu2+/Eu3+ ratio and enhanced the ligand field strength surrounding the Eu2+ ions, decreasing the Eu2+ luminescence intensity and red-shifting the luminescence peak. The addition of F− had the effect of diminishing the optical basicity, decreasing the OH groups content and eliminating Eu2+ clusters, which not only mitigated the effects of the Ba2+ ions, but also significantly enhanced the luminescence intensity of Eu2+ ions. An increase in the Eu ion concentration led to a red-shift in the Eu2+ fluorescence, which was attributed to the nephelauxetic effect. Therefore, the luminescence color of these glass samples could be manipulated by adjusting the doping concentrations of Ba2+, F−, and Eu2+.

Perspective from a Hubbard U-density corrected scheme towards a spin crossover-mediated change in gas affinity.

By employing a recently proposed Hubbard U density-corrected scheme within density functional theory, we provide design principles towards the design of materials exhibiting a spin crossover-assisted gas release. Small molecular fragments are used as case study to identify two main mechanisms behind the change in binding energy upon spin transitions. The feasibility of the proposed mechanism in porous crystals is assessed by correlating the change in binding energy of CO2, CO, N2, and H2, upon spin crossover, with the adiabatic energy difference associated with the spin state change of the square-planar metal in Hofmann-type clathrates (M = Fe, Mn, Ni). A few promising cases are identified for the adsorption of intermediate ligand field strength molecules such as N2 and H2. The latter stands out as the most original result as the strong interaction in low spin, as expected from a Kubas mechanism, results in a large change in binding energy. This work provides a general perspective towards the engineering of open-metal site frameworks exhibiting local environments designed to have a spin crossover upon adsorption of specific gas molecules.

Tailoring ligand fields of metal-azolate frameworks for highly selective electroreduction of CO2 to hydrocarbons at industrial current density

The catalytic activity of a metal complex is often contingent upon factors such as its valence state, coordination configuration of the metal ion, and coordination ability of the ligand. Hence, revealing the influence of the ligand field of the active metal center on the selectivity of the product for electrochemical CO2 reduction is crucial. Herein, three isostructural metal-azolate frameworks (MAFs) (Cu-BTP, Cu-BTTri, and Cu-BTT) with the same cyclic tetracopper(II) cluster units, namely [Cu3(BTP)2] (Cu-BTP, H3BTP = 1,3,5-tris(1H-pyrazol-4-yl)benzene), [Cu3(BTTri)2] (Cu-BTTri, H3BTTri = 1,3,5-tris(1H-1,2,3-triazol-5-yl)benzene), and [Cu3(BTT)2] (Cu-BTT, H3BTT = 1,3,5-tris(2H-tetrazol-5-yl)benzene) were synthesized using pyrazolate-, triazolate-, and tetrazolate-based ligands, respectively. The synthesized MAFs were subjected to analysis to evaluate their electrochemical capabilities for reducing CO2 under identical reaction conditions. Among them, the pyrazolate MAF, Cu-BTP, delivers a current density of 1.25 A cm2 in a flow cell device with the highest Faradiac efficiency for hydrocarbons (CH4, 60%; C2H4, 22%). Furthermore, the system shows no obvious degradation over 60 h of continuous operation. The order of selectivity of the three MAFs for hydrocarbon production is consistent with the corresponding pKa values of the azolate ligands. Theoretical calculations show that a stronger Lewis basicity of the organic ligand, resulting in a stronger ligand field strength, is conducive to strengthening the binding of metal centers with key intermediates, such as *CO and *CHO. This ultimately leads to the deep reduction of CO2 to hydrocarbons.

Manganese incorporation for cesium zinc chloride crystals and the resultant structural, and optical characteristics

Here, we have successfully synthesized manganese (Mn) doped cesium zinc chloride (Cs2ZnCl4) crystals for the first time by a simple solvothermal method, which alters the optical properties due to the structural transformation. When Mn2+ feeding ratio x is lower than 0.4, tetrahedral structure of Cs2ZnCl4 crystals is dominant with green emission of Mn2+ doping, but both tetrahedral and octahedral structure show green–red emission when Mn2+ feeding ratio exceeds 0.4. Combining experimental analysis and density functional theory (DFT) calculations, different energy transfer pathways and photoluminescence (PL) emission are revealed. When the host lattice crystal field surroundings of tetrahedral coordination, due to the incorporation of Mn2+, the exciton relaxes to 4T1 and then transitions to 6A1. However, when the host lattice crystal field surroundings have a strong ligand field strength, the excitons are more advantageously confined to the octahedron. Our work provides deeper insights into the structural transformation of zero-dimensional all-inorganic metal halide due to the Mn2+ incorporation from doping to substitution of B site.

Controlling Spin Crossover in a Family of Dinuclear Fe(III) Complexes via the Bis(catecholate) Bridging Ligand.

Spin crossover (SCO) complexes can reversibly switch between low spin (LS) and high spin (HS) states, affording possible applications in sensing, displays, and molecular electronics. Dinuclear SCO complexes with access to [LS-LS], [LS-HS], and [HS-HS] states may offer increased levels of functionality. The nature of the SCO interconversion in dinuclear complexes is influenced by the local electronic environment. We report the synthesis and characterization of [{FeIII(tpa)}2spiro](PF6)2 (1), [{FeIII(tpa)}2Br4spiro](PF6)2 (2), and [{FeIII(tpa)}2thea](PF6)2 (3) (tpa = tris(2-pyridylmethyl)amine, spiroH4 = 3,3,3',3'-tetramethyl-1,1'-spirobi(indan)-5,5',6,6'-tetraol, Br4spiroH4 = 3,3,3',3'-tetramethyl-1,1'-spirobi(indan)-4,4',7,7'-tetrabromo-5,5',6,6'-tetraol, theaH4 = 2,3,6,7-tetrahydroxy-9,10-dimethyl-9,10-dihydro-9,10-ethanoanthracene), utilizing non-conjugated bis(catecholate) bridging ligands. In the solid state, magnetic and structural analysis shows that 1 remains in the [HS-HS] state, while 2 and 3 undergo a partial SCO interconversion upon cooling from room temperature involving the mixed [LS-HS] state. In solution, all complexes undergo SCO from [HS-HS] at room temperature, via [LS-HS] to mixtures including [LS-LS] at 77 K, with the extent of SCO increasing in the order 1 < 2 < 3. Gas phase density functional theory calculations suggest a [LS-LS] ground state for all complexes, with the [LS-HS] and [HS-HS] states successively destabilized. The relative energy separations indicate that ligand field strength increases following spiro4- < Br4spiro4- < thea4-, consistent with solid-state magnetic and EPR behavior. All three complexes show stabilization of the [LS-HS] state in relation to the midpoint energy between [LS-LS] and [HS-HS]. The relative stability of the [LS-HS] state increases with increasing ligand field strength of the bis(catecholate) bridging ligand in the order 1 < 2 < 3. The bromo substituents of Br4spiro4- increase the ligand field strength relative to spiro4-, while the stronger ligand field provided by thea4- arises from extension of the overlapping π-orbital system across the two catecholate units. This study highlights how SCO behavior in dinuclear complexes can be modulated by the bridging ligand, providing useful insights for the design of molecules that can be interconverted between more than two states.

BEG spin-1 model with random exchange magnetic interactions for spin-crossover solids

We have investigated magnetic phase diagrams of spin-crossover (SCO) solids throughout the Blume–Emery–Griffiths spin-1 model where the spin states ±1 and 0 are associated to high-spin state and low-spin states respectively. In the present work, the quadrupolar interaction, K, parameter depends linearly on temperature and accounts for the role of the lattice phonons in the elastic interactions between the SCO units. Magnetic interactions are randomly distributed in the system and are controlled by a factor such that for γ = 0 (), magnetic ordering is not expected. The crystal-field that acts on SCO sites depends both on the ligand-field strength and the degeneracy ratio between HS and LS states as in some previous works. The system is also under the effect of a random local magnetic field hi acting on each site i. The model is solved using a homogeneous mean field theory. Our investigations reveal the occurrence of thermally-induced gradual, and first-order spin-transitions by varying the model parameters. At vicinity of first-order transition, various types of isothermal magnetic hysteresis loops are obtained and their corresponding coercive field and loop patterns are discussed as function of temperature.

Impacts of BaO additives on the mechanical, optical and radiation shielding properties of BaO–K2O– CoO–Al2O3–B2O3 glasses

This article reports the influence of barium oxide (BaO) on mechanical and radiation protection characteristics of BaO–K2O– CoO–Al2O3–B2O3 glass. The obtained results confirmed the enhanced the elastic moduli, confirming a high cross-linked density, high impact resistance, and toughness of the network, with the good mechanical stability of samples with further additives of BaO. In detail, with increasing BaO contents, it is observed that the shear modulus increased from 33.8 GPa reaching 37.7 GPa (increased by about 11.5%), while the longitudinal modulus enhanced from 100.5 GPa up to 117.4 GPa (enhanced by ⁓ 16.8%), besides Young's modulus augmented from 84.4 GPa to 95.3 GPa (augmented by ⁓ 13%), and bulk modulus is increased from 55.4 GPa reaching 67.2 GPa (increased by ⁓ 21.3%). These enhancements in the elastic moduli are attributed to the increased tetrahedral units (BO4 and AlO4 units) inside the glass matrix with increasing BaO additives. On the other hand, with increasing BaO, optical band gaps increase from 3.07 eV to 3.58 eV, and ligand field strength values decrease from 3494 cm−1 to 3273 cm−1. Furthermore, the addition of BaO reduces the linear and nonlinear refractive indices. Moreover, the obtained radiation shielding parameters were studied and compared to those of well-known shielding materials. The comparison confirmed that the glass specimen with the highest barium oxide content has better radiation shielding ability than others and is suitable for radiation shielding applications.

The structure, optical basicity, ligand field strength and shielding parameters of alkali/alkaline borate glasses doped with V2O5

In this work, we study the structural, optical and radiation shielding properties of Na2O–CaO-borate glass doped with different amounts of V2O5. A glass system with the composition (10.5CaO+ 16.5Na2O+ (73-x)B2O3+ xV2O5; where x = 0, 2.5, 5 and 10.5 mol%) was produced following the melt quenching technique. The molar volume and density of glasses both increase with the increase in V2O5:B2O3 ratios. Moreover, the average ligand field strength reduced from 2.32 to 2.15 × 1016 cm2 with the increase in V2O5:B2O3 ratios, which correlates with the increased values of molar volume and interatomic separations. Furthermore, the optical basicity of the glass samples increased from 0.601 to 0.666 with increasing V2O5:B2O3 ratios. The optical absorption spectra are studied for further investigation of the optical features. To extract the absorption edge and the absorption bands, a deconvolution process was applied to the absorption spectra. The obtained bands from this deconvolution process confirmed the presence of vanadium in its oxidation states V3+, V4+ and V5+. Furthermore, more additions of V2O5 produced an obvious reduction in Eg values from 3.69 to 3.08 eV along with a redshift in the fundamental absorption edges. These results were attributed to the further creation of nonbridging oxygens within the glass matrix. Furthermore, the addition of V2O5 rather than B2O3 enhances the radiation shielding parameters. Accordingly, the CaNaBV10.5 glass sample is the best attenuator among the fabricated CaO–Na2O–B2O3–V2O5 glasses due to the highest mass attenuation coefficient and lowest half-value layer. Moreover, the half-value layer values of the present glasses were compared to some common materials in the radiation shielding field. From this comparison, we concluded that all glass samples are better than commercial glass windows and ordinary concrete.

Enhanced Understanding of Structure-Function Relationships for Oxomanganese(IV) Complexes.

A series of manganese(II) and oxomanganese(IV) complexes supported by neutral, pentadentate ligands with varied equatorial ligand-field strength (N3pyQ, N2py2I, and N4pyMe2) were synthesized and then characterized using structural and spectroscopic methods. On the basis of electronic absorption spectroscopy, the [MnIV(O)(N4pyMe2)]2+ complex has the weakest equatorial ligand field among a set of similar MnIV-oxo species. In contrast, [MnIV(O)(N2py2I)]2+ shows the strongest equatorial ligand-field strength for this same series. We examined the influence of these changes in electronic structure on the reactivity of the oxomanganese(IV) complexes using hydrocarbons and thioanisole as substrates. The [MnIV(O)(N3pyQ)]2+ complex, which contains one quinoline and three pyridine donors in the equatorial plane, ranks among the fastest MnIV-oxo complexes in C-H bond and thioanisole oxidation. While a weak equatorial ligand field has been associated with high reactivity, the [MnIV(O)(N4pyMe2)]2+ complex is only a modest oxidant. Buried volume plots suggest that steric factors dampen the reactivity of this complex. Trends in reactivity were examined using density functional theory (DFT)-computed bond dissociation free energies (BDFEs) of the MnIIIO-H and MnIV ═ O bonds. We observe an excellent correlation between MnIV═O BDFEs and rates of thioanisole oxidation, but more scatter is observed between hydrocarbon oxidation rates and the MnIIIO-H BDFEs.

Dinuclear Iron(II) Triple Helicates Exhibiting Room Temperature Spin-Transition Behaviour in Solid and Solution Phase.

Herein, three dinuclear iron(II) helicates bearing the molecular formula [Fe2 (L1)3 ](ClO4 )4 ⋅ 2CH3 OH ⋅ 3H2 O (complex 1), [Fe2 (L2)3 ](ClO4 )4 ⋅ 6CH3 CN (complex 2), and [Fe2 (L3)3 ](ClO4 )4 ⋅ 0.5H2 O (complex 3) have been synthesized using imidazole and pyridine-imine-based ligands having fluorene moiety in the backbone. A change in the ligand field strength by terminal modulation led to a change in the spin-transition behaviour from incomplete, multi-step to complete, around room temperature in the solid state. Spin transition behaviour has also been observed in the solution phase characterized using variable temperature 1 H nuclear magnetic resonance spectroscopy (Evans method) and correlated using UV-visible spectroscopy. Fitting the NMR data using the ideal solution model yielded the transition temperature in the order T1/2 (1)<T1/2 (2)<T1/2 (3), which indicates an increase in the ligand field strength from complexes 1 to 3. This study accentuates the interplay between the ligand field strength, crystal packing, and supramolecular interactions in fine-tuning the spin transition behaviour effectively.

Coupled Potential Energy Surfaces Strongly Impact the Lowest-Energy Spin-Flip Transition in Six-Coordinate Nickel(II) Complexes.

Luminescent complexes of earth-abundant first-row transition metals are of renewed, broad interest due to their spectroscopic and photochemical properties as well as emerging applications. New strong-field polypyridine ligands have led to six-coordinate 3d3 chromium(III) complexes with intense spin-flip luminescence in solution at room temperature. The ground and emissive states both arise from the (t2)3 electron configuration involving the dπ levels (O point group symmetry labels). Pseudoctahedral 3d8 nickel(II) complexes with such strong ligands are a priori also promising candidates for spin-flip luminescence. In contrast, the relevant electron configurations involve the dσ orbitals and (e)2 configurations. We have prepared the known nickel(II) complexes [Ni(terpy)2]2+, [Ni(phen)3]2+, and [Ni(ddpd)2]2+ as well as the novel complexes [Ni(dgpy)2]2+ and [Ni(tpe)2]2+ forming a series with increasing ligand field strengths (terpy = 2,2':6',2″-terpyridine; phen = 1,10-phenanthroline; ddpd = N,N'-dimethyl-N,N'-dipyridine-2-ylpyridine-2,6-diamine; dgpy = 2,6-diguanidylpyridine; tpe = 1,1,1-tris(pyrid-2-yl)ethane). The lowest-energy singlet and triplet excited states of these nickel(II) complexes are analyzed based on absorption spectra using ligand field theory and CASSCF-NEVPT2 calculations for vertical transition energies and a model based on coupled potential energy surfaces, leading to calculated absorption spectra in good agreement with the experimental data. No photoluminescence signal was observed in the wavelength ranges identified through the analyses of the absorption spectra. The models provide insight into key differences between the nickel(II) complexes and their strongly luminescent chromium(III) analogues.

The Nephelauxetic Effect Becomes an Important Design Factor for Photoactive First‐Row Transition Metal Complexes

AbstractThe expansion of d‐orbitals as a result of metal‐ligand bond covalence, the so‐called nephelauxetic effect, is a well‐established concept of coordination chemistry, yet its importance for the design of new photoactive complexes based on first‐row transition metals is only beginning to be recognized. Until recently, much focus has been on optimizing the ligand field strength, coordination geometries, and molecular rigidity, but now it becomes evident that the nephelauxetic effect can be a game changer regarding the photophysical properties of 3d metal complexes in solution at room temperature. In CrIII and MnIV complexes with the d3 valence electron configuration, the nephelauxetic effect was exploited to shift the well‐known ruby‐like red luminescence to the near‐infrared spectral region. In FeII and CoIII complexes with the low‐spin d6 electron configuration, charge‐transfer excited states were stabilized with respect to detrimental metal‐centered excited states, to improve their properties and to enhance their application potential. In isoelectronic (3d6) isocyanide complexes of Cr0 and MnI, the nephelauxetic effect is likely at play as well, enabling luminescence and other favorable photoreactivity. This minireview illustrates the broad applicability of the nephelauxetic effect in tailoring the photophysical and photochemical properties of new coordination compounds made from abundant first‐row transition metals.

The Nephelauxetic Effect Becomes an Important Design Factor for Photoactive First-Row Transition Metal Complexes.

The expansion of d-orbitals as a result of metal-ligand bond covalence, the so-called nephelauxetic effect, is a well-established concept of coordination chemistry, yet its importance for the design of new photoactive complexes based on first-row transition metals is only beginning to be recognized. Until recently, much focus has been on optimizing the ligand field strength, coordination geometries, and molecular rigidity, but now it becomes evident that the nephelauxetic effect can be a game changer regarding the photophysical properties of 3d metal complexes in solution at room temperature. In CrIII and MnIV complexes with the d3 valence electron configuration, the nephelauxetic effect was exploited to shift the well-known ruby-like red luminescence to the near-infrared spectral region. In FeII and CoIII complexes with the low-spin d6 electron configuration, charge-transfer excited states were stabilized with respect to detrimental metal-centered excited states, to improve their properties and to enhance their application potential. In isoelectronic (3d6 ) isocyanide complexes of Cr0 and MnI , the nephelauxetic effect is likely at play as well, enabling luminescence and other favorable photoreactivity. This minireview illustrates the broad applicability of the nephelauxetic effect in tailoring the photophysical and photochemical properties of new coordination compounds made from abundant first-row transition metals.

Impactive cadmium modifications to enhance the structural-optical relationship in nickel borate glasses

Cadmium-doped borate glass composition was prepared via the melt-quenching technique. The nature of the glass structure was detected by X-ray diffraction (XRD). The physical parameters, such as density (ρ) from Archimedes’ principle, molar volume (Vm), Cd2+ ions concentration (NCd), and inter-atomic distance (Ri) were evaluated, providing structural information on glass samples. Fourier transform infrared (FT-IR) analysis was used to study the fundamental vibrational modes of structural units, confirming the conversion of BO3 to BO4 units, indicating a strongly bonded and high connectivity of the network. Some important optical findings were extracted from the analysis of optical absorption spectra. For example, the mitigation in the optical band gap, the increase in Urbach energy, the deterioration in the metallization criterion, and the enhancement in the electron-phonon interaction were obtained with cadmium oxide addition. The nonlinearity characteristics were enhanced, making these glass samples have viability in the non-linear optics sector. The obtained data from the electron spin resonance (ESR) revealed that the nickel ions exist in a divalent oxidation state with octahedral symmetry. Interestingly, the optical absorption transitions of Ni2+ ions were accurately deconvoluted and assigned to octahedral and tetrahedral positions. The equations of ligand field parameters of octahedral Ni2+ ions were correctly presented. The equation of Racah C parameter was deduced for the first time. Then, the ligand field parameters, such as the ligand field strength (10 Dq), Racah parameters (B and C), and other related parameters, were precisely assessed. The covalent nature between Ni2+ ions and the ligands was detected from the nephelauxetic effect.

Inverse design of ligands using a deep generative model semi‐supervised by a data‐driven ligand field strength metric

AbstractTransition metal (TM) complexes exhibit diverse structural and electronic properties. The properties of a TM complex can be tuned by modulating the ligand field strength (LFS) inflicted by its ligands. Current quantification of the LFS of a ligand is mainly derived from experimental measurements on a subset of highly symmetrical TM complexes and is limited in ligand scope. Herein, we report a data‐driven method to quantify the LFS of ligands assigned from experimental crystal structures of TM complexes. We first show that the experimental metal–ligand bond lengths of over 4,000 mononuclear Fe, Co, and Mn complexes form bimodal distributions. Using Gaussian fits on the bimodal distributions, each TM complex is assigned a spin state (SS) label. These SS labels can then be used to calculate the LFS of the ligands of the complexes. Using the obtained data‐driven LFS metric, we establish that a semi‐supervised deep generative model, junction tree variational autoencoder (JTVAE), can be employed to predict LFS values. Our model exhibits a mean absolute error (MAE) of 0.047 and root mean squared error of 0.072 on the training set. The model also allows the generation of novel ligands with desirable LFS values.

Nanosecond Metal-to-Ligand Charge-Transfer State in an Fe(II) Chromophore: Lifetime Enhancement via Nested Potentials.

Examples of Fe complexes with long-lived (≥1 ns) charge-transfer states are limited to pseudo-octahedral geometries with strong σ-donor chelates. Alternative strategies based on varying both coordination motifs and ligand donicity are highly desirable. Reported herein is an air-stable, tetragonal FeII complex, Fe(HMTI)(CN)2 (HMTI = 5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradeca-1,3,8,10-tetraene), with a 1.25 ns metal-to-ligand charge-transfer (MLCT) lifetime. The structure has been determined, and the photophysical properties have been examined in a variety of solvents. The HMTI ligand is highly π-acidic due to low-lying π*(C═N), which enhances ΔFe via stabilizing t2g orbitals. The inflexible geometry of the macrocycle results in short Fe-N bonds, and density functional theory calculations show that this rigidity results in an unusual set of nested potential energy surfaces. Moreover, the lifetime and energy of the MLCT state depends strongly on the solvent environment. This dependence is caused by modulation of the axial ligand-field strength by Lewis acid-base interactions between the solvent and the cyano ligands. This work represents the first example of a long-lived charge transfer state in an FeII macrocyclic species.

Spin-Crossover Behaviors of Iron(II) Complexes Bearing Halogen Ligands in Solid State and Solution.

Numerous Fe(II) spin-crossover (SCO) compounds have been developed in the past decades, while the reports on the SCO materials with halogen atoms acting as coordinating ligands remain rare. In this study, we synthesize three iron(II) halide complexes with a general formula of [FeII(Py5Me2)X]+ (Py5Me2 = 2,6-bis[1,1-bis(2-pyridyl)ethyl]pyridine, X = Cl- or Br-) that undergo complete SCO transitions at near room temperature. The SCO properties of these compounds are investigated in detail by magnetic measurements, variable-temperature single-crystal X-ray diffractions, and Mössbauer spectra analyses. Because of the good stability of the coordination structures and suitable ligand-field strength, these compounds show robust spin transitions in both solid state and solution.