High-Spin Blatter's Triradicals.

Robust organic triradicals with high-spin quartet ground states provide promising applications in molecular magnets, spintronics, etc. In this context, a triradical based on Blatter's radical has been synthesized recently, having two low-lying non-degenerate doublet states with a quartet ground state. The traditional broken-symmetry (BS)-DFT computed doublet-quartet energy gaps are reported to be somewhat overestimated in comparison to the experimentally observed values. In this work, we have employed different ab initio methods on this prototypical system to obtain more accurate doublet-quartet energy gaps for this triradical. The spin-constraint broken-symmetry (CBS)-DFT method has been used to reduce the overestimation of energy gaps from BS-DFT. To address the issues of spin-contamination and the multireference nature of low-spin states affecting the DFT methods, we have computed the energy gaps using appropriately state-averaged CASSCF and NEVPT2 computations. Using a series of active spaces, our calculations are shown to provide quite accurate values in concordance with the experimentally observed results. Furthermore, we have proposed and modeled another two triradicals based on Blatter's radical, which are of interest for experimental synthesis and characterization. Our computations show that all these triradicals also have a quartet ground state with a similar energy difference between the excited doublet states.

Single-Molecule Magnetism in Linear Fe(I) Complexes with Aufbau and Non-Aufbau Ground States.

With the ongoing efforts on synthesizing mononuclear single-ion magnets (SIMs) with promising applications in high-density data storage and spintronics devices, the linear or quasi-linear Fe(I) complexes emerge as the enticing candidates possessing large unquenched angular momentum. Herein, we have studied five experimentally synthesized linear Fe(I) complexes to uncover the origin of single-molecule magnetic behavior of these complexes. To begin with, we benchmarked the methodology on the experimentally and theoretically well-studied complex [Fe(C(SiMe3)3)2]-1 (1) (SiMe3 = trimethylsilyl), which is characterized with a large spin-reversal barrier of 226 cm-1. Subsequently, the spin-phonon coupling coefficients are calculated for the low-frequency vibrational modes to understand the relaxation mechanism of the complex. Furthermore, the two Fe(I) complexes, that is, [Fe(cyIDep)2]+1 (2) (cyIDep = 1,3-bis(2',6'-diethylphenyl)-4,5-(CH2)4-imidazole-2-ylidene) and [Fe(sIDep)2]+1 (3) (sIDep = 1,3-bis(2',6'-diethylphenyl)-imidazolin-2-ylidene), are studied that are experimentally reported with no SIM behavior under ac or dc magnetic fields; however, they exhibit large opposite axial zero field splitting (-62.4 and +34.0 cm-1, respectively) from ab initio calculations. We have unwrapped the origin of this contrasting observation between experiment and theory by probing their magnetic relaxation pathways and the pattern of d orbital splitting. Additionally, the two experimentally synthesized Fe(I) complexes, that is, [(η6-C6H6)FeAr*-3,5-Pr2i] (4) (Ar*-3,5-Pr2i = C6H-2,6-(C6H2-2,4,6-Pr3i)2-3,5-Pr2i) and [(CAAC)2Fe]+1 (5) (CAAC = cyclic (alkyl) (amino)carbene), are investigated for SIM behavior, since there is no report on their magnetic anisotropy. To this end, complex 4 presents itself as the possible candidate for SIM.

Harnessing Colossal Magnetic Anisotropy in Sandwiched 3d2-Metallocenes.

Single-molecule magnets are gaining attention in recent years with the growing focus on achieving higher barriers of magnetization reversal. Metallocenes, owing to their unique sandwiched structure, assure themselves as plausible molecular systems for the development of novel single-molecule magnets (SMMs). Here in this work, we have explicitly investigated metallocenes of first-row transition elements, along with their one-electron-oxidized (cationic) and -reduced (anionic) analogues, for their magnetic anisotropies by adopting multireference ab initio calculations. Herein, we report a high magnetic anisotropy for 3d2 systems among all 3d-metallocenes.

semiaza-Bambusurils are anion-specific transmembrane transporters.

semiaza-Bambus[6]urils efficiently transport anions across lipid membranes. A systematic modification of their lipophilic side chains to include various alkyl groups and thioethers reveals that the most efficient chloride transporters are those that agree with Lipinski's rule-of-lipophilicity, exhibiting clog Po/w values close to 5. Furthermore, vesicle anion-transport assays show that the new anion-transporters are independent of the cation identity but exhibit high anion selectivity, NO3- > Br- > Cl- > SO42-, in agreement with the Hofmeister series. These findings will allow for the design of highly specific anion transporters for biomedical applications, particularly for managing anion channelopathies.

Tuning the magnetic properties of a diamagnetic di-Blatter's zwitterion to antiferro- and ferromagnetically coupled diradicals.

In the quest of obtaining organic molecular magnets based on stable diradicals, we have tuned the inherent zwitterionic ground state of tetraphenylhexaazaanthracene (TPHA), a molecule containing two Blatter's moieties, by adopting two different strategies. In the first strategy, we have increased the length of the coupler between the two radical moieties and observed a transition from the zwitterionic ground state to the diradicalized state. With a larger coupler, ferromagnetic interactions are realized based on density functional theory (DFT) and wave-function theory (WFT) based complete active space self-consistent field (CASSCF)-N-electron valence state perturbation theory (NEVPT2) methods. An analysis based on the extent of spin contamination, diradical character, CASSCF orbital occupation number, Head-Gordon's index, HOMO-LUMO and SOMOs energy gaps is demonstrated that marks the transition of the ground state in these systems. In another approach, we systematically explore the effect of push-pull substitution on the way to obtain molecules based on a TPHA skeleton with diradicaloid state and, in some cases, even a triplet ground state.

Auxiliary Atomic Relay Center Facilitates Enhanced Magnetic Couplings in Blatter's Radical.

The recent accomplishments in obtaining strong ferromagnetic exchange interactions in organic diradicals have made the field quite fascinating and even more promising toward its technological applications. In this context, herein, we report a unique combination of remarkably strong ferromagnetic exchange interactions coupled with molecular rigidity, utilizing superstable Blatter's radical as a spin source. The planar analogues of the parent Blatter's radical obtained by annulation with a chalcogen coupled to nitronyl nitroxide (NN) are investigated using density functional theory along with the wave function-based multiconfigurational self-consistent field methods, for example, complete active space self-consistent field (CASSCF)-N-electron valence state perturbation theory (NEVPT2). The calculations reveal phenomenal modulation in exchange couplings upon annulation such that remarkably strong ferromagnetic interactions are realized especially for a certain class of the Blatter-NN diradicals. The modulation of spin-spin interactions is rationalized by variation in spin density distribution and molecular torsional angles. We demonstrate that annulation in OMMs opens an additional coupling pathway via auxiliary X-atom acting as the atomic relay center which strongly manipulates the magnitude of exchange couplings.

First-Principles Investigations of Magnetic Anisotropy and Spin-Crossover Behavior of Fe(III)-TBP Complexes.

With the ongoing effort to obtain mononuclear 3d-transition-metal complexes that manifest slow relaxation of magnetization and, hence, can behave as single-molecule magnets (SMMs), we have modeled 14 Fe(III) complexes based on an experimentally synthesized (PMe3)2FeCl3 complex [J. Am. Chem. Soc. 2017, 139 (46), 16474-16477], by varying the axial ligands with group XV elements (N, P, and As) and equatorial halide ligands from F, Cl, Br, and I. Out of these, nine complexes possess large zero field splitting (ZFS) parameter D in the range of -40 to -60 cm-1. The first-principles investigation of the ground-spin state applying density functional theory (DFT) and wave function-based multiconfigurations methods, e.g., SA-CASSCF/NEVPT2, are found to be quite consistent except for few delicate cases with near-degenerate spin states. In such cases, the hybrid B3LYP functional is found to be biased toward high-spin (HS) state. Altering the percentage of exact exchange admixed in the B3LYP functional leads to intermediate-spin (IS) ground state consistent with the multireference calculations. The origin of large zero field splitting (ZFS) in the Fe(III)-based trigonal bipyramidal (TBP) complexes is investigated. Furthermore, a number of complexes are identified with very small ΔGHS-ISadia. values indicating the possible spin-crossover phenomenon between the bistable spin states.

How Plausible Is Getting Ferromagnetic Interactions by Coupling Blatter's Radical via Its Fused Benzene Ring?

With ongoing efforts to synthesize super-stable Blatter's diradicals having strong ferromagnetic exchange interactions, all the 10 possible isomers of di-Blatter diradical coupled through the fused benzene rings are investigated. A variety of electronic structure theory such as broken-symmetry methods in density functional theory (DFT), spin-constraint DFT (CDFT), and wave function-based multi-configurational methods, e.g., CASSCF/NEVPT2 are applied to compute the magnetic exchange interactions. Surprisingly, anti-ferromagnetic interactions are revealed for all the stable isomers of di-Blatter diradicals. Indeed, it is commensurate with the experimental observations for the only available synthesized isomer. However, the other nine isomeric diradicals in the series are yet to be synthesized. Despite a good match between theory and experiment, the anti-ferromagnetic exchange interactions could not be explained based on the spin alternation rule due to unique spin distributions in the triazinyl ring. Thus, we propose the zonal spin-alternation rule, which explains the observed ground spin-state for the conjugated di-Blatter diradicals quite accurately. Further, the fractional spin-moment localization on the N-atoms activates multiple exchange pathways and the dominating exchange interactions render anti-ferromagnetic interactions in the conjugated isomers. The study further reveals that, due to strong steric hindrance in certain coupled isomers, the exchange interaction switches from anti-ferromagnetic to weak ferromagnetic interactions with the cost of stabilization energy of the radicals. Thus, it questions the possibility of synthesizing ferromagnetic di-Blatter diradicals.