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Structural Insights into Hysteretic Spin-Crossover in a Set of Iron(II)-2,6-bis(1H-Pyrazol-1-yl)Pyridine) Complexes.

ABSTRACT: Bistable spin-crossover (SCO) complexes that undergo abrupt and hysteretic (ΔT_1/2 ) spin-state switching are desirable for molecule-based switching and memory applications. In this study, we report on structural facets governing hysteretic SCO in a set of iron(II)-2,6-bis(1H-pyrazol-1-yl)pyridine) (bpp) complexes - [Fe(bpp-COOEt)₂ ](X)₂ ⋅CH₃ NO₂ (X=ClO₄ , 1; X=BF₄ , 2). Stable spin-state switching - T_1/2 =288 K; ΔT_1/2 =62 K - is observed for 1, whereas 2 undergoes above-room-temperature lattice-solvent content-dependent SCO - T_1/2 =331 K; ΔT_1/2 =43 K. Variable-temperature single-crystal X-ray diffraction studies of the complexes revealed pronounced molecular reorganizations - from the Jahn-Teller-distorted HS state to the less distorted LS state - and conformation switching of the ethyl group of the COOEt substituent upon SCO. Consequently, we propose that the large structural reorganizations rendered SCO hysteretic in 1 and 2. Such insights shedding light on the molecular origin of thermal hysteresis might enable the design of technologically relevant molecule-based switching and memory elements.

SUBMITTER: Suryadevara N

PROVIDER: S-EPMC9305185 | biostudies-literature |

REPOSITORIES: biostudies-literature

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Spin-Crossover in Supramolecular Iron(II)-2,6-bis(1<i>H</i>-Pyrazol-1-yl)pyridine Complexes: Toward Spin-State Switchable Single-Molecule Junctions.

Project description:Spin-crossover (SCO) active iron(II) complexes are an integral class of switchable and bistable molecular materials. Spin-state switching properties of the SCO complexes have been studied in the bulk and single-molecule levels to progress toward fabricating molecule-based switching and memory elements. Supramolecular SCO complexes featuring anchoring groups for metallic electrodes, for example, gold (Au), are ideal candidates to study spin-state switching at the single-molecule level. In this study, we report on the spin-state switching characteristics of supramolecular iron(II) complexes 1 and 2 composed of functional 4-([2,2'-bithiophen]-5-ylethynyl)-2,6-di(1H-pyrazol-1-yl)pyridine (L1) and 4-(2-(5-(5-hexylthiophen-2-yl)thiophen-2-yl)ethynyl)-2,6-di(1H-pyrazol-1-yl)pyridine (L2) ligands, respectively. Density functional theory (DFT) studies revealed stretching-induced spin-state switching in a molecular junction composed of complex 1, taken as a representative example, and gold electrodes. Single-molecule conductance traces revealed the unfavorable orientation of the complexes in the junctions to demonstrate the spin-state dependence of the conductance.

| S-EPMC9088905 | biostudies-literature

2,6-Bis(3-phenyl-1H-pyrazol-5-yl)pyridine monohydrate.

Project description:In the title compound, C(23)H(17)N(5)·H(2)O, the pyrazole rings are slightly twisted from the central pyridine ring, forming dihedral angles of 5.3 (2) and 3.5 (2)°. The pyrazole and phenyl rings on each side of the pyridine ring are also approximately coplanar, making dihedral angles of 6.0 (2) and 4.5 (2)°. In the crystal structure, 2,6-bis-(3-phenyl-1H-pyrazol-5-yl)pyridine and water mol-ecules are linked together via N-H⋯O and O-H⋯N hydrogen bonds, forming a column running parallel to the a axis.

| S-EPMC2961158 | biostudies-literature

2,6-Bis(1-isopropyl-5-phenyl-1H-pyrazol-3-yl)pyridine.

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Crystal structure of 2,6-bis-[(1H-pyrazol-1-yl)meth-yl]pyridine.

Project description:In the title compound, C13H13N5, the planes of the pyrazolyl groups are nearly perpendicular to that of the central pyridine ring, making dihedral angles of 87.77?(8) and 85.73?(7)°. In the crystal, weak C-H?N hydrogen bonds link the mol-ecules into layers extending parallel to (10-1).

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Iron(II) Complexes of 2,6-Di[4-(ethylcarboxy)pyrazol-1-yl]pyridine with Reversible Guest-Modulated Spin-Crossover Behavior.

Project description:Three solvatomorphs of the iron(II) complex of 2,6-di[4-(ethylcarboxy)pyrazol-1-yl]pyridine (bpCOOEt2p) of formulas [Fe(bpCOOEt2p)2](ClO4)2·1.5MeNO2 (1), [Fe(bpCOOEt2p)2](ClO4)2·MeNO2 (2), and [Fe(bpCOOEt2p)2](ClO4)2·2MeNO2 (3) have been prepared and characterized. They show interesting spin-crossover (SCO) properties ranging from partial to complete thermal spin transitions and a light-induced excited spin-state trapping (LIESST) effect. In solvatomorph 2, a robust structure is formed with channels that enable the entrance or removal of solvent molecules by vapor diffusion without losing the crystallinity. Thus, solvent-exchanged samples [Fe(bpCOOEt2p)2](ClO4)2·MeNO2 (2·MeNO 2 ), [Fe(bpCOOEt2p)2](ClO4)2·MeCN (2·MeCN), [Fe(bpCOOEt2p)2](ClO4)2·0.5Me2CO (2·Me 2 CO), and [Fe(bpCOOEt2p)2](ClO4)2·MeCOOH (2·MeCOOH) were prepared by vapor diffusion of the solvents in a crystal of the compound previously heated to 400 K in a single-crystal to single-crystal (SCSC) fashion. Interestingly, this causes a change of spin state with a stabilization of the low-spin state in 2·Me 2 CO and the high-spin state in 2·MeCN. Therefore, the SCO properties of 2 can be tuned in a reversible way by exposure to different solvents.

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Bis(acetato-κO,O')[2,6-bis-(1H-pyrazol-3-yl-κN)pyridine-κN]manganese(II).

Project description:In the title complex, [Mn(CH(3)CO(2))(2)(C(11)H(9)N(5))], the Mn(II) atom is coordinated by the pyridine N atom and two pyrazole N atoms from a 2,6-bis-(pyrazol-3-yl)pyridine ligand and four O atoms from two bidentate acetate ligands. The complex mol-ecules are linked by inter-molecular N-H⋯O hydrogen bonds into a chain along [010]. π-π inter-actions between the pyridine rings and between the pyrazole rings [centroid-centroid distances = 3.772 (2) and 3.546 (2) Å] connect the chains.

| S-EPMC3099944 | biostudies-literature

Bis[2,6-bis-(3,5-dimethyl-1H-pyrazol-1-yl)pyridine]di-?(3)-iodido-diiodidotetra-copper(I).

Project description:In the title centrosymmetric tetra-nuclear complex, [Cu(4)I(4)(C(15)H(17)N(5))(2)], the two distinct Cu(I) atoms adopt similar tetra-hedral arrangements, each being ligated by two I atoms, and two N atoms from one 2,6-bis-(3,5-dimethyl-1H-pyrazol-1-yl)pyridine ligand. In the crystal, there are no hydrogen bonds present, and only very weak ?-? inter-actions are observed [centroid-centroid distance = 3.985?(4)?Å], which connect neighbouring tetra-nuclear units into a chain motif along the b axis.

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High-Temperature Spin Crossover in Iron(II) Complexes with 2,6-Bis(1<i>H</i>-imidazol-2-yl)pyridine.

Project description:Novel iron(II) coordination compounds containing a ligand 2,6-bis(1H-imidazol-2-yl)pyridine (L), having such a composition as [FeL2]SO4·0.5H2O, [FeL2]Br2·H2O, [FeL2](ReO4)2, [FeL2]B10H10∙H2O, [FeL2]B12H12∙1.5H2O had been synthesized and studied using UV-Vis (diffuse reflectance), infrared, extended X-ray absorption fine structure (EXAFS), and Mössbauer spectroscopy methods, as well as X-ray diffraction and static magnetic susceptibility methods. The analysis of the μeff(T) dependence in the temperature range of 80-600 K have shown that all the obtained complexes exhibit a high-temperature spin crossover 1A1 ↔ 5T2.

| S-EPMC9415506 | biostudies-literature

3,5-Bis[1-acetyl-5-(4-chloro-phen-yl)-4,5-dihydro-1H-pyrazol-3-yl]-2,6-dimethyl-pyridine.

Project description:The title compound, C(29)H(27)Cl(2)N(5)O(2), contains a central pyridine ring and two functionalized pyrazoline rings. The pyridine ring and the two attached pyrazoline rings are nearly coplanar, whereas the terminal chloro-phenyl rings are nearly perpendicular to the attached pyrazoline rings [dihedral angles = 86.78?(1) and 77.70?(1)°]. Mol-ecules are linked by weak inter-molecular C-H?O hydrogen bonding.

| S-EPMC2960675 | biostudies-literature

Crystal structure of di-chlorido-{2,6-bis-[(3-phenyl-1H-pyrazol-1-yl)meth-yl]pyridine}cobalt(II).

Project description:In the title complex, [CoCl2(C25H21N5)], the Co(II) atom is coordinated by two Cl atoms and two N atoms, provided by a tridentate pyrazolylpyridyl ligand, forming a slightly distorted tetra-hedral geometry [range of angles: 96.51 (10) (chelate ring) to 118.60 (9)°]. The dihedral angle between Cl/Co/Cl and N/Co/N planes is 86.83 (7)°. The chelate ring has the conformation of a distorted boat. The dihedral angle between pyridyl ring and the coordinated pyrazolyl ring is 56.16 (12)°. The uncoordinated pyrazolyl ring is almost perpendicular to the pyridyl ring with the dihedral angle of 87.49 (10)°. In the crystal packing, inter-molecular phenyl-C-H ⋯π(pyrid-yl) inter-actions generate dimeric aggregates. These are connected into a zigzag supra-molecular chain along the c-axis direction via π-π inter-actions [inter-centroid distance between pyridyl and phenyl rings = 3.664 (2) Å].

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