scholarly journals Spin-Crossover 2-D Hofmann Frameworks Incorporating an Amide-Functionalized Ligand: N-(pyridin-4-yl)benzamide

Chemistry ◽  
2021 ◽  
Vol 3 (1) ◽  
pp. 360-372
Author(s):  
Xandria Ong ◽  
Manan Ahmed ◽  
Luonan Xu ◽  
Ashley T. Brennan ◽  
Carol Hua ◽  
...  
Keyword(s):  
Hydrogen Bonding ◽  
Spin State ◽  
Spin Crossover ◽  
Variable Temperature ◽  
Spin Transition ◽  
Single Step ◽  
Amide Group ◽  
State Transitions ◽  
Structure Property ◽  
Scanning Calorimetry

Two analogous 2-D Hofmann-type frameworks, which incorporate the novel ligand N-(pyridin-4-yl)benzamide (benpy) [FeII(benpy)2M(CN)4]·2H2O (M = Pd (Pd(benpy)) and Pt (Pt(benpy))) are reported. The benpy ligand was explored to facilitate spin-crossover (SCO) cooperativity via amide group hydrogen bonding. Structural analyses of the 2-D Hofmann frameworks revealed benpy-guest hydrogen bonding and benpy-benpy aromatic contacts. Both analogues exhibited single-step hysteretic spin-crossover (SCO) transitions, with the metal-cyanide linker (M = Pd or Pt) impacting the SCO spin-state transition temperature and hysteresis loop width (Pd(benpy): T½↓↑: 201, 218 K, ∆T: 17 K and Pt(benpy): T½↓↑: 206, 226 K, ∆T: 20 K). The parallel structural and SCO changes over the high-spin to low-spin transition were investigated using variable-temperature, single-crystal, and powder X-ray diffraction, Raman spectroscopy, and differential scanning calorimetry. These studies indicated that the ligand–guest interactions facilitated by the amide group acted to support the cooperative spin-state transitions displayed by these two Hofmann-type frameworks, providing further insight into cooperativity and structure–property relationships.

scholarly journals High-temperature Spin Crossover of a Solvent-Free Iron(II) Complex with the Linear Hexadentate Ligand [Fe(L2-3-2Ph)](AsF6)2 (L2-3-2Ph = bis[N-(1-Phenyl-1H-1,2,3-triazol-4-yl)methylidene-2-aminoethyl]-1,3- propanediamine)

2019 ◽  
Vol 5 (1) ◽  
pp. 10 ◽  
Author(s):  
Hiroaki Hagiwara
Keyword(s):  
Room Temperature ◽  
Spin Crossover ◽  
Variable Temperature ◽  
Spin Transition ◽  
Three Dimensional ◽  
Solvent Free ◽  
Supramolecular Network ◽  
Scanning Calorimetry ◽  
Mononuclear Iron ◽  
3D Network

A novel mononuclear iron(II) complex with a linear hexadentate N6 ligand, containing two 1,2,3-triazole moieties, [Fe(L2-3-2Ph)](AsF6)2 (1), was synthesized (L2-3-2Ph = bis[N-(1-Phenyl-1H-1,2,3-triazol-4-yl)methylidene-2-aminoethyl]-1,3-propanediamine). Variable-temperature magnetic susceptibility measurements revealed a gradual one-step spin crossover (SCO) between the high-spin (HS, S = 2) and low-spin (LS, S = 0) states above room temperature (T1/2 = 468 K). The spin transition was further confirmed by differential scanning calorimetry (DSC). A single-crystal X-ray diffraction study showed that the complex was in the LS state (S = 0) at room temperature (296 K). In the crystal lattice, a three-dimensional (3D) supramolecular network was formed by intermolecular CH⋯ and – interactions of neighboring complex cations [Fe(L2-3-2Ph)]2+. AsF6− ions were located interstitially in the 3D network of complex cations, with no solvent-accessible voids. The crystal structure at 448 K (mixture of HS and LS species) was also successfully determined thanks to the thermal stability of the solvent-free crystal.

scholarly journals Solvent Effects on the Spin-Transition in a Series of Fe(II) Dinuclear Triple Helicate Compounds

Crystals ◽  
2018 ◽  
Vol 8 (10) ◽  
pp. 376 ◽  
Author(s):  
Alexander Craze ◽  
Mohan Bhadbhade ◽  
Cameron Kepert ◽  
Leonard Lindoy ◽  
Christopher Marjo ◽  
...  
Keyword(s):  
Spin Crossover ◽  
Condensation Product ◽  
Variable Temperature ◽  
Spin Transition ◽  
Single Step ◽  
Spin Conversion ◽  
Dinuclear Iron ◽  
Solvent Molecules ◽  
State Spin ◽  
Triple Helicate

This work explores the effect of lattice solvent on the observed solid-state spin-transition of a previously reported dinuclear Fe(II) triple helicate series 1–3 of the general form [FeII2L3](BF4)4(CH3CN)n, where L is the Schiff base condensation product of imidazole-4-carbaldehyde with 4,4-diaminodiphenylmethane (L1), 4,4′-diaminodiphenyl sulfide (L2) and 4,4′-diaminodiphenyl ether (L3) respectively, and 1 is the complex when L = L1, 2 when L = L2 and 3 when L = L3 (Craze, A.R.; Sciortino, N.F.; Bhadbhade, M.M.; Kepert, C.J.; Marjo, C.E.; Li, F. Investigation of the Spin Crossover Properties of Three Dinuclear Fe(II) Triple Helicates by Variation of the Steric Nature of the Ligand Type. Inorganics. 2017, 5 (4), 62). Desolvation of 1 and 2 during measurement resulted not only in a decrease in T1/2 and completeness of spin-crossover (SCO) but also a change in the number of steps in the spin-profile. Compounds 1 and 2 were observed to change from a two-step 70% complete transition when fully solvated, to a single-step half complete transition upon desolvation. The average T1/2 value of the two-steps in the solvated materials was equivalent to the single T1/2 of the desolvated sample. Upon solvent loss, the magnetic profile of 3 experienced a transformation from a gradual SCO or weak antiferromagnetic interaction to a single half-complete spin-transition. Variable temperature single-crystal structures are presented and the effects of solvent molecules are also explored crystallographically and via a Hirshfeld surface analysis. The spin-transition profiles of 1–3 may provide further insight into previous discrepancies in dinuclear triple helicate SCO research reported by the laboratories of Hannon and Gütlich on analogous systems (Tuna, F.; Lees, M. R.; Clarkson, G. J.; Hannon, M. J. Readily Prepared Metallo-Supramolecular Triple Helicates Designed to Exhibit Spin-Crossover Behaviour. Chem. Eur. J. 2004, 10, 5737–5750 and Garcia, Y.; Grunert, C. M.; Reiman, S.; van Campenhoudt, O.; Gütlich, P. The Two-Step Spin Conversion in a Supramolecular Triple Helicate Dinuclear Iron(II) Complex Studied by Mössbauer Spectroscopy. Eur. J. Inorg. Chem. 2006, 3333–3339).

scholarly journals Quadruple Hydrogen Bond-Containing A-AB-A Triblock Copolymers: Probing the Influence of Hydrogen Bonding in the Central Block

Molecules ◽  
2021 ◽  
Vol 26 (15) ◽  
pp. 4705
Author(s):  
Boer Liu ◽  
Xi Chen ◽  
Glenn A. Spiering ◽  
Robert B. Moore ◽  
Timothy E. Long
Keyword(s):  
Hydrogen Bonding ◽  
Self Assembly ◽  
Microphase Separation ◽  
Triblock Copolymers ◽  
Random Copolymer ◽  
Thermomechanical Properties ◽  
Structure Property ◽  
Scanning Calorimetry ◽  
Central Block ◽  
Quadruple Hydrogen Bonding

This work reveals the influence of pendant hydrogen bonding strength and distribution on self-assembly and the resulting thermomechanical properties of A-AB-A triblock copolymers. Reversible addition-fragmentation chain transfer polymerization afforded a library of A-AB-A acrylic triblock copolymers, wherein the A unit contained cytosine acrylate (CyA) or post-functionalized ureido cytosine acrylate (UCyA) and the B unit consisted of n-butyl acrylate (nBA). Differential scanning calorimetry revealed two glass transition temperatures, suggesting microphase-separation in the A-AB-A triblock copolymers. Thermomechanical and morphological analysis revealed the effects of hydrogen bonding distribution and strength on the self-assembly and microphase-separated morphology. Dynamic mechanical analysis showed multiple tan delta (δ) transitions that correlated to chain relaxation and hydrogen bonding dissociation, further confirming the microphase-separated structure. In addition, UCyA triblock copolymers possessed an extended modulus plateau versus temperature compared to the CyA analogs due to the stronger association of quadruple hydrogen bonding. CyA triblock copolymers exhibited a cylindrical microphase-separated morphology according to small-angle X-ray scattering. In contrast, UCyA triblock copolymers lacked long-range ordering due to hydrogen bonding induced phase mixing. The incorporation of UCyA into the soft central block resulted in improved tensile strength, extensibility, and toughness compared to the AB random copolymer and A-B-A triblock copolymer comparisons. This study provides insight into the structure-property relationships of A-AB-A supramolecular triblock copolymers that result from tunable association strengths.

scholarly journals Stabilization of the Low-Spin State in a Mononuclear Iron(II) Complex and High-Temperature Cooperative Spin Crossover Mediated by Hydrogen Bonding

2015 ◽  
Vol 22 (1) ◽  
pp. 331-339 ◽  
Author(s):  
Sipeng Zheng ◽  
Niels R. M. Reintjens ◽  
Maxime A. Siegler ◽  
Olivier Roubeau ◽  
Elisabeth Bouwman ◽  
...  
Keyword(s):  
Hydrogen Bonding ◽  
High Temperature ◽  
Spin State ◽  
Spin Crossover ◽  
Mononuclear Iron

scholarly journals Spin State Behavior of A Spin-Crossover Iron(II) Complex with N,N′-Disubstituted 2,6-bis(pyrazol-3-yl)pyridine: A Combined Study by X-ray Diffraction and NMR Spectroscopy

Crystals ◽  
2020 ◽  
Vol 10 (9) ◽  
pp. 793
Author(s):  
Elizaveta K. Melnikova ◽  
Dmitry Yu. Aleshin ◽  
Igor A. Nikovskiy ◽  
Gleb L. Denisov ◽  
Yulia V. Nelyubina
Keyword(s):  
Nmr Spectroscopy ◽  
Spin State ◽  
Metal Ion ◽  
Spin Crossover ◽  
Molecular Design ◽  
Chemical Shifts ◽  
Variable Temperature ◽  
High Spin State ◽  
X Ray Diffraction ◽  
X Ray

A series of three different solvatomorphs of a new iron(II) complex with N,N′-disubstituted 2,6-bis(pyrazol-3-yl)pyridine, including those with the same lattice solvent, has been identified by X-ray diffraction under the same crystallization conditions with the metal ion trapped in the different spin states. A thermally induced switching between them, however, occurs in a solution, as unambiguously confirmed by the Evans technique and an analysis of paramagnetic chemical shifts, both based on variable-temperature NMR spectroscopy. The observed stabilization of the high-spin state by an electron-donating substituent contributes to the controversial results for the iron(II) complexes of 2,6-bis(pyrazol-3-yl)pyridines, preventing ‘molecular’ design of their spin-crossover activity; the synthesized complex being only the fourth of the spin-crossover (SCO)-active kind with an N,N′-disubstituted ligand.

scholarly journals Spin state switching in iron coordination compounds

2013 ◽  
Vol 9 ◽  
pp. 342-391 ◽  
Author(s):  
Philipp Gütlich ◽  
Ana B Gaspar ◽  
Yann Garcia
Keyword(s):  
Spin State ◽  
Coordination Compounds ◽  
Spin Crossover ◽  
Spin Transition ◽  
Pressure Sensors ◽  
Ligand Field ◽  
Thermally Induced ◽  
Practical Applications ◽  
State Switching ◽  
Switching Phenomenon

The article deals with coordination compounds of iron(II) that may exhibit thermally induced spin transition, known as spin crossover, depending on the nature of the coordinating ligand sphere. Spin transition in such compounds also occurs under pressure and irradiation with light. The spin states involved have different magnetic and optical properties suitable for their detection and characterization. Spin crossover compounds, though known for more than eight decades, have become most attractive in recent years and are extensively studied by chemists and physicists. The switching properties make such materials potential candidates for practical applications in thermal and pressure sensors as well as optical devices. The article begins with a brief description of the principle of molecular spin state switching using simple concepts of ligand field theory. Conditions to be fulfilled in order to observe spin crossover will be explained and general remarks regarding the chemical nature that is important for the occurrence of spin crossover will be made. A subsequent section describes the molecular consequences of spin crossover and the variety of physical techniques usually applied for their characterization. The effects of light irradiation (LIESST) and application of pressure are subjects of two separate sections. The major part of this account concentrates on selected spin crossover compounds of iron(II), with particular emphasis on the chemical and physical influences on the spin crossover behavior. The vast variety of compounds exhibiting this fascinating switching phenomenon encompasses mono-, oligo- and polynuclear iron(II) complexes and cages, polymeric 1D, 2D and 3D systems, nanomaterials, and polyfunctional materials that combine spin crossover with another physical or chemical property.

scholarly journals Measurements, Thermodynamic Modeling, and a Hydrogen Bonding Study on the Solubilities of Metoprolol Succinate in Organic Solvents

Molecules ◽  
2018 ◽  
Vol 23 (10) ◽  
pp. 2469 ◽  
Author(s):  
Jian Shen ◽  
Xianrui Liang ◽  
Hao Lei
Keyword(s):  
Density Functional Theory ◽  
Hydrogen Bonding ◽  
Ethyl Acetate ◽  
Density Functional ◽  
Structure Property ◽  
Scanning Calorimetry ◽  
Fixed Temperature ◽  
Functional Theory ◽  
Metoprolol Succinate ◽  
Bonding Structure

The solubilities of metoprolol succinate (a cardioselective β1 adrenergic receptor) in methanol, ethanol, n-propanol, isopropanol, n-butanol, ethyl acetate, and acetone were measured at temperatures ranging from (278.2 to 318.2) K using a solid–liquid equilibrium method. The solubility of metoprolol succinate increases with increasing temperature. At a fixed temperature, the solubility decreases in the order methanol > ethanol > n-butanol > n-propanol > isopropanol > acetone > ethyl acetate. The enthalpy of fusion and the melting point of metoprolol succinate were determined by differential scanning calorimetry. The thermodynamic properties of the dissolution process, determined by a van’t Hoff analysis, have been obtained and are discussed. The modified Apelblat equation, Wilson model, and non-random two-liquid (NRTL) model were employed to correlate the solubilities of metoprolol succinate in different solvents. Finally, a quantitative structure–property relationship (QSPR) study of physical properties of solvents and density functional theory simulations of hydrogen-bonding structure were carried out to give the explanation for the sequence of solubility in alcohols. The density functional theory (DFT) calculations well illustrated that the solubility of metoprolol succinate in various alcohols can be mainly attributed to the intra- and intermolecular hydrogen bonds in metoprolol succinate-solvent complexes.

scholarly journals Structure:function relationships for thermal and light-induced spin-crossover in isomorphous molecular materials

2020 ◽  
Vol 8 (25) ◽  
pp. 8420-8429
Author(s):  
Rafal Kulmaczewski ◽  
Elzbieta Trzop ◽  
Eric Collet ◽  
Sergi Vela ◽  
Malcolm A. Halcrow
Keyword(s):  
High Spin ◽  
Spin State ◽  
Spin Crossover ◽  
Spin Transition ◽  
Molecular Materials

The complicated light-induced spin state trapping behaviour of a family of isomorphous solvate crystals reflects reorientation of the lattice solvent during the spin-transition (white = high-spin, brown = low-spin).

Coordination of Pyridine-Substituted Pyrazoles and Their Influence on the Spin State of Iron(II)

1988 ◽  
Vol 41 (11) ◽  
pp. 1645 ◽  
Author(s):  
KH Sugiyarto ◽  
HA Goodwin
Keyword(s):  
Hydrogen Bonding ◽  
Cooling Rate ◽  
High Spin ◽  
Low Temperatures ◽  
Singlet State ◽  
Variable Temperature ◽  
Spin Transition ◽  
Spectral Studies ◽  
Quintet State ◽  
Substituted Pyrazoles

Iron(II) and nickel(II) [MN6]X2 type complexes have been prepared from 2-(pyrazol-1-yl]pyridine (1pp), 2-(pyrazol-1-yl) imidazoline (pi), 2- (pyrazol-3-yl)pyridine (3pp) and 2,6-bis(pyrazol-3-yl)pyridine ( bpp ). Variable-temperature magnetic and Mossbauer spectral studies establish that [Fe(1pp)3]X2 is low spin and [Fe(pi)3]X2 is high spin over an extended temperature range, while both [Fe(3pp)3]X2 and [Fe( bpp )2]X2 undergo temperature-induced low-spin ↔ high-spin transitions. The nature of the transition depends on the extent of hydration and for salts of both cations the singlet state is generally stabilized as the extent of hydration increases. Hydrogen bonding effects are believed to be responsible for this. For anhydrous [Fe( bpp )2] [BF4]2 the transition is discontinuous and associated with hysteresis with Tc ↓ 173 K for decreasing temperature and Tc ↑ 183 K for increasing temperatures. The transition to the singlet state species is complete at low temperatures provided that the cooling rate is relatively slow. Rapid cooling to 77 K results in the trapping of a fraction of metastable quintet state species. For all other species containing either [Fe(3pp)3]2+ or [Fe( bpp )2]2+ the spin transition is continuous. Spectral data for [NiN6]X2 complexes establish an order of field strengths for the ligands pi < 3pp < 1pp < bpp , which, for the bidentate species only, is consistent with the observed electronic properties of the corresponding [FeN6]X2 complexes.

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