Cyanido‐Bridged Fe<sup>II</sup>–M<sup>I</sup> Dimetallic Hofmann‐Like Spin‐Crossover Coordination Polymers Based on 2,6‐Naphthyridine

Piñeiro‐López, Lucía; Valverde‐Muñoz, Francisco Javier; Seredyuk, Maksym; Bartual‐Murgui, Carlos; Muñoz, M. Carmen; Real, José Antonio

doi:10.1002/ejic.201700920

Cited by 26 publications

(23 citation statements)

References 42 publications

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“…Enthalpy and entropy changes associated to the phase transition were obtained by integrating the excess heat capacity (after subtraction of the lattice contribution) over T and ln T , respectively. The calculated values (Δ H =−14.3 KJ mol −1 and Δ S =−52.8 JK −1 mol −1 ) compare well with those reported for other related complexes showing also very abrupt spin crossover and strong cooperativity [38–42] . The entropy change is much higher than the sum of the electronic part ( R ln5≈13.4 JK −1 mol −1 ) and the expected vibronic contribution based on the change of Fe−N distances.…”

Section: Resultssupporting

confidence: 85%

A Reversible Hydrogen‐Bond Isomerization Triggered by an Abrupt Spin Crossover near Room Temperature

Jornet‐Mollá

Giménez‐Saiz

Yufit

et al. 2020

Chemistry A European J

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The spin crossover salt [Fe(bpp)2](isonicNO)2⋅ 2.4 H2O (1⋅2.4 H2O) (bpp=2,6‐bis(pyrazol‐3‐yl)pyridine; isonicNO=isonicotinate N‐oxide anion) exhibits a very abrupt spin crossover at T1/2=274.4 K. This triggers a supramolecular linkage (H‐bond) isomerization that responds reversibly towards light irradiation or temperature change. Isotopic effects in the thermomagnetic behavior reveal the importance of hydrogen bonds in defining the magnetic state. Further, the title compound can be reversibly dehydrated to afford 1, a material that also exhibits spin crossover coupled to H‐bond isomerization, leading to strong kinetic effects in the thermomagnetic properties.

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Section: Resultssupporting

confidence: 85%

A Reversible Hydrogen‐Bond Isomerization Triggered by an Abrupt Spin Crossover near Room Temperature

Jornet‐Mollá

Giménez‐Saiz

Yufit

et al. 2020

Chemistry A European J

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“…It is concluded that the weak interlayer contacts 2). [83] The densely packed 1 exhibited a relatively abrupt two-step SCO in the temperature interval 150-215 K, whereas 2, with nitrobenzene as guest molecules, featured an incomplete one-step SCO behavior (T 1/2 = 166 K) that extended over 150 K.…”

Section: Chemical Compositional Modulationsmentioning

confidence: 98%

“…discovered an in situ generated elongated [Ag 2 (CN) 3 ] − linker in a triply interpenetrated framework {Fe(2,6‐naphthy)[Ag(CN) 2 ][Ag 2 (CN) 3 ]} (2,6‐naphthy = 2,6‐naphthyridine) (1) compared to the prototypical doubly interpenetrated {Fe(2,6‐naphthy)[Au(CN) 2 ] 2 }·0.5PhNO 2 (2). [ 83 ] The densely packed 1 exhibited a relatively abrupt two‐step SCO in the temperature interval 150–215 K, whereas 2, with nitrobenzene as guest molecules, featured an incomplete one‐step SCO behavior ( T 1/2 = 166 K) that extended over 150 K.…”

Section: Applications Of Cyanide‐based Porous Materialsmentioning

confidence: 99%

Old Materials for New Functions: Recent Progress on Metal Cyanide Based Porous Materials

2021

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Cyanide is the simplest ligand with strong basicity to construct open frameworks including some of the oldest compounds reported in the history of coordination chemistry. Cyanide can form numerous cyanometallates with different transition metal ions showing diverse geometries. Rational design of robust extended networks is enabled by the strong bonding nature and high directionality of cyanide ligand. By virtue of a combination of cyanometallates and/or organic linkers, multifunctional framework materials can be targeted and readily synthesized for various applications, ranging from molecular adsorptions/separations to energy conversion and storage, and spin-crossover materials. External guest-and stimuli-responsive behaviors in cyanide-based materials are also highlighted for the development of the next-generation smart materials. In this review, an overview of the recent progress of cyanide-based multifunctional materials is presented to demonstrate the great potential of cyanide ligands in the development of modern coordination chemistry and material science.

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“…In recent years, some examples by using the [Ag 2 (CN) 3 ] − unit were reported. 8 Although an isostructural series of Fe II (L) 2 [Au(CN) 2 ] 2 and Fe II (L) 2 [Ag(CN) 2 ] 2 have been much reported, the [Au 2 (CN) 3 ] − unit is still not found. Thus, the [Ag 2 (CN) 3 ] species is a rare building unit.…”

Section: Introductionmentioning

confidence: 99%

A New Systematic Construction of Novel Three-Dimensional Spin Crossover Coordination Polymers Based on the [Ag^I₂(CN)₃] Building Unit

et al. 2021

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New three-dimensional spin crossover (SCO) coordination polymers systematically constructed by the novel building unit [Ag I 2 (CN) 3 ], Fe II (3-Br-5-CH 3 pyridine) 2 [Ag I 2 (CN) 3 ][Ag I (CN) 2 ] ( 1 ), Fe II (3-Br-5-Clpyridine) 2 [Ag I 2 (CN) 3 ][Ag I (CN) 2 ] ( 2 ), and Fe II (3,5-Brpyridine) 2 [Ag I 2 (CN) 3 ][Ag I (CN) 2 ] ( 3 ), have been synthesized and characterized. The bismonodentate binuclear [Ag 2 (CN) 3 ] − and mononuclear [Ag I (CN) 2 ] − units and Fe II atoms assemble to form a 3D network structure. The structures of 1 – 3 are crystallographically identical, which made up the triply interpenetration combined with complicated intermolecular interactions including Ag···Ag, Ag···X (pyridine substituents) and π-stacking interactions. Magnetic and differential scanning calorimetry studies were performed for 1 – 3 . These compounds display a similar SCO behavior, while the critical temperatures ( T c ) are shifted by the substituent effect. Due to the identical structures of 1 – 3 , the order of T c clearly corresponds with the Hammett constant.

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Cyanido‐Bridged Fe^II–M^I Dimetallic Hofmann‐Like Spin‐Crossover Coordination Polymers Based on 2,6‐Naphthyridine

Abstract: Abstract:Two new 3D spin-crossover (SCO) Hofmann-type coordination polymers {Fe (2,6-naphthy) -linkers define wide rectangular windows that favor the interpenetration of three identical 3D networks, strong

Cited by 26 publications

References 42 publications

A Reversible Hydrogen‐Bond Isomerization Triggered by an Abrupt Spin Crossover near Room Temperature

A Reversible Hydrogen‐Bond Isomerization Triggered by an Abrupt Spin Crossover near Room Temperature

Old Materials for New Functions: Recent Progress on Metal Cyanide Based Porous Materials

A New Systematic Construction of Novel Three-Dimensional Spin Crossover Coordination Polymers Based on the [Ag^I₂(CN)₃] Building Unit

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Cyanido‐Bridged FeII–MI Dimetallic Hofmann‐Like Spin‐Crossover Coordination Polymers Based on 2,6‐Naphthyridine

Abstract: Abstract:Two new 3D spin-crossover (SCO) Hofmann-type coordination polymers {Fe (2,6-naphthy) -linkers define wide rectangular windows that favor the interpenetration of three identical 3D networks, strong

Cited by 26 publications

References 42 publications

A Reversible Hydrogen‐Bond Isomerization Triggered by an Abrupt Spin Crossover near Room Temperature

A Reversible Hydrogen‐Bond Isomerization Triggered by an Abrupt Spin Crossover near Room Temperature

Old Materials for New Functions: Recent Progress on Metal Cyanide Based Porous Materials

A New Systematic Construction of Novel Three-Dimensional Spin Crossover Coordination Polymers Based on the [AgI2(CN)3] Building Unit

Contact Info

Product

Resources

About

Cyanido‐Bridged Fe^II–M^I Dimetallic Hofmann‐Like Spin‐Crossover Coordination Polymers Based on 2,6‐Naphthyridine

A New Systematic Construction of Novel Three-Dimensional Spin Crossover Coordination Polymers Based on the [Ag^I₂(CN)₃] Building Unit