Spiral Assembly of the 1D Chain Sheet of Fe(NCBH3)2(bpa)2·(biphenyl) (bpa = 1,2-bis(4-pyridyl)ethane) and its Stepwise Spin-Crossover Phenomenon

Nakashima, Satoru; Morita, Toshiyuki; Inoue, Katsuya; Hayami, Shinya

doi:10.3390/polym4010880

Cited by 4 publications

(4 citation statements)

References 32 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…From the point of view of space-filling, 1D chain and biphenyl molecule formed a crystal, leading to the threefold spiral structure. Such structure conducts stepwise SCO if the anionic ligand is changed from NCS − to NCBH 3 − , as reported by the present author et al [25]. Although the propeller structure of pyridines around the iron atom is a key point to showing SCO, the slight difference in ligand field between NCS − to NCBH 3 − also affects the SCO phenomenon.…”

Section: Discussionsupporting

confidence: 83%

“…This shows that the ligands can easily approach iron in the chiral propeller type local structure when the spin state becomes an LS state. It had been reported that [Fe(NCS)2(bpa)2]n has a 1D chain structure and shows HS state [25]. We became interested in [Fe(NCS)2(bpa)2]n, because the bpa has an anti-gauche conformation and NCS − can be changed with other anionic ligands.…”

Section: Introductionmentioning

confidence: 99%

“…[[Fe(NCBH 3 ) 2 (bpa) 2 ]•biphenyl] n usually had 1D chain structure and showed one-step spin transition [15]. In special cases, the 1D chain self-assembled sheet of [[Fe(NCBH 3 ) 2 (bpa) 2 ]•biphenyl] n was stacked spirally, having a threefold axis [25], and this spiral structure showed a stepwise spin transition. Stepwise SCO phenomena play an important role in tuning the spin state precisely.…”

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

Threefold Spiral Structure Constructed by 1D Chains of [[M(NCS)2(bpa)2]·biphenyl]n (M = Fe, Co; bpa = 1,2-bis(4-pyridyl)ethane)

2019

Self Cite

View full text Add to dashboard Cite

Assembled complexes [[M(NCS)2(bpa)2]·biphenyl]n (M = Fe, Co; bpa = 1,2-bis(4-pyridyl)ethane) have been synthesized because [Fe(NCBH3)2(bpa)2·biphenyl]n has a novel threefold spiral structure and shows stepwise spin-crossover phenomenon. We attempted to obtain spiral structures for [[Fe(NCS)2(bpa)2]·biphenyl]n and [[Co(NCS)2(bpa)2]·biphenyl]n using a one-step diffusion method, while the reported spiral structure of [[Fe(NCBH3)2(bpa)2]·biphenyl]n was obtained by diffusion method after synthesizing Fe(II)-pyridine complex. X-ray structural analysis revealed that [[Fe(NCS)2(bpa)2]·biphenyl]n and [[Co(NCS)2(bpa)2]·biphenyl]n had a chiral propeller structure of pyridines around the central metal, and they had a novel spiral structure and chiral space group P3121 without the presence of chiral auxiliaries. It was shown that the host 1D chain, having a chiral propeller structure of pyridines around the central metal along with its concerted interaction with an atropisomer of biphenyl, made a threefold spiral structure.

show abstract

Section: Discussionsupporting

confidence: 83%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Threefold Spiral Structure Constructed by 1D Chains of [[M(NCS)2(bpa)2]·biphenyl]n (M = Fe, Co; bpa = 1,2-bis(4-pyridyl)ethane)

2019

Self Cite

View full text Add to dashboard Cite

show abstract

“…The BH 3 CN – anion is also suitable for designing polymeric SCO complexes. They can be 1D helical chains, 2D square grid networks, or even 3D porous coordination polymers when a tetradentate N,N′-bridging ligand is used. In the case when large aromatic ligands are employed, pores of various sizes can be achieved.…”

Section: Introductionmentioning

confidence: 99%

Cooperative Spin Crossover above Room Temperature in the Iron(II) Cyanoborohydride–Pyrazine Complex

Bibik

Shova²,

Rotaru

et al. 2022

Inorg. Chem.

View full text Add to dashboard Cite

Hysteretic spin crossover in coordination complexes of 3d-metal ions represents one of the most spectacular phenomena of molecular bistability. In this paper we describe a self-assembly of pyrazine (pz) and Fe(BH3CN)2 that afforded the new 2D coordination polymer [Fe(pz)2(BH3CN)2]∞. It undergoes an abrupt, hysteretic spin crossover (SCO) with a T 1/2 of 338 K (heating) and 326 K (cooling) according to magnetic susceptibility measurements. Mössbauer spectroscopy revealed a complete transition between the low-spin (LS) and the high-spin (HS) states of the iron centers. This LS-to-HS transition induced an increase of the unit cell volume by 10.6%. Meanwhile, a modulation of multiple [C–Hδ+···Hδ−–B] dihydrogen bonds stimulates a contraction in direction c (2.2%). The simplicity of the synthesis, mild temperatures of transition, a pronounced thermochromism, stability upon thermal cycling, a striking volume expansion upon SCO, and an easy processability to composite films make this new complex an attractive material for switchable components of diverse applications.

show abstract

Size Effect and Role of Short‐ and Long‐Range Interactions on 1D Spin‐Crossover Systems within the Framework of an Ising‐Like Model

et al. 2013

View full text Add to dashboard Cite

This contribution, motivated by an experimental study of the influence of long‐range interactions on the hysteresis loop, presents a theoretical study of spin‐state transitions within the framework of an Ising‐like model. The Hamiltonian includes both short‐ and long‐range interactions and takes into account different degeneracies between molecular states. The problem is solved exactly for one‐dimensional systems by using a transfer matrix method and the effects of temperature, long‐ and short‐range interactions, and system size (number of molecules) are analysed in depth. The width of the thermal hysteresis loop of spin‐crossover compounds decreases when reducing the long‐range interactions, down to a critical value, calculated for the first time in this contribution, at which the hysteresis vanishes. This dependence is similar to the one generated by the decrease in short‐range interactions assuming that the corresponding variation is proportional. An increase in the system size contributes to a larger influence of long‐range interactions and the hysteretic loop approaches a rectangular shape and reaches a saturation width, which is predicted for the first time. These results are important for the design of novel spin‐crossover materials featuring sharp spin transitions along with wide hysteresis loops, which are particularly suited for potential applications in display and data storage devices.

show abstract

Spiral Assembly of the 1D Chain Sheet of Fe(NCBH3)2(bpa)2·(biphenyl) (bpa = 1,2-bis(4-pyridyl)ethane) and its Stepwise Spin-Crossover Phenomenon

Cited by 4 publications

References 32 publications

Threefold Spiral Structure Constructed by 1D Chains of [[M(NCS)2(bpa)2]·biphenyl]n (M = Fe, Co; bpa = 1,2-bis(4-pyridyl)ethane)

Threefold Spiral Structure Constructed by 1D Chains of [[M(NCS)2(bpa)2]·biphenyl]n (M = Fe, Co; bpa = 1,2-bis(4-pyridyl)ethane)

Cooperative Spin Crossover above Room Temperature in the Iron(II) Cyanoborohydride–Pyrazine Complex

Size Effect and Role of Short‐ and Long‐Range Interactions on 1D Spin‐Crossover Systems within the Framework of an Ising‐Like Model

Contact Info

Product

Resources

About