An Investigation of Photo- and Pressure-Induced Effects in a Pair of Isostructural Two-Dimensional Spin-Crossover Framework Materials

2014 ◽  
Vol 20 (24) ◽  
pp. 7448-7457 ◽  
Author(s):  
Natasha F. Sciortino ◽  
Suzanne M. Neville ◽  
Cédric Desplanches ◽  
Jean-François Létard ◽  
Victor Martinez ◽  
...  
Keyword(s):  
Spin Crossover ◽  
Two Dimensional ◽  
Framework Materials

Thermal Spin Crossover Behaviour of Two-Dimensional Hofmann-Type Coordination Polymers Incorporating Photoactive Ligands

2014 ◽  
Vol 67 (11) ◽  
pp. 1563 ◽  
Author(s):  
Florence Ragon ◽  
Korcan Yaksi ◽  
Natasha F. Sciortino ◽  
Guillaume Chastanet ◽  
Jean-François Létard ◽  
...  
Keyword(s):  
Solid State ◽  
Structural Analysis ◽  
Spin State ◽  
Coordination Polymers ◽  
Spin Crossover ◽  
Pore Space ◽  
Free Ligand ◽  
Two Dimensional ◽  
Framework Materials ◽  
Active Isomer

Two spin crossover (SCO)-active 2D Hofmann-type framework materials, [Fe(3-PAP)2Pd(CN)4] (A) and [Fe(4-PAP)2Pd(CN)4] (B) containing the photoactive azo-benzene-type ligands 3-phenylazo-pyridine (3-PAP) and 4-phenylazo-pyridine (4-PAP) were prepared. These materials form non-porous Hofmann-type structures whereby 2D [FeIIPd(CN)4] grids are separated by 3- or 4-PAP ligands. The iron(ii) sites of both materials (A and B) undergo abrupt and hysteretic spin transitions with characteristic transition temperatures T1/2↓,↑: 178, 190 K (ΔT: 12 K) and T1/2↓,↑: 233, 250 K (ΔT: 17 K), respectively. Photo-magnetic characterisations reveal light-induced excited spin state trapping (LIESST) activity in both A and B with characteristic T(LIESST) values of 45 and 40 K. Although both free ligands show trans- to-cis isomerisation in solution under UV-irradiation, as evidenced via absorption spectroscopy, such photo-activity was not observed in the ligands or complexes A and B in the solid state. Structural analysis of a further non-SCO active isomer to B, [Fe(4-PAP)2Pd(CN)4]·1/2(4-PAP) (B·(4-PAP)), which contains free ligand in the pore space is reported.

Two-Dimensional Coordination Polymers with Spin Crossover Functionality

2014 ◽  
Vol 67 (11) ◽  
pp. 1553 ◽  
Author(s):  
Natasha F. Sciortino ◽  
Suzanne M. Neville
Keyword(s):  
Solid State ◽  
Coordination Polymers ◽  
Spin Crossover ◽  
Two Dimensional ◽  
Additional Function ◽  
Framework Materials ◽  
Sensing Applications ◽  
Two Dimensional Materials ◽  
Packing Interactions ◽  
Important Structure

In the solid state, the propagation of spin crossover (SCO) information is governed by a complex interplay between inner and outer coordination sphere effects. In this way, lattice cooperativity can be enhanced through solid state packing interactions (i.e. hydrogen-bonding and π-stacking) and via coordinatively linking spin switching sites (i.e. coordination polymers). SCO framework materials have successfully provided an avenue for enhanced cooperativity and additional function as host–guest sensors via their potential porosity. In this review, we explore two-dimensional SCO coordination polymers: (1) spin crossover frameworks (SCOFs) consisting of (4,4) grids and (2) Hofmann-type materials where layers are separated by organic ligands. These families have each allowed the elucidation of important structure–function properties and provided a novel platform for molecular sensing applications. Towards advancing the field of infinite polymeric SCO materials, two-dimensional materials can offer flexible porosity, potentially leading to novel spin state-switching functionality.

A spin-crossover phenomenon in a 2D heterometallic coordination polymer with [Pd(SCN)4]2− building blocks

2021 ◽  
Vol 50 (12) ◽  
pp. 4152-4158
Author(s):  
Kai-Ping Xie ◽  
Si-Guo Wu ◽  
Long-Fei Wang ◽  
Guo-Zhang Huang ◽  
Zhao-Ping Ni ◽  
...  
Keyword(s):  
Coordination Polymer ◽  
Spin Crossover ◽  
Building Blocks ◽  
Two Dimensional ◽  
Heterometallic Coordination Polymer

The first spin-crossover example of a two-dimensional coordination polymer containing [Pd(SCN)4]2− building blocks was explored.

Atomically Thin Two-Dimensional Nanosheets with Tunable Spin-Crossover Properties

2018 ◽  
Vol 9 (24) ◽  
pp. 7052-7058 ◽  
Author(s):  
Yang-Hui Luo ◽  
Chen Chen ◽  
Guo-Wei Lu ◽  
Dan-Li Hong ◽  
Xiao-Tong He ◽  
...  
Keyword(s):  
Spin Crossover ◽  
Two Dimensional

Two-Step Spin-Crossover with Three Inequivalent FeII Sites in a Two-Dimensional Hofmann-Type Coordination Polymer

2017 ◽  
Vol 23 (42) ◽  
pp. 10034-10037 ◽  
Author(s):  
Yan Meng ◽  
Qing-Qing Sheng ◽  
Md. Najbul Hoque ◽  
Yan-Cong Chen ◽  
Si-Guo Wu ◽  
...  
Keyword(s):  
Coordination Polymer ◽  
Spin Crossover ◽  
Two Dimensional

Spin-Crossover Phenomenon in Microcrystals and Nanoparticles of a [Fe(2-mpz)2Ni(CN)4] Two-Dimensional Hofmann-Type Polymer: A Detailed Nano-Topographic Study

2019 ◽  
Vol 58 (20) ◽  
pp. 13733-13736 ◽  
Author(s):  
Christina D. Polyzou ◽  
Ondřej Malina ◽  
Jiri Tuček ◽  
Radek Zbořil ◽  
Nikos Panagiotou ◽  
...  
Keyword(s):  
Spin Crossover ◽  
Two Dimensional

scholarly journals Four-step iron(ii) spin state cascade driven by antagonistic solid state interactions

2017 ◽  
Vol 8 (1) ◽  
pp. 701-707 ◽  
Author(s):  
Natasha F. Sciortino ◽  
Katrina A. Zenere ◽  
Maggie E. Corrigan ◽  
Gregory J. Halder ◽  
Guillaume Chastanet ◽  
...  
Keyword(s):  
Solid State ◽  
Spin State ◽  
Spin Crossover ◽  
Type Material ◽  
Two Dimensional ◽  
Crossover Transition

A rare four-step spin crossover transition has been attained in a two-dimensional Hofmann-type material through the presence of an array of antagonistic host–host and host–guest interactions.

Structure and Magnetic Studies on a Series of Two-Dimensional Iron(II) Framework Materials with Varying Ligand Characteristics

2017 ◽  
Vol 70 (5) ◽  
pp. 623 ◽  
Author(s):  
Matthew A. D. Roxburgh ◽  
Samantha Zaiter ◽  
Xina I. B. Hudson ◽  
Benjamin R. Mullaney ◽  
John E. Clements ◽  
...  
Keyword(s):  
Spin Crossover ◽  
Large Family ◽  
Structural Motif ◽  
Magnetic Studies ◽  
Bridging Ligands ◽  
Coordination Environment ◽  
Pyridyl Ligands ◽  
Framework Materials ◽  
Grid Topology ◽  
Varying Length

Targeting the general (4,4)-grid structural motif, we have prepared seven new coordination polymers in the general family [Fe(NCX)2(L)2]·(guest) (L = bis-pyridyl-type bridging ligands; X = S, Se) as an extension of the well-established spin crossover framework (SCOF) family. In all cases, the (4,4)-grid topology is formed by the bridging of octahedral iron(ii) sites in the equatorial plane by bis-pyridyl ligands of varying length, flexibility, and intermolecular interaction capacity. In particular, the six ligands n-(4-pyridyl)-isonicotinamide (pin), trans-1,2-bis(4′-pyridyl)ethane (tvp), 1,2-dibromo-1,2-bis(4′-pyridyl)ethane (dbbpe), bis(4-pyridyl)-1,2,4,5-tetrazine (bptz), 4,4′-bis(pyridyl)acetylene (bpac), and 1,4-bis(4-pyridylethynyl)benzene (bpeben) have been utilised. The seven new materials [Fe(NCS)2(pin)2]·2(MeCN) (pin-S), [Fe(tvp)2(NCS)2]·1/2(tvp)·(CH3CH2OH) (tvp-S), [Fe(dbbpe)2(NCS)2]·6(CH3CN) (dbbpe-S), [Fe(NCS)2(bptz)2]·2(CHCl3)·6(EtOH) (bptz-S), [Fe(NCSe)2(bptz)2]·4(CHCl3)·(EtOH)·(H2O) (bptz-Se), [Fe(NCS)2(bpac)2]·2(PrOH) (bpac-S), and [Fe(NCS)2(bpeben)2]·2(CHCl3) (bpeben-S) all form (4,4)-grids of varying size that are arranged in a parallel stacked topology. Despite being in the [FeN6] coordination environment known to be conducive to spin crossover, these materials all remain high-spin with thermal variation. These results are discussed in context with the large family of SCOFs that show varied spin crossover behaviours.

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