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.

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.

scholarly journals Different Benzendicarboxylate-Directed Structural Variations and Properties of Four New Porous Cd(II)-Pyridyl-Triazole Coordination Polymers

2020 ◽  
Vol 8 ◽  
Author(s):  
Ying Zhao ◽  
Jin Jing ◽  
Ning Yan ◽  
Min-Le Han ◽  
Guo-Ping Yang ◽  
...  
Keyword(s):  
Solid State ◽  
Coordination Polymers ◽  
Three Dimensional ◽  
Two Dimensional ◽  
Gas Sorption ◽  
Structural Variations ◽  
Benzenedicarboxylic Acid ◽  
Topological Framework ◽  
The Stability

Four new different porous crystalline Cd(II)-based coordination polymers (CPs), i. e., [Cd(mdpt)2]·2H2O (1), [Cd2(mdpt)2(m-bdc)(H2O)2] (2), [Cd(Hmdpt)(p-bdc)]·2H2O (3), and [Cd3(mdpt)2(bpdc)2]·2.5NMP (4), were obtained successfully by the assembly of Cd(II) ions and bitopic 3-(3-methyl-2-pyridyl)-5-(4-pyridyl)-1,2,4-triazole (Hmdpt) in the presence of various benzendicarboxylate ligands, i.e., 1,3/1,4-benzenedicarboxylic acid (m-H2bdc, p-H2bdc) and biphenyl-4,4′-bicarboxylate (H2bpdc). Herein, complex 1 is a porous 2-fold interpenetrated four-connected 3D NbO topological framework based on the mdpt− ligand; 2 reveals a two-dimensional (2D) hcb network. Interestingly, 3 presents a three-dimensional (3D) rare interpenetrated double-insertion supramolecular net via 2D ···ABAB··· layers and can be viewed as an fsh topological net, while complex 4 displays a 3D sqc117 framework. Then, the different gas sorption performances were carried out carefully for complexes 1 and 4, the results of which showed 4 has preferable sorption than that of 1 and can be the potential CO2 storage and separation material. Furthermore, the stability and luminescence of four complexes were performed carefully in the solid state.

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

ChemInform Abstract: Dynamics of Spin-State Interconversion and Cooperativity for Ferric Spin-Crossover Complexes in the Solid State.

1986 ◽  
Vol 17 (23) ◽  
Author(s):  
M. D. TIMKEN ◽  
C. E. STROUSE ◽  
S. M. SOLTIS ◽  
S. A. DAVERIO ◽  
D. N. HENDRICKSON ◽  
...  
Keyword(s):  
Solid State ◽  
Spin State ◽  
Spin Crossover ◽  
Spin Crossover Complexes

Spin state variability in Fe2+ complexes of substituted (2-(pyridin-2-yl)-1,10-phenanthroline) ligands as versatile terpyridine analogues

2017 ◽  
Vol 46 (19) ◽  
pp. 6218-6229 ◽  
Author(s):  
Holm Petzold ◽  
Paul Djomgoue ◽  
Gerald Hörner ◽  
Silvio Heider ◽  
Charles Lochenie ◽  
...  
Keyword(s):  
Solid State ◽  
Spin State ◽  
In Silico ◽  
Spin Crossover ◽  
Spin Crossover Complexes ◽  
Phenanthroline Ligands

Fe2+ spin crossover complexes [Fe(L)2]2+ (L = substituted (pyridin-2-yl)-1,10-phenanthroline) were prepared and SCO properties were investigated in solution and in the solid state by an experiment and in silico.

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