scholarly journals Reversible guest-induced gate-opening with multiplex spin crossover responses in two-dimensional Hofmann clathrates

2020 ◽  
Vol 11 (41) ◽  
pp. 11224-11234
Author(s):  
Rubén Turo-Cortés ◽  
Carlos Bartual-Murgui ◽  
Javier Castells-Gil ◽  
M. Carmen Muñoz ◽  
Carlos Martí-Gastaldo ◽  
...  

Layered Hofmann-type iron(ii) coordination polymers functionalised with 5-aminopyrimidine ligands show gate-opening driven guest-exchange accompanied by drastic structural and spin-crossover modulations.

RSC Advances ◽  
2020 ◽  
Vol 10 (9) ◽  
pp. 5040-5049 ◽  
Author(s):  
Jong Won Shin ◽  
Ah Rim Jeong ◽  
Jong Hwa Jeong ◽  
Hikaru Zenno ◽  
Shinya Hayami ◽  
...  

Two-dimensional Fe-based coordination polymers with square-grid shapes were prepared by self-assembly and exhibited an interesting spin crossover behavior depending on the coordinated counter ions.


2015 ◽  
Vol 54 (17) ◽  
pp. 8711-8716 ◽  
Author(s):  
Wei Liu ◽  
Lu Wang ◽  
Yu-Jun Su ◽  
Yan-Cong Chen ◽  
Jiri Tucek ◽  
...  

2014 ◽  
Vol 67 (11) ◽  
pp. 1563 ◽  
Author(s):  
Florence Ragon ◽  
Korcan Yaksi ◽  
Natasha F. Sciortino ◽  
Guillaume Chastanet ◽  
Jean-François Létard ◽  
...  

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.


2009 ◽  
Vol 62 (9) ◽  
pp. 1155 ◽  
Author(s):  
Gloria Agustí ◽  
Ana Belén Gaspar ◽  
M. Carmen Muñoz ◽  
Pascal G. Lacroix ◽  
José Antonio Real

The suitability of the stilbazole push–pull ligands, 4′-dimethylaminostilbazole (DMAS) and 4′-diethylaminostilbazole (DEAS), for the construction of bimetallic FeII–AgI/AuI cyanide-based coordination polymers that exhibit spin crossover properties is investigated. The structural and physical characterization of four novel two-dimensional FeII polymers formulated as {Fe(DMAS)2[Ag(DMAS)(CN)2]2} (1) and {Fe(L)2[M(CN)2]2} (L = DMAS, M = Au (2); DEAS, Ag (3); DEAS, Au (4)) is reported. Polymers 1 and 4 are paramagnetic over the whole range of temperatures studied (5–300 K), whereas 2 and 3 exhibit spin crossover properties.


2014 ◽  
Vol 67 (11) ◽  
pp. 1553 ◽  
Author(s):  
Natasha F. Sciortino ◽  
Suzanne M. Neville

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.


2010 ◽  
Vol 22 (14) ◽  
pp. 4271-4281 ◽  
Author(s):  
Víctor Martínez ◽  
Ishtvan Boldog ◽  
Ana Belén Gaspar ◽  
Vadim Ksenofontov ◽  
Ashis Bhattacharjee ◽  
...  

2021 ◽  
Author(s):  
Mickaele Bonneau ◽  
Kunihisa Sugimoto ◽  
Ken‐ichi Otake ◽  
Yukiko Tsuji ◽  
Nanae Shimanaka ◽  
...  

2021 ◽  
Vol 9 (15) ◽  
pp. 5082-5087
Author(s):  
Yu Gong ◽  
Wang-Kang Han ◽  
Hui-Shu Lu ◽  
Qing-Tao Hu ◽  
Huan Tu ◽  
...  

New Hofmann-type metal–organic frameworks display rare and complete ligand exchange induced single crystal to single crystal transformations from 3D frameworks to 2D layers, accompanied by magnetic properties transition from two-step SCO behavior to hysteretic SCO behavior.


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