Thermo- and photoinduced spin state switching in an iron(II) 2D coordination network associated with large light-induced thermal hysteresis and tuning of dimensionality via ligand modulation

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F61989592%3A15310%2F21%3A73609428" target="_blank" >RIV/61989592:15310/21:73609428 - isvavai.cz</a>

Výsledek na webu

<a href="https://pubs.rsc.org/en/content/articlelanding/2021/DT/D1DT00212K" target="_blank" >https://pubs.rsc.org/en/content/articlelanding/2021/DT/D1DT00212K</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1039/d1dt00212k" target="_blank" >10.1039/d1dt00212k</a>

Jazyk výsledku

angličtina

Název v původním jazyce

Thermo- and photoinduced spin state switching in an iron(II) 2D coordination network associated with large light-induced thermal hysteresis and tuning of dimensionality via ligand modulation

Popis výsledku v původním jazyce

Three iron(II) complexes, [Fe(L1)(2)(NCS)(2)(MeOH)(2)] (1), [Fe(L1)(2)(NCSe)(2)(MeOH)(2)] (2), and [Fe(L2)(2)(NCS)(2)](n) (3) (L1 = 2,5-dipyridyl-3,4-ethylenedioxythiophene and L2 = 2,5-diethynylpyridinyl-3,4-ethylenedioxythiophene), have been synthesized using redox-active luminescent ethylenedioxythiophene (EDOT)-based ligands, and characterized by variable temperature single-crystal X-ray diffraction, (photo)magnetic, optical reflectivity, and spectroscopy studies. Magneto-structural investigations revealed that 1 and 2 are mononuclear with a FeN4O2 octahedral coordination geometry and remain in a high-spin (HS) (S = 2) state in a temperature range of 2-280 K. Interestingly, a 2D coordination network structure with FeN6 surrounding each iron center was observed for 3, which exhibits reversible thermo-induced spin-state switching between the paramagnetic high-spin (HS) (S = 2) and diamagnetic low-spin (LS) (S = 0) states at around 105 K (T-1/2). Furthermore, optical reflectivity and photomagnetic measurements at low temperature confirmed that 3 shows reversible ON/OFF switching between the photoinduced excited paramagnetic HS metastable state and diamagnetic LS state under light irradiation (ON mode using red light and OFF mode using green light). Finally, the photoinduced excited HS state can be reversibly relaxed back to the diamagnetic ground LS state by heating the system at ca. 88 K (T-LIESST = 88 K) (light-induced excited spin state trapping (LIESST) effect). Furthermore, 3 also showed an exciting and unique 18 K wide light-induced thermal hysteresis (LITH) effect above liquid nitrogen temperature (100 K). DFT and CASSCF level theoretical calculations were utilized to better understand the magneto-structural correlations of these complexes.

Název v anglickém jazyce

Thermo- and photoinduced spin state switching in an iron(II) 2D coordination network associated with large light-induced thermal hysteresis and tuning of dimensionality via ligand modulation

Popis výsledku anglicky

Three iron(II) complexes, [Fe(L1)(2)(NCS)(2)(MeOH)(2)] (1), [Fe(L1)(2)(NCSe)(2)(MeOH)(2)] (2), and [Fe(L2)(2)(NCS)(2)](n) (3) (L1 = 2,5-dipyridyl-3,4-ethylenedioxythiophene and L2 = 2,5-diethynylpyridinyl-3,4-ethylenedioxythiophene), have been synthesized using redox-active luminescent ethylenedioxythiophene (EDOT)-based ligands, and characterized by variable temperature single-crystal X-ray diffraction, (photo)magnetic, optical reflectivity, and spectroscopy studies. Magneto-structural investigations revealed that 1 and 2 are mononuclear with a FeN4O2 octahedral coordination geometry and remain in a high-spin (HS) (S = 2) state in a temperature range of 2-280 K. Interestingly, a 2D coordination network structure with FeN6 surrounding each iron center was observed for 3, which exhibits reversible thermo-induced spin-state switching between the paramagnetic high-spin (HS) (S = 2) and diamagnetic low-spin (LS) (S = 0) states at around 105 K (T-1/2). Furthermore, optical reflectivity and photomagnetic measurements at low temperature confirmed that 3 shows reversible ON/OFF switching between the photoinduced excited paramagnetic HS metastable state and diamagnetic LS state under light irradiation (ON mode using red light and OFF mode using green light). Finally, the photoinduced excited HS state can be reversibly relaxed back to the diamagnetic ground LS state by heating the system at ca. 88 K (T-LIESST = 88 K) (light-induced excited spin state trapping (LIESST) effect). Furthermore, 3 also showed an exciting and unique 18 K wide light-induced thermal hysteresis (LITH) effect above liquid nitrogen temperature (100 K). DFT and CASSCF level theoretical calculations were utilized to better understand the magneto-structural correlations of these complexes.

Druh

J_imp - Článek v periodiku v databázi Web of Science

CEP obor

—

OECD FORD obor

10402 - Inorganic and nuclear chemistry

Projekt

—

Návaznosti

I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace

Rok uplatnění

2021

Kód důvěrnosti údajů

S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů

Název periodika

Dalton Transactions

ISSN

1477-9226

e-ISSN

—

Svazek periodika

50

Číslo periodika v rámci svazku

22

Stát vydavatele periodika

GB - Spojené království Velké Británie a Severního Irska

Počet stran výsledku

11

Strana od-do

7725-7735

Kód UT WoS článku

000650205100001

EID výsledku v databázi Scopus

2-s2.0-85107837139