Novel Lanthanide(III) Porphyrin-Based Metal-Organic Frameworks: Structure, Gas Adsorption, and Magnetic Properties

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F00216208%3A11310%2F21%3A10432919" target="_blank" >RIV/00216208:11310/21:10432919 - isvavai.cz</a>

Výsledek na webu

<a href="https://verso.is.cuni.cz/pub/verso.fpl?fname=obd_publikace_handle&handle=YT95t7w2JO" target="_blank" >https://verso.is.cuni.cz/pub/verso.fpl?fname=obd_publikace_handle&handle=YT95t7w2JO</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1021/acsomega.1c03327" target="_blank" >10.1021/acsomega.1c03327</a>

Jazyk výsledku

angličtina

Název v původním jazyce

Novel Lanthanide(III) Porphyrin-Based Metal-Organic Frameworks: Structure, Gas Adsorption, and Magnetic Properties

Popis výsledku v původním jazyce

The present work focuses on the hydrothermal synthesis and properties of porous coordination polymers of metal-porphyrin framework (MPF) type, namely, {[Pr(4)(H2TPPS)(3)] . 11H2O}(n) (UPJS-10), {[Eu/Sm(H2TPPS)] . H3O(+) . 16H2O}(n) (UPJS-11), and {[Ce(4)(H2TPPS)(3)] . 11H2O}(n) (UPJS-12) (H2TPPS = 4,4&apos;,4&apos;&apos;,4&apos;&apos;&apos;-(porphyrin-5,10,15,20-tetrayptetrakisbenzenesulfonate(4)). The compounds were characterized using several analytical techniques: infrared spectroscopy, thermogravimetric measurements, elemental analysis, gas adsorption measurements, and single-crystal structure analysis (SXRD). The results of SXRD revealed a three-dimensional open porous framework containing crossing cavities propagating along all crystallographic axes. Coordination of H2TPPS4- ligands with Ln(III) ions leads to the formation of 1D polymeric chains propagating along the c crystallographic axis. Argon sorption measurements at -186 degrees C show that the activated MPFs have apparent BET surface areas of 260 m(2)g(-1) (UPJS-10) and 230 m(2) g(-1) (UPJS-12). Carbon dioxide adsorption isotherms at 0 degrees C show adsorption capacities up to 1 bar of 9.8 wt % for UPJS-10 and 8.6 wt % for UPJS-12. At a temperature of 20 degrees C, the respective CO2 adsorption capacities decreased to 6.95 and 5.99 wt %, respectively. The magnetic properties of UPJS-10 are characterized by the presence of a close-lying nonmagnetic ground singlet and excited doublet states in the electronic spectrum of Pr(III) ions. A much larger energy difference was suggested between the two lowest Kramers doublets of Ce(III) ions in UPJS-12. Finally, the analysis of X-band EPR spectra revealed the presence of radical spins, which were tentatively assigned to be originating from the porphyrin ligands.

Název v anglickém jazyce

Novel Lanthanide(III) Porphyrin-Based Metal-Organic Frameworks: Structure, Gas Adsorption, and Magnetic Properties

Popis výsledku anglicky

The present work focuses on the hydrothermal synthesis and properties of porous coordination polymers of metal-porphyrin framework (MPF) type, namely, {[Pr(4)(H2TPPS)(3)] . 11H2O}(n) (UPJS-10), {[Eu/Sm(H2TPPS)] . H3O(+) . 16H2O}(n) (UPJS-11), and {[Ce(4)(H2TPPS)(3)] . 11H2O}(n) (UPJS-12) (H2TPPS = 4,4&apos;,4&apos;&apos;,4&apos;&apos;&apos;-(porphyrin-5,10,15,20-tetrayptetrakisbenzenesulfonate(4)). The compounds were characterized using several analytical techniques: infrared spectroscopy, thermogravimetric measurements, elemental analysis, gas adsorption measurements, and single-crystal structure analysis (SXRD). The results of SXRD revealed a three-dimensional open porous framework containing crossing cavities propagating along all crystallographic axes. Coordination of H2TPPS4- ligands with Ln(III) ions leads to the formation of 1D polymeric chains propagating along the c crystallographic axis. Argon sorption measurements at -186 degrees C show that the activated MPFs have apparent BET surface areas of 260 m(2)g(-1) (UPJS-10) and 230 m(2) g(-1) (UPJS-12). Carbon dioxide adsorption isotherms at 0 degrees C show adsorption capacities up to 1 bar of 9.8 wt % for UPJS-10 and 8.6 wt % for UPJS-12. At a temperature of 20 degrees C, the respective CO2 adsorption capacities decreased to 6.95 and 5.99 wt %, respectively. The magnetic properties of UPJS-10 are characterized by the presence of a close-lying nonmagnetic ground singlet and excited doublet states in the electronic spectrum of Pr(III) ions. A much larger energy difference was suggested between the two lowest Kramers doublets of Ce(III) ions in UPJS-12. Finally, the analysis of X-band EPR spectra revealed the presence of radical spins, which were tentatively assigned to be originating from the porphyrin ligands.

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

ACS Omega [online]

ISSN

2470-1343

e-ISSN

—

Svazek periodika

6

Číslo periodika v rámci svazku

38

Stát vydavatele periodika

US - Spojené státy americké

Počet stran výsledku

13

Strana od-do

24637-24649

Kód UT WoS článku

000703535900034

EID výsledku v databázi Scopus

2-s2.0-85116200586