Host–Guest Interactions in Metal–Organic Frameworks Doped with Acceptor Molecules as Revealed by Resonance Raman Spectroscopy

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F61388955%3A_____%2F20%3A00534518" target="_blank" >RIV/61388955:_____/20:00534518 - isvavai.cz</a>

Výsledek na webu

<a href="http://hdl.handle.net/11104/0312702" target="_blank" >http://hdl.handle.net/11104/0312702</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1021/acs.jpcc.0c07473" target="_blank" >10.1021/acs.jpcc.0c07473</a>

Jazyk výsledku

angličtina

Název v původním jazyce

Host–Guest Interactions in Metal–Organic Frameworks Doped with Acceptor Molecules as Revealed by Resonance Raman Spectroscopy

Popis výsledku v původním jazyce

Metal–organic frameworks (MOFs) represent a class of porous materials whose properties can be altered by doping with redox-active molecules. Despite advanced properties such as enhanced electrical conduction that doped MOFs exhibit, understanding physical mechanisms remains challenging because of their heterogeneous nature hindering experimental observations of host–guest interactions. Here, we show a study of charge transfer between Mn-MOF-74 and electron acceptors, 7,7,8,8-tetracyanoquinodimethane (TCNQ) and XeF2, employing selective enhancement of Raman scattering of different moieties under various optical-resonance conditions. We identify Raman modes of molecular components and elucidate that TCNQ gets oxidized into dicyano-p-toluoyl cyanide (DCTC–) while XeF2 fluorinates the MOF upon infiltration. The framework’s linker in both cases acts as an electron donor as deduced from blue shifts of the C–O stretching mode accompanied by the emergence of a quinone-like mode. This work demonstrates a generally applicable methodology for investigating charge transfer in various donor–acceptor systems by means of resonance Raman spectroscopy.

Název v anglickém jazyce

Host–Guest Interactions in Metal–Organic Frameworks Doped with Acceptor Molecules as Revealed by Resonance Raman Spectroscopy

Popis výsledku anglicky

Metal–organic frameworks (MOFs) represent a class of porous materials whose properties can be altered by doping with redox-active molecules. Despite advanced properties such as enhanced electrical conduction that doped MOFs exhibit, understanding physical mechanisms remains challenging because of their heterogeneous nature hindering experimental observations of host–guest interactions. Here, we show a study of charge transfer between Mn-MOF-74 and electron acceptors, 7,7,8,8-tetracyanoquinodimethane (TCNQ) and XeF2, employing selective enhancement of Raman scattering of different moieties under various optical-resonance conditions. We identify Raman modes of molecular components and elucidate that TCNQ gets oxidized into dicyano-p-toluoyl cyanide (DCTC–) while XeF2 fluorinates the MOF upon infiltration. The framework’s linker in both cases acts as an electron donor as deduced from blue shifts of the C–O stretching mode accompanied by the emergence of a quinone-like mode. This work demonstrates a generally applicable methodology for investigating charge transfer in various donor–acceptor systems by means of resonance Raman spectroscopy.

Druh

J_imp - Článek v periodiku v databázi Web of Science

CEP obor

—

OECD FORD obor

10403 - Physical chemistry

Projekt

Výsledek vznikl pri realizaci vícero projektů. Více informací v záložce Projekty.

Návaznosti

I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace

Rok uplatnění

2020

Kód důvěrnosti údajů

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

Název periodika

Journal of Physical Chemistry C

ISSN

1932-7447

e-ISSN

—

Svazek periodika

124

Číslo periodika v rámci svazku

44

Stát vydavatele periodika

US - Spojené státy americké

Počet stran výsledku

6

Strana od-do

24245-24250

Kód UT WoS článku

000589917300024

EID výsledku v databázi Scopus

2-s2.0-85096077566