Novel Metallo-Supramolecular Polymers with 1-Thioxophosphole Main-Chain Units and Remarkable Photoinduced Changes in Their Resonance Raman Spectra

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F00216208%3A11310%2F22%3A10453132" target="_blank" >RIV/00216208:11310/22:10453132 - isvavai.cz</a>

Výsledek na webu

<a href="https://verso.is.cuni.cz/pub/verso.fpl?fname=obd_publikace_handle&handle=gjCuykR3so" target="_blank" >https://verso.is.cuni.cz/pub/verso.fpl?fname=obd_publikace_handle&handle=gjCuykR3so</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.3390/polym14235207" target="_blank" >10.3390/polym14235207</a>

Jazyk výsledku

angličtina

Název v původním jazyce

Novel Metallo-Supramolecular Polymers with 1-Thioxophosphole Main-Chain Units and Remarkable Photoinduced Changes in Their Resonance Raman Spectra

Popis výsledku v původním jazyce

New low-bandgap unimers, with the central thiophene-(1-thioxophosphole)-thiophene (TPT) ring sequence and 2,2&apos;:6&apos;,2&quot;-terpyridin-4&apos;-yl (tpy) end groups connected to the central unit via conjugated linkers of different size, are prepared and assembled with Zn(II) and Fe(II) ions to metallo-supramolecular polymers (MSPs) that are studied regarding their properties. The most interesting feature of Zn-MSPs is the luminescence extended deep into the NIR region. Fe-MSPs not only show the metal-to-ligand charge transfer (MLCT) manifested by the MLCT band (an expected feature) but also an as-yet-undescribed remarkable phenomenon: specific damping of the bands of the TPT sequence in the resonance Raman spectra taken from solid Fe-MSPs using the excitation to the MLCT band (532 nm). The damping is highly reversible at the low laser power of 0.1 mW but gradually becomes irreversible as the power reaches ca. 5 mW. The revealed phenomenon is not shown by the same Fe-MSPs in solutions, nor by Fe-MSPs containing no phosphole units. A hypothesis is proposed that explains this phenomenon and its dependence on the irradiation intensity as a result of the interplay of three factors: (i) enhancement of the MLCT process by excitation radiation, (ii) the electron-acceptor character of the 1-thioxophosphole ring, and (iii) morphological changes of the lattice and their dependence on the population of new structures in the lattice.

Název v anglickém jazyce

Novel Metallo-Supramolecular Polymers with 1-Thioxophosphole Main-Chain Units and Remarkable Photoinduced Changes in Their Resonance Raman Spectra

Popis výsledku anglicky

New low-bandgap unimers, with the central thiophene-(1-thioxophosphole)-thiophene (TPT) ring sequence and 2,2&apos;:6&apos;,2&quot;-terpyridin-4&apos;-yl (tpy) end groups connected to the central unit via conjugated linkers of different size, are prepared and assembled with Zn(II) and Fe(II) ions to metallo-supramolecular polymers (MSPs) that are studied regarding their properties. The most interesting feature of Zn-MSPs is the luminescence extended deep into the NIR region. Fe-MSPs not only show the metal-to-ligand charge transfer (MLCT) manifested by the MLCT band (an expected feature) but also an as-yet-undescribed remarkable phenomenon: specific damping of the bands of the TPT sequence in the resonance Raman spectra taken from solid Fe-MSPs using the excitation to the MLCT band (532 nm). The damping is highly reversible at the low laser power of 0.1 mW but gradually becomes irreversible as the power reaches ca. 5 mW. The revealed phenomenon is not shown by the same Fe-MSPs in solutions, nor by Fe-MSPs containing no phosphole units. A hypothesis is proposed that explains this phenomenon and its dependence on the irradiation intensity as a result of the interplay of three factors: (i) enhancement of the MLCT process by excitation radiation, (ii) the electron-acceptor character of the 1-thioxophosphole ring, and (iii) morphological changes of the lattice and their dependence on the population of new structures in the lattice.

Druh

J_imp - Článek v periodiku v databázi Web of Science

CEP obor

—

OECD FORD obor

10404 - Polymer science

Projekt

<a href="/cs/project/GA22-02005S" target="_blank" >GA22-02005S: Transformace excitonů v supramolekulárních polymerech pro konverzi energie</a><br>

Návaznosti

P - Projekt vyzkumu a vyvoje financovany z verejnych zdroju (s odkazem do CEP)

Rok uplatnění

2022

Kód důvěrnosti údajů

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

Název periodika

Polymers [online]

ISSN

2073-4360

e-ISSN

2073-4360

Svazek periodika

14

Číslo periodika v rámci svazku

23

Stát vydavatele periodika

CH - Švýcarská konfederace

Počet stran výsledku

21

Strana od-do

5207

Kód UT WoS článku

000896530800001

EID výsledku v databázi Scopus

2-s2.0-85143598633