Multicolor photoluminescence of Cu14 clusters modulated using surface ligands

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F61388980%3A_____%2F24%3A00588530" target="_blank" >RIV/61388980:_____/24:00588530 - isvavai.cz</a>

Výsledek na webu

<a href="https://hdl.handle.net/11104/0355578" target="_blank" >https://hdl.handle.net/11104/0355578</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1039/d4sc01566e" target="_blank" >10.1039/d4sc01566e</a>

Jazyk výsledku

angličtina

Název v původním jazyce

Multicolor photoluminescence of Cu14 clusters modulated using surface ligands

Popis výsledku v původním jazyce

Copper nanoclusters exhibit unique structural features and their molecular assembly results in diverse photoluminescence properties. In this study, we present ligand-dependent multicolor luminescence observed in a Cu-14 cluster, primarily protected by ortho-carborane-9,12-dithiol (o-CBDT), featuring an octahedral Cu-6 inner kernel enveloped by eight isolated copper atoms. The outer layer of the metal kernel consists of six bidentate o-CBDT ligands, in which carborane backbones are connected through mu(3)-sulphide linkages. The initially prepared Cu-14 cluster, solely protected by six o-CBDT ligands, did not crystallize in its native form. However, in the presence of N,N-dimethylformamide (DMF), the cluster crystallized along with six DMF molecules. Single-crystal X-ray diffraction (SCXRD) revealed that the DMF molecules were directly coordinated to six of the eight capping Cu atoms, while oxygen atoms were bound to the two remaining Cu apices in antipodal positions. Efficient tailoring of the cluster surface with DMF shifted its luminescence from yellow to bright red. Luminescence decay profiles showed fluorescence emission for these clusters, originating from the singlet states. Additionally, we synthesized microcrystalline fibers with a one-dimensional assembly of DMF-appended Cu-14 clusters and bidentate DPPE linkers. These fibers exhibited bright greenish-yellow phosphorescence emission, originating from the triplet state, indicating the drastic surface tailoring effect of secondary ligands. Theoretical calculations provided insights into the electronic energy levels and associated electronic transitions for these clusters. This work demonstrated dynamic tuning of the emissive excited states of copper nanoclusters through the efficient engineering of ligands.

Název v anglickém jazyce

Multicolor photoluminescence of Cu14 clusters modulated using surface ligands

Popis výsledku anglicky

Copper nanoclusters exhibit unique structural features and their molecular assembly results in diverse photoluminescence properties. In this study, we present ligand-dependent multicolor luminescence observed in a Cu-14 cluster, primarily protected by ortho-carborane-9,12-dithiol (o-CBDT), featuring an octahedral Cu-6 inner kernel enveloped by eight isolated copper atoms. The outer layer of the metal kernel consists of six bidentate o-CBDT ligands, in which carborane backbones are connected through mu(3)-sulphide linkages. The initially prepared Cu-14 cluster, solely protected by six o-CBDT ligands, did not crystallize in its native form. However, in the presence of N,N-dimethylformamide (DMF), the cluster crystallized along with six DMF molecules. Single-crystal X-ray diffraction (SCXRD) revealed that the DMF molecules were directly coordinated to six of the eight capping Cu atoms, while oxygen atoms were bound to the two remaining Cu apices in antipodal positions. Efficient tailoring of the cluster surface with DMF shifted its luminescence from yellow to bright red. Luminescence decay profiles showed fluorescence emission for these clusters, originating from the singlet states. Additionally, we synthesized microcrystalline fibers with a one-dimensional assembly of DMF-appended Cu-14 clusters and bidentate DPPE linkers. These fibers exhibited bright greenish-yellow phosphorescence emission, originating from the triplet state, indicating the drastic surface tailoring effect of secondary ligands. Theoretical calculations provided insights into the electronic energy levels and associated electronic transitions for these clusters. This work demonstrated dynamic tuning of the emissive excited states of copper nanoclusters through the efficient engineering of ligands.

Druh

J_imp - Článek v periodiku v databázi Web of Science

CEP obor

—

OECD FORD obor

10402 - Inorganic and nuclear chemistry

Projekt

<a href="/cs/project/LTAIN19152" target="_blank" >LTAIN19152: Karboranovými ligandy chráněné kovové nanoklastry: nová třída materiálů s atomárním rozlišením</a><br>

Návaznosti

I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace

Rok uplatnění

2024

Kód důvěrnosti údajů

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

Název periodika

Chemical Science

ISSN

2041-6520

e-ISSN

2041-6539

Svazek periodika

15

Číslo periodika v rámci svazku

34

Stát vydavatele periodika

GB - Spojené království Velké Británie a Severního Irska

Počet stran výsledku

12

Strana od-do

13741-13752

Kód UT WoS článku

001283026100001

EID výsledku v databázi Scopus

2-s2.0-85200385716