Site-specific substitution in atomically precise carboranethiol-protected nanoclusters and concomitant changes in electronic properties

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F61388980%3A_____%2F25%3A00617315" target="_blank" >RIV/61388980:_____/25:00617315 - isvavai.cz</a>

Výsledek na webu

<a href="https://hdl.handle.net/11104/0364256" target="_blank" >https://hdl.handle.net/11104/0364256</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1038/s41467-025-56385-w" target="_blank" >10.1038/s41467-025-56385-w</a>

Jazyk výsledku

angličtina

Název v původním jazyce

Site-specific substitution in atomically precise carboranethiol-protected nanoclusters and concomitant changes in electronic properties

Popis výsledku v původním jazyce

We report the synthesis of [Ag17(o1-CBT)12]3- abbreviated as Ag17, a stable 8e(-) anionic cluster with a unique Ag@Ag12@Ag4 core-shell structure, where o1-CBT is ortho-carborane-1-thiol. By substituting Ag atoms with Au and/or Cu at specific sites we created isostructural clusters [AuAg16(o1-CBT)12]3- (AuAg16), [Ag13Cu4(o1-CBT)12]3- (Ag13Cu4) and [AuAg12Cu4(o1-CBT)12]3- (AuAg12Cu4). These substitutions make systematic modulation of their structural and electronic properties. We show that Au preferentially occupies the core, while Cu localizes in the tetrahedral shell, influencing stability and structural diversity of the clusters. The band gap expands systematically (2.09 eV for Ag17 to 2.28 eV for AuAg12Cu4), altering optical absorption and emission. Ultrafast optical measurements reveal longer excited-state lifetimes for Cu-containing clusters, highlighting the effect of heteroatom incorporation. These results demonstrate a tunable platform for designing nanoclusters with tailored electronic properties, with implications for optoelectronics and catalysis.

Název v anglickém jazyce

Site-specific substitution in atomically precise carboranethiol-protected nanoclusters and concomitant changes in electronic properties

Popis výsledku anglicky

We report the synthesis of [Ag17(o1-CBT)12]3- abbreviated as Ag17, a stable 8e(-) anionic cluster with a unique Ag@Ag12@Ag4 core-shell structure, where o1-CBT is ortho-carborane-1-thiol. By substituting Ag atoms with Au and/or Cu at specific sites we created isostructural clusters [AuAg16(o1-CBT)12]3- (AuAg16), [Ag13Cu4(o1-CBT)12]3- (Ag13Cu4) and [AuAg12Cu4(o1-CBT)12]3- (AuAg12Cu4). These substitutions make systematic modulation of their structural and electronic properties. We show that Au preferentially occupies the core, while Cu localizes in the tetrahedral shell, influencing stability and structural diversity of the clusters. The band gap expands systematically (2.09 eV for Ag17 to 2.28 eV for AuAg12Cu4), altering optical absorption and emission. Ultrafast optical measurements reveal longer excited-state lifetimes for Cu-containing clusters, highlighting the effect of heteroatom incorporation. These results demonstrate a tunable platform for designing nanoclusters with tailored electronic properties, with implications for optoelectronics and catalysis.

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

2025

Kód důvěrnosti údajů

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

Název periodika

Nature Communications

ISSN

2041-1723

e-ISSN

2041-1723

Svazek periodika

16

Číslo periodika v rámci svazku

1

Stát vydavatele periodika

DE - Spolková republika Německo

Počet stran výsledku

13

Strana od-do

1197

Kód UT WoS článku

001414647200017

EID výsledku v databázi Scopus

2-s2.0-85217623688