TY - JOUR
T1 - Gold Au(I)6 Clusters with Ligand-Derived Atomic Steric Locking
T2 - Multifunctional Optoelectrical Properties and Quantum Coherence
AU - Chandra, Sourov
AU - Sciortino, Alice
AU - Das, Susobhan
AU - Ahmed, Faisal
AU - Jana, Arijit
AU - Roy, Jayoti
AU - Li, Diao
AU - Liljeström, Ville
AU - Jiang, Hua
AU - Johansson, Leena Sisko
AU - Chen, Xi
AU - Nonappa, null
AU - Cannas, Marco
AU - Pradeep, Thalappil
AU - Peng, Bo
AU - Ras, Robin H.A.
AU - Sun, Zhipei
AU - Ikkala, Olli
AU - Messina, Fabrizio
N1 - Funding Information:
This work was supported by the ERC Advanced grant (DRIVEN, ERC‐2016‐AdG‐742829), the ERC grant (834742), the EU H2020‐MSCA‐RISE‐872049 (IPN‐Bio), the Academy of Finland's Centre of Excellence in Molecular Engineering of Biosynthetic Hybrid Materials Research (HYBER, 2014–2019), and Life‐Inspired Hybrid Materials (LIBER, 346108), Academy of Finland project fundings (No. 352900, 314810, 333982, 336144, 352780, 352930 and 353364), FinnCERES and Photonics Research and Innovation (PREIN) flagship programs. The authors acknowledge the provision of facilities and technical support by Aalto University OtaNano – Nanomicroscopy Center (Aalto‐NMC).
Publisher Copyright:
© 2023 Wiley-VCH GmbH.
PY - 2023
Y1 - 2023
N2 - An atomically precise ultrasmall Au(I)6 nanocluster where the six gold atoms are complexed by three sterically interlocking stabilizing ligands is reported, allowing a unique combination of efficient third harmonic generation (THG), intense photoluminescence quantum yield (35%), ultrafast quantum coherence, and electron accepting properties. The reaction of 6-(dibutylamino)-1,3,5-triazine-2,4-dithiol (TRZ) with HAuCl4 leads to complexation by thiolation. However, intriguingly, another reduction step is needed to form the centrosymmetric Au(I)6TRZ3 clusters with the multifunctional properties. Here, ascorbic acid is employed as a mild reducing agent, in contrast to the classic reducing agents, like NaBH4 and NaBH3CN, which often produce mixtures of clusters or gold nanoparticles. Such Au(I)6 nanocluster films produce very strong THG response, never observed for nanoclusters. The clusters also produce brilliant single and multiphoton luminescence with exceptional stability. Density functional theory calculations and femtosecond transient absorption studies suggest ultrafast ligand-to-metal charge transfer, quantum coherence with long decoherence time 200–300 fs, and fast propagation of excitation from the core to the surrounding solvent. Finally, novel electron-accepting ground state properties allow p-doping of 2D field-effect transistor devices. Summarizing, the potential of ultrasmall sterically interlocked Au(I) clusters, i.e., complexes allowed by the new sequential reduction protocol, towards multifunctional devices, fast photoswitches, and quantum colloidal devices is shown.
AB - An atomically precise ultrasmall Au(I)6 nanocluster where the six gold atoms are complexed by three sterically interlocking stabilizing ligands is reported, allowing a unique combination of efficient third harmonic generation (THG), intense photoluminescence quantum yield (35%), ultrafast quantum coherence, and electron accepting properties. The reaction of 6-(dibutylamino)-1,3,5-triazine-2,4-dithiol (TRZ) with HAuCl4 leads to complexation by thiolation. However, intriguingly, another reduction step is needed to form the centrosymmetric Au(I)6TRZ3 clusters with the multifunctional properties. Here, ascorbic acid is employed as a mild reducing agent, in contrast to the classic reducing agents, like NaBH4 and NaBH3CN, which often produce mixtures of clusters or gold nanoparticles. Such Au(I)6 nanocluster films produce very strong THG response, never observed for nanoclusters. The clusters also produce brilliant single and multiphoton luminescence with exceptional stability. Density functional theory calculations and femtosecond transient absorption studies suggest ultrafast ligand-to-metal charge transfer, quantum coherence with long decoherence time 200–300 fs, and fast propagation of excitation from the core to the surrounding solvent. Finally, novel electron-accepting ground state properties allow p-doping of 2D field-effect transistor devices. Summarizing, the potential of ultrasmall sterically interlocked Au(I) clusters, i.e., complexes allowed by the new sequential reduction protocol, towards multifunctional devices, fast photoswitches, and quantum colloidal devices is shown.
KW - field effect transistors
KW - nanoclusters
KW - photoluminescence
KW - quantum coherence
KW - third-harmonic generation
U2 - 10.1002/adom.202202649
DO - 10.1002/adom.202202649
M3 - Article
AN - SCOPUS:85148441545
SN - 2195-1071
VL - 11
JO - Advanced Optical Materials
JF - Advanced Optical Materials
IS - 8
M1 - 2202649
ER -