Carborane-thiol protected copper nanoclusters: stimuli-responsive materials with tunable phosphorescence

0568400 - ÚACH 2024 RIV GB eng J - Článek v odborném periodiku
Jana, A. - Jash, M. - Dar, W. A. - Roy, J. - Chakraborty, P. - Paramasivam, G. - Lebedkin, S. - Kirakci, Kaplan - Manna, S. - Antharjanam, S. - Macháček, Jan - Kučeráková, Monika - Ghosh, S. - Lang, Kamil - Kappes, M. M. - Baše, Tomáš - Pradeep, T.
Carborane-thiol protected copper nanoclusters: stimuli-responsive materials with tunable phosphorescence.
Chemical Science. Roč. 14, č. 6 (2023), s. 1613-1626. ISSN 2041-6520. E-ISSN 2041-6539
Grant CEP: GA MŠMT(CZ) LTAIN19152; GA MŠMT LM2018110
Výzkumná infrastruktura: e-INFRA CZ - 90140
Institucionální podpora: RVO:61388980 ; RVO:68378271
Klíčová slova: luminescence thermochromism * photophysical properties * iodide clusters
Obor OECD: Inorganic and nuclear chemistry; Condensed matter physics (including formerly solid state physics, supercond.) (FZU-D)
Impakt faktor: 8.4, rok: 2022
Způsob publikování: Open access

Atomically precise nanomaterials with tunable solid-state luminescence attract global interest. In this work, we present a new class of thermally stable isostructural tetranuclear copper nanoclusters (NCs), shortly Cu4@oCBT, Cu4@mCBT and Cu4@ICBT, protected by nearly isomeric carborane thiols: ortho-carborane-9-thiol, meta-carborane-9-thiol and ortho-carborane 12-iodo 9-thiol, respectively. They have a square planar Cu4 core and a butterfly-shaped Cu4S4 staple, which is appended with four respective carboranes. For Cu4@ICBT, strain generated by the bulky iodine substituents on the carboranes makes the Cu4S4 staple flatter in comparison to other clusters. High-resolution electrospray ionization mass spectrometry (HR ESI-MS) and collision energy-dependent fragmentation, along with other spectroscopic and microscopic studies, confirm their molecular structure. Although none of these clusters show any visible luminescence in solution, bright μs-long phosphorescence is observed in their crystalline forms. The Cu4@oCBT and Cu4@mCBT NCs are green emitting with quantum yields (Φ) of 81 and 59%, respectively, whereas Cu4@ICBT is orange emitting with a Φ of 18%. Density functional theory (DFT) calculations reveal the nature of their respective electronic transitions. The green luminescence of Cu4@oCBT and Cu4@mCBT clusters gets shifted to yellow after mechanical grinding, but it is regenerated after exposure to solvent vapour, whereas the orange emission of Cu4@ICBT is not affected by mechanical grinding. Structurally flattened Cu4@ICBT didn't show mechanoresponsive luminescence in contrast to other clusters, having bent Cu4S4 structures. Cu4@oCBT and Cu4@mCBT are thermally stable up to 400 °C. Cu4@oCBT retained green emission even upon heating to 200 °C under ambient conditions, while Cu4@mCBT changed from green to yellow in the same window. This is the first report on structurally flexible carborane thiol appended Cu4 NCs having stimuli-responsive tunable solid-state phosphorescence.
Trvalý link: https://hdl.handle.net/11104/0339712


Vědecká data: CCDC