A temperature-sensitive luminescent Ag20 nanocluster templated by carbonate in situ generated from atmospheric CO2 fixation

Yuan, Shuai; Deng, Yongkai; Wang, Xing‐Po; Sun, Di

doi:10.1039/c3nj00645j

Cited by 58 publications

(45 citation statements)

References 81 publications

(9 reference statements)

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“…8b , compound SD/Ag9 is emission silent at room temperature, however, it emits yellow light at 77 K with a maximum at 587 nm ( λ ex = 400 nm), which is probably due to a ligand-to-metal charge transfer (LMCT, charge transfer from the S 3p to Ag 5s orbital) transition disturbed by Ag⋯Ag interactions 65 . This temperature-sensitive emission behaviours should be related to the variations of molecule rigidity and argentophilicity under different temperatures and have been previously observed in other silver-thiolate clusters such as [(CO 3 )@Ag 20 (SBu t ) 10 (DMF) 6 (NO 3 ) 8 ] 66 and [S@Ag 56 S 12 (SBu t ) 20 ](CH 3 COO) 10 67 . Compounds SD/Ag11 and SD/Ag12 emit green light at room temperature with a similar maximum emission peak at ca .…”

Section: Resultssupporting

confidence: 70%

Trapping an octahedral Ag6 kernel in a seven-fold symmetric Ag56 nanowheel

et al. 2018

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High-nuclearity silver clusters are appealing synthetic targets for their remarkable structures, but most are isolated serendipitously. We report here six giant silver-thiolate clusters mediated by solvents, which not only dictate the formation of an octahedral Ag64+ kernel, but also influence the in situ-generated Mo-based anion templates. The typical sevenfold symmetric silver nanowheels show a hierarchical cluster-in-cluster structure that comprises an outermost Ag56 shell and an inner Ag64+ kernel in the centre with seven MoO42− anion templates around it. Electrospray ionization mass spectrometry analyses reveal the underlying rule for the formation of such unique silver nanowheels. This work establishes a solvent–intervention approach to construct high-nuclearity silver clusters in which both the formation of octahedral Ag64+ kernel and in situ generation of various Mo-based anion templates can be simultaneously controlled.

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Section: Resultssupporting

confidence: 70%

Trapping an octahedral Ag6 kernel in a seven-fold symmetric Ag56 nanowheel

et al. 2018

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“…At 77 K, the quantum yield of 2 sharply rises to Φ f =11.8 %, and the lifetime value is on the scale of microseconds (1.34 μs, Figure S23 in the Supporting Information). The increase of quantum yield at low temperature may be related to the enhanced rigidity and faster intersystem crossing process by the presence of the heavy‐metal ion when cooling, which effectively reduces the loss of energy by nonradiation decay 18…”

mentioning

confidence: 99%

“…[17] Investigation of luminescent behavior based on silver thiolate clusters is still in its infancy, the only impressive example being the novel luminescent molecular silver thiolate cluster [Ag 62 S 13 -(StBu) 32 ](BF 4 ) 4 that displays intense red emission in both solid state and solution at room temperature, as reported by Wang. [1d] Although there are sporadic reports on luminescence thermochromism, [18] some of them are just emissive in the solid state at 77 K but are not emissive at room temperature. [8a] In this work, a systematic investigation of thermochromism based on silver thiolate clusters was carried out for the first time.…”

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confidence: 99%

“…The increase of quantum yield at low temperature may be related to the enhanced rigidity and faster intersystem crossing process by the presence of the heavy-metal ion when cooling, which effectively reduces the loss of energy by nonradiation decay. [18] To reveal the relationship between the photoemission behavior and molecular structure in the crystalline state, we performed variable-temperature single-crystal X-ray analyses (VT-SCXRD) on complexes 1 and 2 (110, 200, and 298 K). No phase transition occurs in the whole temperature range in these crystals.…”

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confidence: 99%

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Thermochromic Luminescent Nest‐Like Silver Thiolate Cluster

Huang

Qin

et al. 2014

Chemistry A European J

138

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A novel discrete open high-nuclearity nest-like silver thiolate cluster complex, [Ag33 S3 (StBu)16 (CF3 COO)9 (NO3 )(CH3 CN)2 ](NO3 ) (1), has been isolated with nitrate and S(2-) anions acting as structure-directing templates. Its similar nest-like structure has been assembled into an extended layer [Ag31 S3 (StBu)16 (NO3 )9 ]n (2) by adjustment of auxiliary ligand. More interestingly, both complexes exhibit temperature-dependent luminescence of high sensitivity with a large fluorescence enhancement (12-fold for 1, 21-fold for 2), which can be easily recognized by the naked-eye (dramatic red-shift Δ=104 nm for 1, larger Δ=113 nm for 2 at 77 K compared to those at 298 K). The correlation between luminescent thermochromism and temperature-dependent variation of the coordination modes of template NO3 (-) anion, Ag⋅⋅⋅S and Ag⋅⋅⋅Ag distances are also elucidated through variable-temperature single-crystal X-ray crystal structure (VT-SCXRD) analyses.

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“…It was surprising that this intermediate 2 contains a CO 3 2− anion template, as no CO 3 2− species was intentionally added into the reaction. We speculated that the CO 3 2− was introduced from the atmospheric carbon dioxide fixation 51,52 . To confirm the reaction pathway and understand the reaction kinetics, we added a small amount of Ag 2 CO 3 (4% molar ratio to AgS t Bu) into the previously described reaction for synthesizing 1.…”

Section: Structure Ofmentioning

confidence: 99%

Catalyzed assembly of hollow silver-sulfide cluster through self-releasable anion template

et al. 2018

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Hollow nanoclusters are intriguing for bridging the gap between small metal-organic cages and hollow nanoparticles and provide enormous opportunities for functional materials. Rational construction of hollow nanoclusters remains a challenge owing to the poor understanding of their formation pathways and difficulties in obtaining the intermediate structures. Here we report a catalyzed assembly strategy to construct hollow silver-sulfide clusters using a self-releasable carbonate template. The hollow Ag 56 cluster and the carbonate-templated Ag 33 intermediate are characterized by single-crystal X-ray analysis. Combining this data with a time-dependent UV-Vis spectroscopic investigation, we reveal the catalyst-like behavior of the self-releasable carbonate template and propose the corresponding mechanism. The assembly of hollow clusters using a self-releasable template may provide insight into understanding the formation mechanisms of other hollow nanoclusters and facilitate the design and construction of new hollow nanoclusters.

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A temperature-sensitive luminescent Ag20 nanocluster templated by carbonate in situ generated from atmospheric CO2 fixation

Cited by 58 publications

References 81 publications

Trapping an octahedral Ag6 kernel in a seven-fold symmetric Ag56 nanowheel

Trapping an octahedral Ag6 kernel in a seven-fold symmetric Ag56 nanowheel

Thermochromic Luminescent Nest‐Like Silver Thiolate Cluster

Catalyzed assembly of hollow silver-sulfide cluster through self-releasable anion template

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