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Carboxylate Ligand‐supported Agn (n=21 and 24) Alkynyl Clusters Induced by Single/Double Carbonate Ions

Von Wiley-VCH zur Verfügung gestellt

Capturing the CO3 2− templates converted from atmospheric CO2 into the [ t BuC≡CAg] n system under the stimulation of carboxylate ligand CF3COO/PhCOO, two functionalized high-nuclear silver alkynyl clusters [(CO3 2−)@Ag21( t BuC≡C)16(CF3COO)3(H2O)] ⋅ DMF ⋅ 2CH2Cl2 (1) and [(CO3 2−)2@Ag24( t BuC≡C)16(PhCOO)4] ⋅ CH3OH ⋅ 4DMF (2) have been successfully isolated, providing positive guidance for constructing silver cluster materials by an anion template strategy.


Structural transformation is important for the study of silver cluster compounds, in which controlled synthesis of their shapes and sizes via anion template-driven is one key scientific question. In this work, the CO3 2− anion templates were captured by the [ t BuC≡CAg] n system under the stimulation induced by carboxylate ligand CF3COO/PhCOO, and two silver alkynyl clusters [(CO3 2−)@Ag21( t BuC≡C)16(CF3COO)3(H2O)]⋅DMF⋅2CH2Cl2 (1) and [(CO3 2−)2@Ag24( t BuC≡C)16(PhCOO)4]⋅CH3OH⋅4DMF (2) have been successfully isolated and charactered. With the increase of the number of CO3 2− templates from single to double, the outer silver atoms from twenty-one to twenty-four, accompanied by the growth of the cluster skeleton from 9.8 Å ×6.9 Å of the (CO3 2−)@Ag21 unit to 10.5 Å ×7.3 Å of the (CO3 2−)2@Ag24 unit. In addition, the syntheses, structures, photocurrent responses, cyclic voltammetry characteristics, luminescence, and photodegradation of compounds 1 and 2 have been studied.

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