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

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.

Abstract

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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