Secondary ligand engineering of nanoclusters: Effects on molecular structures, supramolecular aggregates, and optical properties
Xiao Wei,
Ying Lv,
Honglei Shen,
Hao Li,
Xi Kang,
Haizhu Yu,
Manzhou Zhu
Affiliations
Xiao Wei
Department of Chemistry and Centre for Atomic Engineering of Advanced Materials, Key Laboratory of Structure and Functional Regulation of Hybrid Materials of Ministry of Education, Institutes of Physical Science and Information Technology and Anhui Province Key Laboratory of Chemistry for Inorganic/Organic Hybrid Functionalized Materials Anhui University Hefei China
Ying Lv
Department of Chemistry and Centre for Atomic Engineering of Advanced Materials, Key Laboratory of Structure and Functional Regulation of Hybrid Materials of Ministry of Education, Institutes of Physical Science and Information Technology and Anhui Province Key Laboratory of Chemistry for Inorganic/Organic Hybrid Functionalized Materials Anhui University Hefei China
Honglei Shen
Department of Chemistry and Centre for Atomic Engineering of Advanced Materials, Key Laboratory of Structure and Functional Regulation of Hybrid Materials of Ministry of Education, Institutes of Physical Science and Information Technology and Anhui Province Key Laboratory of Chemistry for Inorganic/Organic Hybrid Functionalized Materials Anhui University Hefei China
Hao Li
Department of Chemistry and Centre for Atomic Engineering of Advanced Materials, Key Laboratory of Structure and Functional Regulation of Hybrid Materials of Ministry of Education, Institutes of Physical Science and Information Technology and Anhui Province Key Laboratory of Chemistry for Inorganic/Organic Hybrid Functionalized Materials Anhui University Hefei China
Xi Kang
Department of Chemistry and Centre for Atomic Engineering of Advanced Materials, Key Laboratory of Structure and Functional Regulation of Hybrid Materials of Ministry of Education, Institutes of Physical Science and Information Technology and Anhui Province Key Laboratory of Chemistry for Inorganic/Organic Hybrid Functionalized Materials Anhui University Hefei China
Haizhu Yu
Department of Chemistry and Centre for Atomic Engineering of Advanced Materials, Key Laboratory of Structure and Functional Regulation of Hybrid Materials of Ministry of Education, Institutes of Physical Science and Information Technology and Anhui Province Key Laboratory of Chemistry for Inorganic/Organic Hybrid Functionalized Materials Anhui University Hefei China
Manzhou Zhu
Department of Chemistry and Centre for Atomic Engineering of Advanced Materials, Key Laboratory of Structure and Functional Regulation of Hybrid Materials of Ministry of Education, Institutes of Physical Science and Information Technology and Anhui Province Key Laboratory of Chemistry for Inorganic/Organic Hybrid Functionalized Materials Anhui University Hefei China
Abstract Developing new templates to evaluate the ligand engineering effect in manipulating nanoclusters from both molecular and supramolecular aspects remains highly desired in cluster science because it allows for an in‐depth understanding of structure‐property correlations. We herein presented the secondary ligand (i.e., the phosphine ligand) engineering based on an Ag29 nanocluster template and its dual effects on intracluster structures and intercluster aggregates. The “dissociation‐combination equilibrium” of phosphine ligands on the nanocluster surface was controlled by tailoring the C–H⋯π interactions within the ligand shell, which led to the fabrication of a family of [Ag29(BDT)12(PR3)x]3– nanoclusters. On the molecular level, the dissociation of phosphine ligands contracted the nanocluster framework, while the overall configuration of [Ag29(BDT)12]3– was retained. On the supramolecular level, the complete dissociation of phosphine ligands yielded a bare nanocluster, which followed a chiral crystallization mode, and its crystals displayed high optical activity, derived from circular dichroism and circularly polarized luminescence characterizations. Overall, this work presents the peripheral ligand effects in directionally controlling intracluster configurations and intercluster aggregations, which hopefully benefit future design and preparation of new nanoclusters or cluster‐based nanomaterials with customized structures and performances.
