A rapid and effective synthetic route to functional cuboctahedron nanospheres
Graphical abstract
Multiferrocenyl and multiadamantyl cuboctahedron nanospheres were synthesized via rapid self-assembly reactions of twelve 90° PdII-containing compounds and twenty-four 120° organic bidentate N-ligands in acetone solution. Multifunctional molecular self-assembly processes offer considerable synthetic advantages including significantly fewer steps, fast and facile formation of final desirable products.
Introduction
Natural evolution has developed a fascinating way to build functional systems with high complexity via the self-assembly of various molecular subunits. Self-assembled polyhedral structures widely exist in chemistry, material science and biology systems. In last decades remarkable progress has been made to employ building blocks encoded with specific stoichiometric features and create prospective high-order supramolecular structures. For instance, synthetic viral capsids were assembled from a 24-mer viral peptide fragment in aqueous solutions [[1], [2], [3], [4], [5], [6]]. Therefore, it is necessary to study such self-assembly processes in the design of novel functional materials and devices. One of the key challenges is to employ coordination self-assembly route in the construction of well-defined nanoscale functional materials with controllable sizes, shapes, and properties [[7], [8], [9], [10], [11], [12]].
In recent twenty years, multifunctional polymers [[13], [14], [15], [16]] and dendrimers [[17], [18], [19]] have extensively been studied for their potential applications in designing functional materials and devices. Stang [20] and co-workers have reported a facile synthetic route to prepare snowflake-shaped metallodendrimers with hexagonal cavities as their cores. Fujita [21] and co-workers have prepared saccharide-coated molecular spheres that can form aggregates after interactions with proteins. These pioneer studies have demonstrated that the addition of special functional groups into individual building blocks not only keeps the original topology of assembling systems invariant but also brings novel multifunctionality with controllable structures [[22], [23], [24], [25]].
Previously, we have presented six ferrocenyl-substituted M6L4 octahedral structures which show interesting electrochemical properties [[26], [27], [28]]. In this work, we try to extend such effort of synthesizing novel multifunctional systems with much larger size and higher symmetry. The designed M12L24 cuboctahedron nanospheres can be rapidly obtained by the combination of twelve metal subunits (M) and twenty-four bidentate ligand subunits (L) in appropriate solvents. The combination of PdII metal subunits and N ligand subunits provides a cuboctahedron assembling complex with a nanosized cavity. Due to the cavity size, functional moieties can be readily attached not only outside but also inside of these assembling structures.
Herein, we present a rapid synthetic route (Scheme 1) by combining 120° organic bidentate ligands (1 and 2, containing ferrocenyl and adamantyl functional groups, respectively) and 90° Pd II-containing compound (4, [Pd(NO3)2]) to obtain peripherally functionalized M12L24 cuboctahedron nanosphere (5 or 6) in acetone solution. Meanwhile, the main core M12L24 complex 7 was built as comparison, which was synthesized from the main framework of 120° organic bidentate ligand 3 (Scheme S2 for details). Both ligand 3 and complex 7 have no additional appended functional groups. Ligand 3 and its corresponding derivatives 1, 2 are utilized to react with a common PdII-containing compound 4, which possesses four coordination sites and 90° coordination angles. Complex 7 can also be rapidly obtained by combining bidentate ligand 3 with compound 4. When functional groups, such as ferrocene or adamantane moieties, are bonded to the vertex of the 120° bidentate ligands (1 or 2), the reactions between ligands and Pd II-containing compound 4 produce assembly complex (5 or 6). Complex 5 or 6 shows new topological connectivity with 24 peripherally appended functional moieties at vertexes after coordination. The multiple functional moieties hanging outside of the nanospheres provide self-assembled coordination systems interesting electrochemical properties.
Section snippets
Results and discussion
Based on our design strategy, the 120° ferrocenyl or adamantyl precursor 1 (or 2) can be prepared via the esterification reaction between ferrocene-1-carboxylic acid (or adamantane-1-carboxylic acid) and 3,5-di(pyridin-4-yl) phenol [28,29] (Scheme S1). Afterwards, by adding 120° bidentate ligand (1 or 2, 0.1 mmol in acetone solution) into 90° Pd II-containing compound 4 [Pd(NO3)2] (0.05 mmol, 0.5 equiv in acetone solution) with the ratio of 2:1, the cuboctahedron M12L24 complex (5 or 6) was
Conclusions
In summary, we presented a rapid and effective method to obtain the functional M12L24 complexes with attached some specific moieties. The coordination self-assembly allows for precise position control of twenty-four ferrocene or adamantane functionalities. The acetone solvent system was proven to facilely prepare the self-assembled complexes compared to previously reported ones, facilitating isolation and purification. DOSY NMR spectroscopy, AFM images and theoretical calculations confirmed the
Material
Reagents were purchased from TCI Co., Ltd., WAKO Pure Chemical Industries Ltd., and Sigma-Aldrich Co. All the chemicals were of reagent grade and used without any further purification.
Synthesis of ligand 1
To a solution of ferrocene-1-carboxylic acid (223.1 mg, 0.97 mmol) in 20 ml anhydrous CH2Cl2 was added catalytic amount (10%) of 4-dimethylamiopryidine (DMAP) and 3,5-bis(pyridinyl)phenol (220.0 mg, 0.88 mmol). N,N′-dicyclohexylcarbodiimide (DCC) (200.1 mg, 0.97 mmol ) was then added to the reaction mixture
Declaration of competing interest
The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.
Acknowledgments
This research is supported by the Natural Science Foundation of China (Grant No. 21805068, 21976123), the Shanghai University Young Teacher Training Program (Grant No. ZZyy16010), and Shanghai Municipal Peak Plateau Construction Program (Grant 1021ZK191601008-A21).
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