A quantum chemical model for a series of self-assembled nanocages: the origin of stability behind the coordination-driven formation of transition metal complexes up to [M₁₂L₂₄]²⁴⁺

Abstract

We present a systematic computational model to study the electronic states and free energies of a self-assembled multi-metal complex series.

Theoretical and computational methodologies for understanding coordination self-assembly complexes

“…38 In addition, the model Hamiltonian for a metal center was applied to compute the structures of a self-assembled nanocage [Pd 12 L 24 ] 24+ and its partial series [Pd n L m ] 2 n + in gas and solution phases, where the solvation was treated implicitly by the GB model. 39 Fig. 1 shows a performance of the model Hamiltonian in terms of single-point binding energies of [Pd n L m ] 2 n + , where a good agreement with the DFT results clearly indicates the reliability of the model Hamiltonian approach.…”

“…The ground state energy of a coordination self-assembly was thus computed by using a sum of the electronic energies of the multiple metal centers, realizing efficient computations on structures of the Pd-based selfassembled systems. [37][38][39] The EHCF method, which also describes the electronic d-d states by construction, has been applied to computing structures and d-d excitations of wider range of transition metal complexes. 18,19,21 For example, the EHCF approach combined with MM could successfully reproduce the structures and spin states of a wide range of Fe(II) and Co(II) complexes having mono-and poly-dentate nitrogen donor ligands.…”

“…Here we briefly mention the MD simulations for MOF or PCP (porous coordination polymer) and the nanocube, by viewing them as analogous systems in the context of tracking the 39 This journal is © the Owner Societies 2023 molecular self-assembly process. In the MOF structure, vertices composed of single metal ions or ion clusters are linked by organic ligands.…”

Unlocking the computational design of metal–organic cages

“…In an example approach, Yoshida et al developed an effective model Hamiltonian that can help make MOC topology evaluation more efficient. 122 However, to develop and apply low-cost methods requires robust data to build from, which emphasises the need for experimental and computational collaboration.…”

Porous Membrane Reactors for Liquid-Phase Heterogeneous Catalysis

“…The use of homogeneous catalysts is advantageous in the high catalytic activity and elucidation of detailed catalytic mechanisms, but it has suffered from some disadvantages, such as high cost, difficult separation, and low recycling performance, limiting their further applications in the catalytic processes . In contrast, heterogeneous catalysts, which are present in the distinct solid phase, are highly favored over the homogeneous counterparts for large-scale industrial production processes, because of their easy separation and recyclability. , Numerous types of catalysts have been synthesized, for example, metal oxides, − transition-metal coordination complexes, − polyoxometalates (POMs), − and metal nanoparticles (NPs) − supported on several solid materials, such as metal–organic frameworks (MOFs), , zeolites, − carbon materials, , silicas, and metal oxides, , which are in very high demand for achieving the goals of green chemistry and sustainable development. The activity and selectivity of catalysts can be enhanced by decreasing the size of the catalyst particles .…”