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Phosphorescent Modulation of Metallophilic Clusters and Recognition of Solvents through a Flexible Host-Guest Assembly: A Theoretical Investigation.

ABSTRACT: MP2 (Second order approximation of Møller?Plesset perturbation theory) and DFT/TD-DFT (Density functional theory/Time-dependent_density_functional_theory) investigations have been performed on metallophilic nanomaterials of host clusters [Au(NHC)?]????[M(CN)?]^-???[Au(NHC)?]? (NHC = N-heterocyclic carbene, M = Au, Ag) with high phosphorescence. The phosphorescence quantum yield order of clusters in the experiments was evidenced by their order of ?_S1/?E_S1-T1 values ( ? S 1 : S? ? S? transition dipole, ? E S 1 - T 1 : splitting energy between the lowest-lying singlet S? and the triplet excited state T? states). The systematic variation of the guest solvents (S1: CH?OH, S2: CH?CH?OH, S3: H?O) are employed not only to illuminate their effect on the metallophilic interaction and phosphorescence but also as the probes to investigate the recognized capacity of the hosts. The simulations revealed that the metallophilic interactions are mainly electrostatic and the guests can subtly modulate the geometries, especially metallophilic Au???M distances of the hosts through mutual hydrogen bond interactions. The phosphorescence spectra of hosts are predicted to be blue-shifted under polar solvent and the excitation from HOMO (highest occupied molecular orbital) to LUMO (lowest unoccupied molecular orbital) was found to be responsible for the ³MLCT (triplet metal-to-ligand charge transfer) characters in the hosts and host-guest complexes. The results of investigation can be introduced as the clues for the design of promising blue-emitting phosphorescent and functional materials.

SUBMITTER: Li ZF

PROVIDER: S-EPMC6163230 | biostudies-literature | 2018 Sep

REPOSITORIES: biostudies-literature

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Phosphorescent Modulation of Metallophilic Clusters and Recognition of Solvents through a Flexible Host-Guest Assembly: A Theoretical Investigation.

Li Zhi-Feng ZF Yang Xiao-Ping XP Li Hui-Xue HX Zuo Guo-Fang GF

Nanomaterials (Basel, Switzerland) 20180902 9

MP2 (Second order approximation of Møller⁻Plesset perturbation theory) and DFT/TD-DFT (Density functional theory/Time-dependent_density_functional_theory) investigations have been performed on metallophilic nanomaterials of host clusters [Au(NHC)₂]⁺⋅⋅⋅[M(CN)₂]-⋅⋅⋅[Au(NHC)₂]⁺ (NHC = N-heterocyclic carbene, M = Au, Ag) with high phosphorescence. The phosphorescence quantum yield order of clusters in the experiments was evidenced by their order of μS1/ΔES1-T ...[more]

PMID: 30200542

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Project description:A hexacationic triangular covalent organic cage, AzaEx2Cage 6+, has been synthesized by means of a tetrabutylammonium iodide-catalyzed SN2 reaction. The prismatic cage is composed of two triangular 2,4,6-triphenyl-1,3,5-triazine (TPT) platforms bridged face-to-face by three 4,4'-bipyridinium (BIPY 2+) spacers. The rigidity of these building blocks leads to a shape-persistent cage cavity with an inter-platform distance of approximately 11.0 Å. This distance allows the cage to accommodate two aromatic guests, each of which is able to undergo π-π interactions with one of the two TPT platform simultaneously, in an A-D-D-A manner. In the previously reported prism-shaped cage, the spacers (pillars) are often considered passive or non-interactive. In the current system, the three BIPY 2+ spacers are observed to play an important role in guest recognition. Firstly, the BIPY 2+ spacers are able to interact with the carbonyl group in a pyrene-1-carbaldehyde (PCA) guest, by introducing lateral dipole-cation or dipole-dipole interactions. As a consequence, the binding affinity of the cage towards the PCA guest is significantly larger than that of pyrene as the guest, even although the latter is often considered to be a better π-electron donor. Secondly, in the case of the guest 1,5-bis[2-(2-(2-(2-hydroxyethoxy)ethoxy)ethoxy)ethoxy]naphthalene (BH4EN), the pillars can provide higher binding forces compared to the TPT platform. Hence, peripheral complexation occurs when AzaEx2Cage 6+ accommodates BH4EN in MeCN. Thirdly, when both PCA and BH4EN are added into a solution of AzaEx2Cage 6+, inclusion and peripheral complexation occur simultaneously to PCA and BH4EN respectively, even though the accommodation of the former guest seems to attenuate the external binding of the latter. This discovery of the importance of lateral interactions highlights the relationship between the electrostatic properties of a highly charged host and its complexation behavior, and as such, provides insight into the design of more complex hosts that bind guests in multiple locations and modes.

Dataset Information

Phosphorescent Modulation of Metallophilic Clusters and Recognition of Solvents through a Flexible Host-Guest Assembly: A Theoretical Investigation.

Publications

Phosphorescent Modulation of Metallophilic Clusters and Recognition of Solvents through a Flexible Host-Guest Assembly: A Theoretical Investigation.

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