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Nanomaterials 2018, 8(9), 685; https://doi.org/10.3390/nano8090685

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

1
College of Chemical Engineering and Technology, Key Laboratory for New Molecule Design and Function of Gansu Universities, Tianshui Normal University, Tianshui 741001, China
2
School of Electronic Information and Electrical Engineering, Tianshui Normal University, Tianshui 741001, China
*
Author to whom correspondence should be addressed.
Received: 15 August 2018 / Revised: 27 August 2018 / Accepted: 28 August 2018 / Published: 2 September 2018
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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)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 μS1ES1−T1 values ( μ S 1 : S0 → S1 transition dipole, E S 1 T 1 : splitting energy between the lowest-lying singlet S1 and the triplet excited state T1 states). The systematic variation of the guest solvents (S1: CH3OH, S2: CH3CH2OH, S3: H2O) 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. View Full-Text
Keywords: TD-DFT; metallophilic; modulation; recognition; spectroscopic properties TD-DFT; metallophilic; modulation; recognition; spectroscopic properties
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Li, Z.-F.; Yang, X.-P.; Li, H.-X.; Zuo, G.-F. Phosphorescent Modulation of Metallophilic Clusters and Recognition of Solvents through a Flexible Host-Guest Assembly: A Theoretical Investigation. Nanomaterials 2018, 8, 685.

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