Phosphorescent Modulation of Metallophilic Clusters and Recognition of Solvents through a Flexible Host-Guest Assembly: A Theoretical Investigation
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]+⋅⋅⋅...
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MDPI AG
2018-09-01
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| Series: | Nanomaterials |
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| Online Access: | http://www.mdpi.com/2079-4991/8/9/685 |
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| author | Zhi-Feng Li Xiao-Ping Yang Hui-Xue Li Guo-Fang Zuo |
| author_facet | Zhi-Feng Li Xiao-Ping Yang Hui-Xue Li Guo-Fang Zuo |
| author_sort | Zhi-Feng Li |
| collection | DOAJ |
| description | 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−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. |
| first_indexed | 2024-12-10T20:35:55Z |
| format | Article |
| id | doaj.art-f16d02ab14f04f4ba5654c148e0aac53 |
| institution | Directory Open Access Journal |
| issn | 2079-4991 |
| language | English |
| last_indexed | 2024-12-10T20:35:55Z |
| publishDate | 2018-09-01 |
| publisher | MDPI AG |
| record_format | Article |
| series | Nanomaterials |
| spelling | doaj.art-f16d02ab14f04f4ba5654c148e0aac532022-12-22T01:34:33ZengMDPI AGNanomaterials2079-49912018-09-018968510.3390/nano8090685nano8090685Phosphorescent Modulation of Metallophilic Clusters and Recognition of Solvents through a Flexible Host-Guest Assembly: A Theoretical InvestigationZhi-Feng Li0Xiao-Ping Yang1Hui-Xue Li2Guo-Fang Zuo3College of Chemical Engineering and Technology, Key Laboratory for New Molecule Design and Function of Gansu Universities, Tianshui Normal University, Tianshui 741001, ChinaSchool of Electronic Information and Electrical Engineering, Tianshui Normal University, Tianshui 741001, ChinaCollege of Chemical Engineering and Technology, Key Laboratory for New Molecule Design and Function of Gansu Universities, Tianshui Normal University, Tianshui 741001, ChinaCollege of Chemical Engineering and Technology, Key Laboratory for New Molecule Design and Function of Gansu Universities, Tianshui Normal University, Tianshui 741001, ChinaMP2 (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−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.http://www.mdpi.com/2079-4991/8/9/685TD-DFTmetallophilicmodulationrecognitionspectroscopic properties |
| spellingShingle | Zhi-Feng Li Xiao-Ping Yang Hui-Xue Li Guo-Fang Zuo Phosphorescent Modulation of Metallophilic Clusters and Recognition of Solvents through a Flexible Host-Guest Assembly: A Theoretical Investigation Nanomaterials TD-DFT metallophilic modulation recognition spectroscopic properties |
| title | Phosphorescent Modulation of Metallophilic Clusters and Recognition of Solvents through a Flexible Host-Guest Assembly: A Theoretical Investigation |
| title_full | Phosphorescent Modulation of Metallophilic Clusters and Recognition of Solvents through a Flexible Host-Guest Assembly: A Theoretical Investigation |
| title_fullStr | Phosphorescent Modulation of Metallophilic Clusters and Recognition of Solvents through a Flexible Host-Guest Assembly: A Theoretical Investigation |
| title_full_unstemmed | Phosphorescent Modulation of Metallophilic Clusters and Recognition of Solvents through a Flexible Host-Guest Assembly: A Theoretical Investigation |
| title_short | Phosphorescent Modulation of Metallophilic Clusters and Recognition of Solvents through a Flexible Host-Guest Assembly: A Theoretical Investigation |
| title_sort | phosphorescent modulation of metallophilic clusters and recognition of solvents through a flexible host guest assembly a theoretical investigation |
| topic | TD-DFT metallophilic modulation recognition spectroscopic properties |
| url | http://www.mdpi.com/2079-4991/8/9/685 |
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