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 μS1/ΔES1−T1 values (: S0 → S1 transition dipole, : 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.
Highlights
The relationship between the luminescent property and metallophilic Au(I)···M bond distance (M = AuI, AgI, CuI, TlI, HgII, BiIII, etc.) has attracted a great deal of attention in the last few years [1,2,3,4,5]
The natural bond orbital (NBO) analysis is achieved by NBO 5.0 procedure [78]
A detailed study of metallophilic Au···M bonding in host clusters from self-assembled [Au(NHC)2]+ and [M(CN)2]− (M = Au, Ag) and the characters of their host–guest complexes are presented by the second-order Møller−Plesset (MP2) method, density functional theory, and qualitative analysis via GKS-EDA and NBO methods with a series of basis sets
Summary
The organometallic complexes were applied extensively as emitters in organic light-emitting diodes (OLEDs) and phosphorescent OLEDs with green and red spectral range, which have already been demonstrated to be high efficiency and stability [10,11,12]. The blue-emitting OLEDs, which are essential for the commercial launch of devices for lighting, still lack stability and efficiency. Designing new materials to show higher energy, such as deep-blue emission, encounters more obstacles than the progress made for obtaining green and red colors. Nanomaterials 2018, 8, 685 progress made for obtaining green and red colors. Considerable investigations have been carried out in developing blue OLEDs with high exterCnaolnsqiduearnatbuleminevfefsictiigeantciyonsashawveeblleeanscaarrideedeopuert inbldueevecloploinr g[b1l3u–e17O]L. The orbital composition analysis is performed by the Multiwfn 3.3 suite of program [77]. The natural bond orbital (NBO) analysis is achieved by NBO 5.0 procedure [78]
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