ABSTRACT
A mesoionic N-heterocyclic carbene-gold(I) complex with a unique Auâ¯H-C(methine) intramolecular hydrogen bonding interaction has been investigated in the solid state. The structure of this new neutral gold(I)-carbene was characterized by FT-IR and NMR spectroscopy, TGA, and X-ray diffraction techniques. Density functional theory (DFT) and atoms-in-molecule (AIM) analysis revealed that the gold-hydrogen bonding situation is more favored. Besides, the photophysical properties of the gold(I) complex were also investigated.
ABSTRACT
The synthesis and the luminescence features of three gold(I)-N-heterocyclic carbene (NHC) complexes are presented to study how the n-alkyl group can influence the luminescence properties in the crystalline state. The mononuclear gold(I)-NHC complexes, [(L1 )Au(Cl)] (1), [(L2 )Au(Cl)] (2), and [(L3 )Au(Cl)] (3) were isolated from the reactions between [(tht)AuCl] and corresponding NHC ligand precursors, [N-(9-acridinyl)-N'-(n-butyl)-imidazolium chloride, (L1 .HCl)], [N-(9-acridinyl)-N'-(n-pentyl)-imidazolium chloride, (L2 .HCl)] and [N-(9-acridinyl)-N'-(n-hexyl)-imidazolium chloride, (L3 .HCl)]. Their single-crystal X-ray analysis reveals the influence of the n-alkyl groups on solid-state packing. A comparison of the luminescence features of 1-3 with n-alkyl substituents is explored. The molecules 1-3 depicted blue emission in the solution state, while the yellow emission (for 1), greenish-yellow emission (for 2), and blue emission (for 3) in the crystalline phase. This paradigm emission shift arises from n-butyl to n-pentyl and n-hexyl in the crystalline state due to the carbon-carbon rotation of the n-alkyl group, which tends to promote unusual solid packing. Hence n-alkyl group adds a novel emission property in the crystalline state. Density Functional Theory and Time-Dependent Density Functional Theory calculations were carried out for monomeric complex, N-(9-acridinyl)-N'-(n-heptyl)imidazole-2-ylidene gold(I) chloride and dimeric complex, N-(9-acridinyl)-N'-(n-heptyl)imidazole-2-ylidene gold(I) chloride to understand the structural and electronic properties.
ABSTRACT
The synthesis and photophysical properties of macrocyclic Zn(ii) selone molecule have been reported. The structural property of Zn(ii) selone was elucidated using single crystal X-ray diffraction study. The solid-state structure of zinc(ii) selone molecule exhibits a perfect zinc(ii) selone 28 membered ring system with tetra coordination geometry around zinc(ii) center. The zinc(ii) selone ring system can be considered as the largest zinc(ii) ring system known without any non-interacting centered guest moiety. Detailed trends in photophysical as well as thermal properties were probed. In photoluminescence study, the solid-state sample of zinc(ii) selone ring system emits the bluish-yellow color with considerable quantum yields, while the solution state sample of zinc(ii) selone ring system in DMSO emits bluish-yellow. The luminescence lifetime of zinc(ii) selone was measured using standard time-correlated single photon counting (TCSPC) technique.
ABSTRACT
Herein, the photophysical properties of an acridine derivative of a bis-N-heterocyclic carbene silver complex were investigated. The HOMO and LUMO energy differences between 9-[(N-methyl imidazol-2-ylidene)]acridine and 4,5-bis[(N-methyl-imidazol-2-ylidene)methyl]acridine were theoretically compared. Based on the calculation, the 4,5-bis N-heterocyclic carbene-tethered acridine type of ligand was found to be a potential source for tuning the fluorescent nature of the resultant metal derivatives. Thus, a 4,5-bis N-heterocyclic carbene (NHC)-tethered acridine silver(i) salt was synthesized, and its photophysical properties were investigated. The 4,5-bis[(N-isopropylimidazol-2-ylidene)methyl]acridine silver(i) hexafluorophosphate complex was obtained from the reaction between [4,5-bis{(N-isopropylimidazolium)methyl}acridine] hexafluorophosphate and Ag2O in very good yield; this molecule was characterized by elemental analysis and FTIR, multinuclear (1H and 13C) NMR, UV-Vis, and fluorescence spectroscopic techniques. The molecular structure has been confirmed by single-crystal X-ray diffraction analysis, which has revealed that the complex is a homoleptic mononuclear silver(i) cationic solid. The charge of the Ag(i)-NHC cation is balanced by the hexafluorophosphate anion. The cationic moieties are closely packed in the chair and inverted chair forms where silver(i) possesses a quasi-linear geometry. Moreover, the silver complex provided blue emission from all the three excitations with good fluorescence quantum yield. The fluorescence lifetime of the silver(i) complex has been determined using the time-correlated single photon counting technique. Interestingly, the fluorescence decay pattern and the fluorescence lifetimes of the silver complex are largely different from those of the parent ligand acridine imidazolium salt. Moreover, the theoretical predictions have been found to be in good agreement with the experimental results.
