Metal Halide/N-Donor Organic Ligand Hybrid Materials with Confined Energy Gaps and Emissions

• Published in: European Journal of Inorganic Chemistry Vol. 2008; no. 19; pp. 3040 - 3045
• Main Authors: Wang, Wei, Qiao, Juan, Dong, Guifang, Wang, Liduo, Duan, Lian, Zhang, Deqiang, Qiu, Yong
• Format: Book Review Journal Article
• Language: English
• Published: Weinheim WILEY-VCH Verlag 01.07.2008; WILEY‐VCH Verlag
• Subjects: Halides; Luminescence; Organic-inorganic hybrid composites
• ISSN: 1434-1948; 1099-0682
• DOI: 10.1002/ejic.200800069

Four group 12 metal halide/N‐donor organic ligand hybrid materials, ZnCl2(AEC)2 (1), ZnI2(AEC)2 (2), CdI2(AEC)2 (3), and HgI2(AEC)2 (4) [AEC=N‐(2‐aminoethyl)carbazole] were synthesized and characterized. Single crystals of ZnCl2(AEC)2·CH3CN (1·CH3CN) and ZnI2(AEC)2·CH3CN (2·CH3CN) were obtained from solutions. Single‐crystal X‐ray diffraction analysis revealed that 1·CH3CN and 2·CH3CN form quasi‐1D structures of (ZnCl2)n and (ZnI2)n chains. The two AEC ligands in one hybrid molecule are dissymmetric due to the steric hindrance effect of the AEC moiety and the hydrogen bonding of the CH3CN guest molecules. The UV/Vis spectra of compounds 1–4 were measured, and the optical energy gaps (Eg) of compounds 1–3 are very close to that of AEC; the value of Eg for compound 4 is a little smaller. Steady and transient photoluminescence studies revealed that the emissions of compounds 1–3 are attributed to the AEC ligands, whereas compound 4 does not emit light owing to the heavy‐atom effect. Theoretical studies of the electronic structures confirmed that the optical energy gaps and emissions of the hybrid materials are almost confined by the AEC organic ligand rather than the metal halides.(© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008) The organic–inorganic hybrid materials ZnCl2(AEC)2 (1), ZnI2(AEC)2 (2), CdI2(AEC)2 (3), and HgI2(AEC)2 (4) were synthesized. The crystal structures of 1·CH3CN and 2·CH3CN reveal quasi‐1Dinorganic frameworks. The optical energy gaps of these materials are influenced by the AEC ligands; compounds 1, 2, and 3 give deep‐blue emissions from the AEC ligands, whereas 4 does not emit light.