Ayers Kaitlynn M, Schley Nathan D, Ung Gaël
Department of Chemistry, University of Connecticut, Storrs, Connecticut 06269, United States.
Department of Chemistry, Vanderbilt University, Nashville, Tennessee 37235, United States.
Inorg Chem. 2020 Jun 1;59(11):7657-7665. doi: 10.1021/acs.inorgchem.0c00628. Epub 2020 May 19.
We report the synthesis and characterization of -symmetrical lanthanide complexes supported by enantiopure hexadentate ligands derived from 1,2-diaminocyclohexane. Coordination of (,)- or (,)-,,','-tetrakis(2-pyridylmethyl)--1,2-diaminocyclohexane (tpdac) to samarium, europium, terbium, and dysprosium generates the corresponding -symmetrical (tpdac)Ln(OTf) complexes in high yields. The tpdac ligands are competent sensitizers for lanthanide luminescence, yielding modest emissions (Φ of ≤28%). Additionally, the complexes exhibit strong circularly polarized luminescence (|| values of up to 0.13, 0.09, 0.22, and 0.15 for Sm, Eu, Tb, and Dy, respectively) in solution. We also observed that some transitions typically associated with small dissymmetry factors exhibit unusually high || values and, therefore, should not be overlooked in future studies.
我们报道了由对映体纯的源自1,2 - 二氨基环己烷的六齿配体支撑的对称镧系元素配合物的合成与表征。(+,+)- 或(-,-)- N,N',N'',N''' - 四(2 - 吡啶甲基)- 1,2 - 二氨基环己烷(tpdac)与钐、铕、铽和镝配位,以高收率生成相应的对称(tpdac)Ln(OTf)配合物。tpdac配体是镧系元素发光的有效敏化剂,产生适度的发射(Φ≤28%)。此外,这些配合物在溶液中表现出强烈的圆偏振发光(Sm、Eu、Tb和Dy的||值分别高达0.13、0.09、0.22和0.15)。我们还观察到一些通常与小不对称因子相关的跃迁表现出异常高的||值,因此在未来的研究中不应被忽视。