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Bathophenanthroline Disulfonate Ligand-Induced Self-Assembly of Ir(III) Complexes in Water: An Intriguing Class of Photoluminescent Soft Materials
ACS Omega ( IF 3.7 ) Pub Date : 2018-10-25 00:00:00 , DOI: 10.1021/acsomega.8b02034 Michelle M. McGoorty 1 , Abhishek Singh 2 , Thomas A. Deaton 2 , Benjamin Peterson 2 , Chelsea M. Taliaferro 1 , Yaroslava G. Yingling 2 , Felix N. Castellano 1
ACS Omega ( IF 3.7 ) Pub Date : 2018-10-25 00:00:00 , DOI: 10.1021/acsomega.8b02034 Michelle M. McGoorty 1 , Abhishek Singh 2 , Thomas A. Deaton 2 , Benjamin Peterson 2 , Chelsea M. Taliaferro 1 , Yaroslava G. Yingling 2 , Felix N. Castellano 1
Affiliation
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Strong evidence of concentration-induced and dissolved electrolyte-induced chromophore aggregation has been universally observed in numerous water soluble bis-cyclometalated Ir(III) photosensitizers bearing the sulfonated diimine ligands bathophenanthroline disulfonate and bathocuproine disulfonate. This new class of aqueous-based soft materials was highly photoluminescent in their aggregated state where detailed spectroscopic investigations of this phenomenon revealed significant blue shifts of their respective photoluminescence emission spectra with concomitant increases in excited-state lifetimes and quantum yields initiating even at micromolar chromophore concentrations in water or upon the addition of a strong electrolyte. A combination of nanoscale particle characterization techniques, static and dynamic photoluminescence spectroscopic studies, along with atomistic molecular dynamics (MD) simulations of these soft materials suggests the formation of small, heterogeneous nanoaggregate structures, wherein the sulfonated diimine ancillary ligand serves as a pro-aggregating subunit in all instances. Importantly, the experimental and MD findings suggest the likelihood of discovering similar aqueous aggregation phenomena occurring in all transition-metal complexes bearing these water-solubilizing diimine ligands.
中文翻译：
邻菲咯啉二磺酸盐配体诱导的Ir（III）配合物在水中的自组装：有趣的一类光致发光软材料
在许多带有磺化二亚胺配体双邻菲咯啉二磺酸盐和双嘧啶二磺酸盐的水溶性双环金属化Ir（III）光敏剂中，普遍观察到浓度诱导和溶解电解质诱导的发色团聚集的有力证据。这类新型的水基软材料在聚集状态下具有高度的光致发光，对这种现象的详细光谱研究表明，即使在微摩尔发色团浓度下，其各自的光致发光发射光谱也发生了显着的蓝移，并伴随着激发态寿命的增加和量子产率的提高。在水中或加入强电解质时。纳米级颗粒表征技术的结合，静态和动态光致发光光谱研究以及这些软材料的原子分子动力学（MD）模拟表明，形成了小的异质纳米聚集结构，其中磺化的二亚胺辅助配体在所有情况下均作为聚集前的亚基。重要的是，实验和MD研究结果表明，可能在所有带有这些水溶性二亚胺配体的过渡金属配合物中发现类似的水聚集现象。
更新日期：2018-10-25
中文翻译：
邻菲咯啉二磺酸盐配体诱导的Ir（III）配合物在水中的自组装：有趣的一类光致发光软材料
在许多带有磺化二亚胺配体双邻菲咯啉二磺酸盐和双嘧啶二磺酸盐的水溶性双环金属化Ir（III）光敏剂中，普遍观察到浓度诱导和溶解电解质诱导的发色团聚集的有力证据。这类新型的水基软材料在聚集状态下具有高度的光致发光，对这种现象的详细光谱研究表明，即使在微摩尔发色团浓度下，其各自的光致发光发射光谱也发生了显着的蓝移，并伴随着激发态寿命的增加和量子产率的提高。在水中或加入强电解质时。纳米级颗粒表征技术的结合，静态和动态光致发光光谱研究以及这些软材料的原子分子动力学（MD）模拟表明，形成了小的异质纳米聚集结构，其中磺化的二亚胺辅助配体在所有情况下均作为聚集前的亚基。重要的是，实验和MD研究结果表明，可能在所有带有这些水溶性二亚胺配体的过渡金属配合物中发现类似的水聚集现象。
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