Solvent and Temperature Induced Switching Between Structural Isomers of Rh<sup>I</sup> Phosphinoalkyl Thioether (PS) Complexes
作者:Michael J. Wiester、Adam B. Braunschweig、Hyojong Yoo、Chad A. Mirkin
DOI:10.1021/ic101021t
日期:2010.8.2
how solvent and ligand binding strength alter the coordination geometry of complexes formed from this method. A series of phosphinoalkyl thioether (PS) hemilabileligands with varying electron donating abilities were synthesized and incorporated into homoligated RhI(PS)2Cl complexes to help understand the effects of solvent and ligand binding strength on the preferred coordination modes. The switching
为了开发基于弱链接方法 (WLA) 的功能系统,了解溶剂和配体结合强度如何改变由该方法形成的复合物的配位几何结构非常重要。合成了一系列具有不同给电子能力的膦基烷基硫醚 (PS) 半稳定配体,并将其掺入均配的 Rh I (PS) 2 Cl 配合物中,以帮助了解溶剂和配体结合强度对首选配位模式的影响。通过变温31 P NMR 光谱在 CH 2 Cl 2 的不同溶剂混合物中研究了这些 Rh I (PS) 2 Cl 配合物的封闭和半开放结构异构体之间的转换和四氢呋喃 (THF) 以获得热力学参数(Δ G °、Δ H °、T Δ S ° 和K eq)。异构体的不同之处在于氯反离子的位置。在封闭异构体中,Cl -阴离子占据外部配位球,而在半开放异构体中,Cl -移动了内部球体并取代了一个 Rh-S 键。CH 2 Cl 2有利于封闭异构体,THF 有利于半开放异构体。平衡时对任一异构体的偏好取决于溶剂极性,基于E
作者:A. M. Lifschitz、R. M. Young、J. Mendez-Arroyo、V. V. Roznyatovskiy、C. M. McGuirk、M. R. Wasielewski、C. A. Mirkin
DOI:10.1039/c4cc01345j
日期:——
Photoinduced electron transfer from a Rh(i) center to an excited Bodipy unit within coordination complexes is regulated in situ by affecting the redox potential of either moiety thought the introduction of neutral and anionic ligands.
Chelating Effect as a Driving Force for the Selective Formation of Heteroligated Pt(II) Complexes with Bidentate Phosphino-Chalcoether Ligands
作者:Mari S. Rosen、Alexander M. Spokoyny、Charles W. Machan、Charlotte Stern、Amy Sarjeant、Chad A. Mirkin
DOI:10.1021/ic101973s
日期:2011.2.21
equivalent of either a bidentate ligand or the monodentate ethyl diphenylphosphine ligand, resulting in the clean formation of the heteroligated species or, in the case of the monodentate ligand with an electron-withdrawing bidentate ligand, a mixture of products. On the basis of competitive exchange reactions between these heteroligated, homoligated, and monoligated complexes, we conclude that ligand chelation
卤化物诱导的配体重排反应 (HILR) 已被用于提供具有二齿膦基-硫醚配体的异连接 Rh(I)、Pd(II) 和 Pt(II) 配合物的选择性和排他性原位形成。为了深入了解这种独特反应的性质,我们通过逐步添加双齿膦基-硫醚(P、X;X = S 或 Se)和相关单齿膦配体与 Pt(II) 金属前体来探索该过程。通过使 1 当量的 P, X 双齿配体与 Pt(II) 反应,以定量产率获得相应的单连接复合物,并通过单晶 X 射线衍射研究和异核(31 P、77 Se 和195Pt) 溶液中的核磁共振光谱。这些物质进一步与第二当量的二齿配体或单齿乙基二苯基膦配体反应,导致杂配体的完全形成,或者在具有吸电子双齿配体的单齿配体的情况下,产品。基于这些异源连接、同源连接和单连接复合物之间的竞争性交换反应,我们得出结论,配体螯合在 Pt(II) HILR 中起着至关重要的作用。稳定的单连接复合物的原位优选形
Heteroligated RhI Tweezer Complexes
作者:Aaron M. Brown、Maxim V. Ovchinnikov、Chad A. Mirkin
DOI:10.1002/anie.200500689
日期:2005.7.4
Self‐Assembly and Aggregation‐Induced Emission in Aqueous Media of Responsive Luminescent Copper(I) Coordination Polymer Nanoparticles
作者:Hugo Hernández‐Toledo、Hugo Torrens、Marcos Flores‐Álamo、Luisa De Cola、Guillermo Moreno‐Alcántar
DOI:10.1002/chem.202100865
日期:2021.6.4
Luminescent copper(I)-based compounds have recently attracted much attention since they can reach very high emission quantum yields. Interestingly, Cu(I) clusters can also be emissive, and the extension from small molecules to larger architecture could represent the first step towards novel materials that could be obtained by programming the units to undergo self-assembly. However, for Cu(I) compounds