92763-60-5Relevant academic research and scientific papers
Modulation of electronics and thermal stabilities of photochromic phosphino-aminoazobenzene derivatives in weak-link approach coordination complexes
Park, Jung Su,Lifschitz, Alejo M.,Young, Ryan M.,Mendez-Arroyo, Jose,Wasielewski, Michael R.,Stern, Charlotte L.,Mirkin, Chad A.
, p. 16988 - 16996 (2013/12/04)
A series of d8 transition-metal (Pt(II) and Pd(II)) coordination complexes incorporating phosphine-functionalized aminoazobenzene derivatives as hemilabile phosphino-amine (P,N) ligands were synthesized and studied as model weak-link approach (WLA) photoresponsive constructs. The optical and photochemical properties of these complexes were found to be highly influenced by various tunable parameters in WLA systems, which include type of metal, coordination mode, type of ancillary ligand, solvent, and outer-sphere counteranions. In dichloromethane, reversible chelation and partial displacement of the P,N coordinating moieties allow for toggling between aminoazobenzene- or pseudostilbene- and azobenzene-type derivatives. The reversible switching between electronic states of azobenzene can be controlled through either addition or extraction of chloride counterions and is readily visualized in the separation between π-π* and n-π* bands in the complexes' electronic spectra. In acetonitrile solution, the WLA variables inherent to semiopen complexes have a significant impact on the half-lives of the corresponding cis isomers, allowing one to tune their half-lives from 20 to 21000 s, while maintaining photoisomerization behaviors with visible light. Therefore, one can significantly increase the thermal stability of a cis-aminoazobenzene derivative to the extent that single crystals for X-ray diffraction analysis can be grown for the first time, uncovering an unprecedented edge-to-face arrangement of the phenyl rings in the cis isomer. Overall, the azobenzene-functionalized model complexes shed light on the design parameters relevant for photocontrolled WLA molecular switches, as well as offer new ways of tuning the properties of azobenzene-based, photoresponsive materials.
Chelating effect as a driving force for the selective formation of heteroligated Pt(II) complexes with bidentate phosphino-chalcoether ligands
Rosen, Mari S.,Spokoyny, Alexander M.,MacHan, Charles W.,Stern, Charlotte,Sarjeant, Amy,Mirkin, Chad A.
, p. 1411 - 1419 (2011/04/17)
The halide-induced ligand rearrangement reaction (HILR) has been employed to provide selective and exclusive in situ formation of heteroligated Rh(I), Pd(II), and Pt(II) complexes with bidentate phosphino-chalcoether ligands. To gain insights on the natur
Carbonylation of phenylplatinum(II) complexes containing bidentate ligands
Anderson, Gordon K.,Lumetta, Gregg J.
, p. 1542 - 1545 (2008/10/08)
A series of complexes of the type [PtClPh(P Y)] (P Y = 1,2-bis(diphenylphosphino)ethane (dppe), 1-(diphenylphosphino)-2-(diphenylarsino)ethane (appe), 1,3-bis(diphenylphosphino)propane (dppp), 1-(diphenylphosphino)-2-(methylthio)ethane (PC2S), or 1-(diphenylphosphino)-2-(dimethylamino)ethane (PC2N)) has been prepared and the carbonylation reactions of these complexes investigated. The corresponding benzoyl complexes have been generated by an alternative route. No reaction of [PtClPh(P Y)] with CO takes place when P Y = dppe or appe, but carbonylation proceeds smoothly, albeit slowly, when P Y = dppp, PC2S, or PC2N. The reaction is most rapid for the dppp complex. These results are rationalized in terms of both dissociative and nondissociative reaction pathways.
Platinum (II) complexes of unsymmetrical, potentially bidentate ligands
Anderson, Gordon K.,Kumar, Ravi
, p. 4064 - 4068 (2008/10/08)
The reactions of a series of unsymmetrical, potentially bidentate ligands Ph2P(CH2)nX (n = 2, X = OMe, NMe2, SMe; n = 3, X = NMe2) with [PtX2(cod)] (X = Cl, I) are described. The tendency of the ligand to bond to the metal in a bidentate fashion is dependent on the nature of the weak donor, and on the size of the chelate ring formed. Halide abstraction by Ag+ promotes coordination of the ether function to yield [PtCl(Ph2PCH2CH2OMe)2]+ and [Pt(Ph2PCH2CH2OMe)2]2+. Reactions of the former with a number of weak donor ligands have been studied by 31P{1H} NMR spectroscopy. Complex mixtures are obtained with Ph2PCH2CH2SMe, and the involvement of ion-paired species is suggested in this case.
