A new series of mono‐ and bis‐alkynyl CoIII(TIM) complexes (TIM=2,3,9,10‐tetramethyl‐1,4,8,11‐tetraazacyclotetradeca‐1,3,8,10‐tetraene) is reported herein. The
We describe the preparation, dynamic, assembly characteristics of vase‐shaped basket
- PAR ID:
- 10478386
- Author(s) / Creator(s):
- ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; more »
- Publisher / Repository:
- Wiley Blackwell (John Wiley & Sons)
- Date Published:
- Journal Name:
- Chemistry – A European Journal
- Volume:
- 29
- Issue:
- 68
- ISSN:
- 0947-6539
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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Abstract trans ‐[Co(TIM)(C2R)Cl]+complexes were prepared from the reaction betweentrans ‐[Co(TIM)Cl2]PF6and HC2R (R=tri(isopropyl)silyl or TIPS (1 ), ‐C6H4‐4‐tBu (2 ), ‐C6H4‐4‐NO2(3 a ), andN ‐mesityl‐1,8‐naphthalimide or NAPMes(4 a )) in the presence of Et3N. The intermediate complexes of the typetrans ‐[Co(TIM)(C2R)(NCMe)](PF6)(OTf),3 b and4 b , were obtained by treating3 a and4 a , respectively, with AgOTf in CH3CN. Furthermore, bis‐alkynyltrans ‐[Co(TIM)(C2R)2]PF6complexes,3 c and4 c , were generated following a second dehydrohalogenation reaction between3 b and4 b , respectively, and the appropriate HC2R in the presence of Et3N. These new complexes have been characterized using X‐ray diffraction (2 ,3 a ,4 a , and4 c ), IR,1H NMR, UV/Vis spectroscopy, fluorescent spectroscopy (4 c ), and cyclic voltammetry. -
Abstract The conformational transition of a fluorinated amphiphilic dendrimer is monitored by the1H signal from water, alongside the19F signal from the dendrimer. High‐field NMR data (chemical shift
δ , self‐diffusion coefficientD , longitudinal relaxation rateR 1, and transverse relaxation rateR 2) for both dendrimer (19F) and water (1H) match each other in detecting the conformational transition. Among all parameters for both nuclei, the water proton transverse‐relaxation rateR 2(1H2O) displays the highest relative scale of change upon conformational transition of the dendrimer. Hydrogen/deuterium‐exchange mass spectrometry reveals that the compact form of the dendrimer has slower proton exchange with water than the extended form. This result suggests that the sensitivity ofR 2(1H2O) toward dendrimer conformation originates, at least partially, from the difference in proton exchange efficiency between different dendrimer conformations. Finally, we also demonstrated that this conformational transition could be conveniently monitored using a low‐field benchtop NMR spectrometer viaR 2(1H2O). The1H2O signal thus offers a simple way to monitor structural changes of macromolecules using benchtop time‐domain NMR. -
Abstract Supramolecular hosts bind to inorganic anions at a fast rate and select them in proportion with thermodynamic stability of the corresponding [anion⊂host] complexes, forming in a reversible manner. In this study, we describe the action of hexapodal capsule
1 and its remarkable ability to select anions based on a large span of rates by which they enter this host. The thermodynamic affinity of1 toward eighteen anions extends over eight orders of magnitude (0<K a<108 M−1;1H NMR spectroscopy). The capsule would retain CO32−(K a=107 M−1) for hours in the presence of eleven competing anions, including stronger binding SO42−, HAsO42−and HPO42−(K a=107–108 M−1). The observed selection resulted from1 possessing narrow apertures (ca. 3×6 Å) comparable in size to anions (d =3.5–7.1 Å) slowing down the encapsulation to last from seconds to days. The unorthodox mode of action of1 sets the stage for creating hosts that pick anions by their ability to access the host. -
Abstract Supramolecular hosts bind to inorganic anions at a fast rate and select them in proportion with thermodynamic stability of the corresponding [anion⊂host] complexes, forming in a reversible manner. In this study, we describe the action of hexapodal capsule
1 and its remarkable ability to select anions based on a large span of rates by which they enter this host. The thermodynamic affinity of1 toward eighteen anions extends over eight orders of magnitude (0<K a<108 M−1;1H NMR spectroscopy). The capsule would retain CO32−(K a=107 M−1) for hours in the presence of eleven competing anions, including stronger binding SO42−, HAsO42−and HPO42−(K a=107–108 M−1). The observed selection resulted from1 possessing narrow apertures (ca. 3×6 Å) comparable in size to anions (d =3.5–7.1 Å) slowing down the encapsulation to last from seconds to days. The unorthodox mode of action of1 sets the stage for creating hosts that pick anions by their ability to access the host. -
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