TY - JOUR
T1 - Remarkably Selective Binding, Behavior Modification, and Switchable Release of (Bipyridine)3Ru(II) vis-à-vis (Phenanthroline)3Ru(II) by Trimeric Cyclophanes in Water
AU - Lin, Hong-Yu
AU - Yao, Chao-Yi
AU - Li, Jialu
AU - Nimal Gunaratne, H. Q.
AU - Singh, Warispreet
AU - Huang, Meilan
AU - Anslyn, Eric V.
AU - De Silva, A. Prasanna
N1 - Funding information: We thank Queen’s University Belfast, Department of Employment and Learning of Northern Ireland, Engineering and Physical Sciences Research Council UK, China Scholarship Council, the Leverhulme Trust (RPG-2019-314), Yixiao Lin, Qin Zhang, Gaoming Yao, Fafeng Huang, Brian Daly, and Amila Norbert for their support. E.V.A. thanks the Welch Regents Chair for support (F-0046). We are grateful to the reviewers for helpful suggestions. In memoriam S. M. G. Bastiam Pillai and M. V. M. D. Pathirana. This paper is dedicated to Fraser Stoddart.
PY - 2023/8/28
Y1 - 2023/8/28
N2 - A recurring dream of molecular recognition is to create receptors that distinguish between closely related targets with sufficient accuracy, especially in water. The more useful the targets, the more valuable the dream becomes. We now present multianionic trimeric cyclophane receptors with a remarkable ability to bind the iconic (bipyridine)3Ru(II) (with its huge range of applications) while rejecting the nearly equally iconic (phenanthroline)3Ru(II). These receptors not only selectively capture (bipyridine)3Ru(II) but also can be redox-switched to release the guest. 1D- and 2D(ROESY)-NMR spectroscopy, luminescence spectroscopy, and molecular modeling enabled this discovery. This outcome allows the control of these applications, e.g., as a photocatalyst or as a luminescent sensor, by selectively hiding or exposing (bipyridine)3Ru(II). Overall, a 3D nanometric object is selected, picked-up, and dropped-off by a discrete molecular host. The multianionic receptors protect excited states of these metal complexes from phenolate quenchers so that the initial step in photocatalytic phenolate oxidation is retarded by nearly 2 orders of magnitude. This work opens the way for (bipyridine)3Ru(II) to be manipulated in the presence of other functional nano-objects so that many of its applications can be commanded and controlled. We have a cyclophane-based toolkit that can emulate some aspects of proteins that selectively participate in cell signaling and metabolic pathways by changing shape upon environmental commands being received at a location remote from the active site.
AB - A recurring dream of molecular recognition is to create receptors that distinguish between closely related targets with sufficient accuracy, especially in water. The more useful the targets, the more valuable the dream becomes. We now present multianionic trimeric cyclophane receptors with a remarkable ability to bind the iconic (bipyridine)3Ru(II) (with its huge range of applications) while rejecting the nearly equally iconic (phenanthroline)3Ru(II). These receptors not only selectively capture (bipyridine)3Ru(II) but also can be redox-switched to release the guest. 1D- and 2D(ROESY)-NMR spectroscopy, luminescence spectroscopy, and molecular modeling enabled this discovery. This outcome allows the control of these applications, e.g., as a photocatalyst or as a luminescent sensor, by selectively hiding or exposing (bipyridine)3Ru(II). Overall, a 3D nanometric object is selected, picked-up, and dropped-off by a discrete molecular host. The multianionic receptors protect excited states of these metal complexes from phenolate quenchers so that the initial step in photocatalytic phenolate oxidation is retarded by nearly 2 orders of magnitude. This work opens the way for (bipyridine)3Ru(II) to be manipulated in the presence of other functional nano-objects so that many of its applications can be commanded and controlled. We have a cyclophane-based toolkit that can emulate some aspects of proteins that selectively participate in cell signaling and metabolic pathways by changing shape upon environmental commands being received at a location remote from the active site.
KW - (bipyridine) Ru(II)
KW - (phenanthroline) Ru(II)
KW - luminescent sensing
KW - molecular switching
KW - selective capture−release
UR - http://www.scopus.com/inward/record.url?scp=85167896819&partnerID=8YFLogxK
U2 - 10.1021/jacsau.3c00279
DO - 10.1021/jacsau.3c00279
M3 - Article
C2 - 37654579
SN - 2691-3704
VL - 3
SP - 2257
EP - 2268
JO - JACS Au
JF - JACS Au
IS - 8
ER -