Rigidifying Qubit Candidates in a Cu‐Porphyrin Nanohoop: Dipolar Coupling in Spin Pairs and Spin‐Polarized Ground State

X Xingmao Chang A Ashley J. Redman (Chemistry Research Laboratory, Department of Chemistry) L Linda Zedler (Leibniz Institute of Photonic Technology, Research Department Spectroscopy and Imaging, Albert-Einstein-Str. 9, Jena 07745, Germany) L Louis Blechschmidt (Institute of Physical Chemistry) A Adriana Sacristán‐Martín (Institute of Organic Chemistry and Center for Integrated Quantum Science and Technology Ulm University Albert‐Einstein‐Allee 11 89081 Ulm Germany) F Fabian Schwer (Institute of Organic Chemistry and Center for Integrated Quantum Science and Technology Ulm University Albert‐Einstein‐Allee 11 89081 Ulm Germany) I Inhar Imaz (Catalan Institute of Nanoscience and Nanotechnology (ICN2), CSIC and Barcelona Institute of Science and Technology, Campus UAB, 08193 Bellaterra, Barcelona, Spain) M Markus P. B. Wiedmaier (Institute of Organic Chemistry and Center for Integrated Quantum Science and Technology Ulm University Albert‐Einstein‐Allee 11 89081 Ulm Germany) X Xavi Ribas (Institut de Quimica Computacional i Catalisi, Departament de Quimica) D Daniel Maspoch (Catalan Institute of Nanoscience and Nanotechnology (ICN2), CSIC, and The Barcelona Institute of Science and Technology) B Benjamin Dietzek‐Ivanšić (Institute for Physical Chemistry Friedrich Schiller University Jena Helmholtzweg 4 07743 Jena Germany) S Sabine Richert (Institute of Physical Chemistry, University of Freiburg, Albertstraße 21, 79104 Freiburg, Germany) M Max von Delius (Institute of Organic Chemistry and Center for Integrated Quantum Science and Technology Ulm University Albert‐Einstein‐Allee 11 89081 Ulm Germany)

Abstract

Abstract Assembling molecular qubit candidates with precise control over the position and orientation of spin centers is an important contemporary challenge for synthesis. In this work, we show that the rigidity of highly strained macrocycles from the cycloparaphenylene family gives rise to distinct spin‐spin and light‐spin interactions that make such few‐qubit systems a promising testing ground for future quantum technologies. We synthesized conjugated nanohoop Cu[3]CPTA that comprises three Cu(II)porphyrin centers ( S  = ½) with a Cu–Cu distance of ca. 18 Å (by single‐crystal X‐ray diffraction). Continuous‐wave (cw) and pulse electron‐paramagnetic resonance (EPR) studies revealed that dipolar coupling in spin pairs is so well defined in this nanohoop that the Cu–Cu distance can be determined accurately via double electron–electron resonance (DEER). By transient cwEPR, we observed a rare case of a light‐induced polarization of a doublet ground state in frozen solution. The fact that ground state polarization was significantly less pronounced in a comparable, but more flexible macrocycle will inspire future efforts to better understand and harness this effect.

Article Details

Volume / Issue Vol. 65, Issue 4
Published January 22, 2026
ISSN 1433-7851
Publisher Wiley

Journal Info

Angewandte Chemie International Edition

Wiley

ISSN: 1433-7851 Physical Sciences

Authors (13)

X

Xingmao Chang

A

Ashley J. Redman

Chemistry Research Laboratory, Department of Chemistry

L

Linda Zedler

Leibniz Institute of Photonic Technology, Research Department Spectroscopy and Imaging, Albert-Einstein-Str. 9, Jena 07745, Germany

L

Louis Blechschmidt

Institute of Physical Chemistry

A

Adriana Sacristán‐Martín

Institute of Organic Chemistry and Center for Integrated Quantum Science and Technology Ulm University Albert‐Einstein‐Allee 11 89081 Ulm Germany

F

Fabian Schwer

Institute of Organic Chemistry and Center for Integrated Quantum Science and Technology Ulm University Albert‐Einstein‐Allee 11 89081 Ulm Germany

I

Inhar Imaz

Catalan Institute of Nanoscience and Nanotechnology (ICN2), CSIC and Barcelona Institute of Science and Technology, Campus UAB, 08193 Bellaterra, Barcelona, Spain

M

Markus P. B. Wiedmaier

Institute of Organic Chemistry and Center for Integrated Quantum Science and Technology Ulm University Albert‐Einstein‐Allee 11 89081 Ulm Germany

X

Xavi Ribas

Institut de Quimica Computacional i Catalisi, Departament de Quimica

D

Daniel Maspoch

Catalan Institute of Nanoscience and Nanotechnology (ICN2), CSIC, and The Barcelona Institute of Science and Technology

B

Benjamin Dietzek‐Ivanšić

Institute for Physical Chemistry Friedrich Schiller University Jena Helmholtzweg 4 07743 Jena Germany

S

Sabine Richert

Institute of Physical Chemistry, University of Freiburg, Albertstraße 21, 79104 Freiburg, Germany

M

Max von Delius

Institute of Organic Chemistry and Center for Integrated Quantum Science and Technology Ulm University Albert‐Einstein‐Allee 11 89081 Ulm Germany