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

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-spi...

Descripción completa

Detalles Bibliográficos
Autores: Chang, Xingmao, Redman, Ashley J., Zedler, Linda, Blechschmidt, Louis, Sacristán-Martín, Adriana, Schwer, Fabian, Imaz, Inhar, Wiedmaier, Markus P. B., Ribas, Xavi, Maspoch, Daniel, Dietzek-Ivanšić, Benjamin, Richert, Sabine, Delius, Max von
Tipo de recurso: artículo
Estado:Versión publicada
Fecha de publicación:2026
País:España
Institución:Consejo Superior de Investigaciones Científicas (CSIC)
Repositorio:DIGITAL.CSIC. Repositorio Institucional del CSIC
OAI Identifier:oai:dnet:digitalcsic_::f8ac13907bf1c9538166d7551e769f48
Acceso en línea:http://hdl.handle.net/10261/425925
https://api.elsevier.com/content/abstract/scopus_id/105024481465
Access Level:acceso abierto
Palabra clave:Copper porphyrins
Electron paramagnetic resonance spectroscopy
Molecular quantum bits
Rigid macrocycles
Transient absorption spectroscopy
Descripción
Sumario: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.