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Herein, we report the synthesis and the study of a novel mixed biradical with BDPA and TEMPO radical units that are covalently bound by an ester group (BDPAesterTEMPO) as a polarizing agent for fast dissolution DNP. The biradical exhibits an extremely high DNP NMR enhancement of >50[thin space (1/6-em)]000 times, which constitutes one of the largest signal enhancements observed so far, to the best of our knowledge., This work was supported by the Intramural Project CIBER-BBN 2016–2017 “ORDECA”; DGI Grants (CTQ2013-40480-R, MAT2016-80826-R, BIO2013-45793-R and BIO2016-78006-R); and AGAUR Grant (2014SGR-0017). ICMAB acknowledges Spanish MINECO through the Severo Ochoa Centres of Excellence Programme Grant SEV-2015-0496. We also thank Dr F. Mentink-Vigier and Dr G. De Paëpe from CEA-Grenoble for fruitful discussions.

Herein we report a water-induced single-crystal to single-crystal transformation that involves the formation of hetero-bimetallic paddlewheel clusters in coordination polymers. Through this transformation, which involves the cleavage and formation of different coordination bonds, two different Cu(II)-Zn(II) and Cu(II)-Ni(II) paddle-wheel units exhibiting a 1 : 1 metal ratio were created., This work was supported by the Spanish MINECO (projects PN MAT2015-65354-C2-1-R and MAT2013-47869-C4-2-P), DGI grant BeWell (CTQ2013-40480-R), the Catalan AGAUR (project 2014-SGR-80 and 2014-SGR-17), and the ERC under the EU FP7 (ERC-Co 615954). J. A. thanks the Generalitat de Catalunya for a FI fellowship (2016FI B 00449). ICN2 and ICMAB acknowledge the support of the Spanish MINECO through the Severo Ochoa Centres of Excellence Programme, under Grants SEV-2013-0295 and SEV-2015-0496. The authors thank Dr N. Clos from the Serveis Cientifíco-Tècnics of the University of Barcelona for her assistance.

The strength of the electronic interactions between the two redox moieties in fullerene-substituted mixed-valence bis(ferrocenylethynyl)ethene derivatives is modulated by the through-space intramolecular electronic interactions of C(60) with the bridging conjugated system.