Molecules Designed to Contain Two Weakly Coupled Spins with a Photoswitchable Spacer

作者：Salinas Uber Jorge; Estrader Marta; Garcia Jordi; Lloyd Williams Paul; Sadurni Anna; Dengler Dominik; van Slageren Joris; Chilton Nicholas F; Roubeau Olivier^*; Teat Simon J; Ribas Arino Jordi; Aromi Guillem^*

来源：Chemistry - A European Journal, 2017, 23(55): 13648-13659.

DOI：10.1002/chem.201702171

• density functional calculations
• heterometallic complexes
• ligand design
• magnetic properties
• transition metals

Controlling the charges and spins of molecules lies at the heart of spintronics. A photoswitchable molecule consisting of two independent spins separated by a photoswitchable moiety was designed in the form of new ligand H4L, which features a dithienylethene photochromic unit and two lateral coordinating moieties, and yields molecules with [MMMM] topology. Compounds [M4L2(py)(6)] (M=Cu, 1; Co, 2; Ni, 3; Zn, 4) were prepared and studied by single-crystal X-ray diffraction (SCXRD). Different metal centers can be selectively distributed among the two chemically distinct sites of the ligand, and this enables the preparation of many double-spin systems. Heterometallic [MMMM] analogues with formulas [Cu2Ni2L2(py)(6)] (5), [Co2Ni2L2(py)(6)] (6), [Co2Cu2L2(py)(6)] (7), [Cu2Zn2L2(py)(6)] (8), and [Ni2Zn2L2(py)(6)] (9) were prepared and analyzed by SCXRD. Their composition was established unambiguously. All complexes exhibit two weakly interacting [MM] moieties, some of which embody two-level quantum systems. Compounds 5 and 8 each exhibit a pair of weakly coupled S=1/2 spins that show quantum coherence in pulsed Q-band EPR spectroscopy, as required for quantum computing, with good phase memory times (T-M=3.59 and 6.03s at 7K). Reversible photoswitching of all the molecules was confirmed in solution. DFT calculations on 5 indicate that the interaction between the two spins of the molecule can be switched on and off on photocyclization.

• 出版日期2017-10-4