Polymorphism control of superconductivity and magnetism in Cs3C60 close to the Mott transition

The crystal structure of a solid controls the interactions between the electronically active units and thus its electronic properties. In the high-temperature superconducting copper oxides, only one spatial arrangement of the electronically active Cu2+ units-a two-dimensional square lattice-is available to study the competition between the cooperative electronic states of magnetic order and superconductivity(1). Crystals of the spherical molecular C-60(3-) anion support both superconductivity and magnetism but can consist of fundamentally distinct three-dimensional arrangements of the anions. Superconductivity in the A(3)C(60) (A = alkali metal) fullerides has been exclusively associated with face-centred cubic (f.c.c.) packing of C-60(3-) (refs 2, 3), but recently the most expanded (and thus having the highest superconducting transition temperature, T-o ref. 4) composition Cs3C60 has been isolated as a body-centred cubic (b.c.c.) packing, which supports both superconductivity and magnetic order(5,6). Here we isolate the f.c.c. polymorph of Cs3C60 to show how the spatial arrangement of the electronically active units controls the competing superconducting and magnetic electronic ground states. Unlike all the other f.c.c. A(3)C(60) fullerides, f.c.c. Cs3C60 is not a superconductor but a magnetic insulator at ambient pressure, and becomes superconducting under pressure. The magnetic ordering occurs at an order of magnitude lower temperature in the geometrically frustrated f.c.c. polymorph (Neel temperature T-N = 2.2 K) than in the b.c.c.-based packing (T-N = 46 K). The different lattice packings of C-60(3-) change T-c from 38 K in b.c.c. Cs3C60 to 35 K in f.c.c. Cs3C60 (the highest found in the f.c.c. A(3)C(60) family). The existence of two superconducting packings of the same electronically active unit reveals that T-c scales universally in a structure-independent dome-like relationship with proximity to the Mott metal-insulator transition, which is governed by the role of electron correlations characteristic of high-temperature superconducting materials other than fullerides.