posted on 2021-07-07, 18:37authored byEmilia Kuzniak-Glanowska, Piotr Konieczny, Robert Pełka, Tadeusz M. Muzioł, Marcin Kozieł, Robert Podgajny
An original example
of modular crystal engineering
involving molecular magnetic {CuII[WV(CN)8]}− bilayers and adeninium cations (AdeH+) toward the new layered molecular magnet (AdeH){CuII[WV(CN)8]}·2H2O (1) is presented. 1 crystallizes within the monoclinic C2 space group (a = 41.3174(12), b = 7.0727(3), c = 7.3180(2) Å, β
= 93.119(3)°, and V = 2135 Å3). The bilayer topology is based on a stereochemical matching between
the square pyramidal shape of CuII moiety and the bicapped
trigonal prismatic shape of [WV(μ-CN)5(CN)3], and the separation between bilayers is significantly
increased (by ∼50%; from ca. 9.5 to ca. 14.5 Å) compared
to several former analogues in this family. This was achieved via
a unique combination of (i) a 1D ribbonlike hydrogen bond system {AdeH+···H2O···AdeH+···}∞ exploiting planar water-assisted
Hoogsteen···Sugar synthons with (ii) parallel 1D π–π
stacks {AdeH+···AdeH+}∞. In-plane 2D XY magnetism is characterized by a Tc close to 33 K, Hc,in‑plane = 60 Oe, and Hc,out‑of‑plane = 750 Oe, high values of in-plane γ critical exponents (γb = 2.34(6) for H||b and
γc = 2.16(5) for H||c), and a Berezinskii–Kosterlitz–Thouless (BKT) topological
phase transition, deduced from crystal-orientation-dependent scaling
analysis. The obtained values of in-plane ν critical exponents,
νb = 0.48(5) for H||b and νc = 0.49(3)
for H||c, confirm the BKT transition
(νBKT = 0.5). Full-range angle-resolved monocrystalline
magnetic measurements supported by dedicated calculations indicated
the occurrence of nonlinear susceptibility performance within the
easy plane in a magnetically ordered state. We refer the occurrence
of this phenomenon to spontaneous resolution in the C2 space group, a tandem not observed in studies on previous analogues
and rarely reported in the field of molecular materials. The above magneto-supramolecular strategy may provide a novel means
for the design of 2D molecular magnetic networks and help to uncover
the inherent phenomena.